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Sample records for abundant clay minerals

  1. Clay Minerals

    SciTech Connect

    Mueller, Karl T.; Sanders, Rebecca L.; Washton, Nancy M.

    2014-03-14

    Clay minerals are important components of the environment and are involved or implicated in processes such as the uptake of pollutants and the release of nutrients and as potential platforms for a number of chemical reactions. Owing to their small particle sizes (typically, on the order of microns or smaller) and mixing with a variety of other minerals and soil components, advanced characterization methods are needed to study their structures, dynamics, and reactivities. In this article, we describe the use of solid-state NMR methods to characterize the structures and chemistries of clay minerals. Early one-pulse magic-angle spinning (MAS) NMR studies of 27Al and 29Si have now been enhanced and extended with new studies utilizing advanced methodologies (such as Multiple Quantum MAS) as well as studies of less-sensitive nuclei. In additional work, the issue of reactivity of clay minerals has been addressed, including studies of reactive surface area in the environment. Utilizations of NMR-sensitive nuclides within the clay minerals themselves, and in molecules that react with specific sites on the clay mineral surfaces, have aided in understanding the reactivity of these complex aluminosilicate systems.

  2. Laboratory reflectance spectra of clay minerals mixed with Mars analog materials: Toward enabling quantitative clay abundances from Mars spectra

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

    Quantitative estimates of clay minerals on the martian surface, via remote sensing observations, provide constraints on activity, timing, duration, and extent of aqueous processes and the geochemical environment in martian history. We describe an analytical study to begin enabling quantitative estimates of phyllosilicates when mixed with martian analog materials. We characterize the chemistry, mineralogy, particle size distribution, and reflectance spectra of the end-member materials: saponite, montmorillonite, pyroxene, and palagonitic soil. Reflectance spectra were obtained for physical mixtures of saponite and montmorillonite with pyroxene, and saponite with palagonitic soil. We analyzed the diagnostic phyllosilicate spectral signatures in the 2.2-2.4 μm wavelength region in detail for the mixtures. This involved fitting the observed ∼2.3 or ∼2.2 μm band depth, associated with the presence of saponite and montmorillonite, respectively, as a function of the abundance of these materials in the mixtures. Based upon the band depth of the spectral features we find that 3-5 wt.% of the clay minerals in the mixture with pyroxene can be recognized and at 25 wt.% their presence is indisputable in the mixtures. When the saponite is mixed with the lower albedo palagonitic soil, its presence is clearly distinguishable via the 1.4 and 2.3 μm features at 25 wt.% abundance. These relationships, between abundance and band depth, provide an ability to quantitatively address the amount of these materials in mixtures. The trends described here provide guidance for estimating the presence of phyllosilicates in matrices on the martian surface.

  3. Green Clay Minerals

    NASA Astrophysics Data System (ADS)

    Velde, B.

    2003-12-01

    Color is a problem for scientific study. One aspect is the vocabulary one used to describe color. Mint green, bottle green, and Kelly green are nice names but not of great utility in that people's physical perception of color is not always the same. In some industries, such as colored fabric manufacture, current use is to send a set of standard colors which are matched by the producer. This is similar to the use of the Munsell color charts in geology. None of these processes makes use of physical optical spectral studies. The reason is that they are difficult to obtain and interpret. For a geologist, color is very important but we rarely have the possibility to standardize the method of our color perception. One reason is that color is both a reflective and transmission phenomenon. The thickness of the sample is critical to any transmission characteristics. Hence, a field color determination is different from one made by using a petrographic microscope. Green glauconite in a hand specimen is not the same color in 30 μm thick thin section seen with a microscope using transmitted light.A second problem is that color in a spectral identification is the result of several absorption emissions,with overlapping signal, forming a complicated spectrum. Interpretation depends very greatly on the spectrum of the light source and the conditions of transmission-reflection of the sample. As a result, for this text, we will not attempt to analyze the physical aspect of green in green clays. In the discussion which follows, reference is made concerning color, to thin section microscopic perception.Very briefly, green clay minerals are green, because they contain iron. This is perhaps not a great revelation to mineralogists, but it is the key to understanding the origin and stability of green clay minerals. In fact, iron can color minerals either red or green or in various shades of orange and brown. The color most likely depends upon the relative abundance of the iron ion valence in the silicate (clay mineral in our case) structure, the specific bonding of these ions, and other factors. In fact, the reasons for coloration are not known completely, but it is certain that a combination of Fe2+ and Fe3+ ions is necessary to give a nice green color to clays. In the green clay minerals discussed here, the colors vary greatly as seen under the optical microscope (not always the same as the one seen in hand specimen). Yellow to blue-green hues can be found. However, for the moment, no clear relation between iron content, iron valence ratio, or other factors such as minor transition element concentrations can be found to explain the greenness of green clay minerals. The fact that a clay is green just indicates a combination of the two oxidation states of iron. The color, however, indicates the key to the formation in nature of green clay minerals.Green clay minerals are in general the product of "mixed valence" conditions of formation, most often in a situation where some iron is reduced from Fe3+ and enters into a silicate mineral structure. In general, iron would rather be an oxide when it is in the trivalent state. The moment iron is reduced to a divalent state under surface or near-surface conditions, it looks for a silicate, sulfide, or carbonate to hide in. The reverse is also true, of course. When a silicate is oxidized, Fe2+ becoming Fe3+, the iron begins to group together in oxide clumps and eventually exits the silicate structure. This is seen in thin section in altered rocks (weathering or hydrothermal action). The production of trivalent, oxidized iron usually results in a brownish or orange mineral.If the geology of the formation of green silicate minerals is relatively well defined, especially at near surface or surface conditions, the question remains how much of the iron is in a reduced oxidation state and how? In the case of reduction of iron in surface environments: if most of the iron goes to Fe2+, one mineral is formed; if only part of it is reduced, another is formed. This is the fundamental geochemical aspect of the genesis of green clay minerals; they contain iron in both oxidation states.Unfortunately modern methods of mineral analysis on a microscopic scale, electron microbeam and others, do not allow the determination of the different oxidation states of iron especially for nonstoichiometric minerals. One can use Mössbauer spectral analysis, but the scales of observations are not the same (Mössbauer needing more material); one method used for observations on a microscale, the other on a macroscale. Given the problems of micro- and macroscale observations, oxidation state information is almost excluded from data gathered since the 1980s or so, and hence information concerning the relations of iron reduction and clay genesis must be taken from older studies. A second, much greater problem is that little X-ray diffraction (XRD) work is done on samples which are analyzed chemically by electron microbeam studies. In the past both types of information, structural and chemical, were available for the same sample. Hence not only do we have no precise chemical data for many samples (oxidation state of iron), but there is a rarity of mineral structural information to go along with the incomplete chemistry. This is critical for the study of clay minerals, because slight chemical changes in a clay mineral are frequently accompanied by changes in its structure, especially when one deals with interstratified clay minerals (mica/smectites for example). In fact, the tendency to obtain more and more precision (analysis of a smaller and smaller sized sample) has led to a total loss of mineralogical data. The Heisenberg principle is unwittingly verified by geologists. We know more about a small part of a sample, but we know less about its whole. As a result, the following discussion is based largely upon old data, those which combine iron oxidation states and XRD information.

  4. Clay Mineral: Radiological Characterization

    NASA Astrophysics Data System (ADS)

    Cotomácio, J. G.; Silva, P. S. C.; Mazzilli, B. P.

    2008-08-01

    Since the early days, clays have been used for therapeutic purposes. Nowadays, most minerals applied as anti-inflammatory, pharmaceutics and cosmetic are the clay minerals that are used as the active ingredient or, as the excipient, in formulations. Although their large use, few information is available in literature on the content of the radionuclide concentrations of uranium and thorium natural series and 40K in these clay minerals. The objective of this work is to determine the concentrations of 238U, 232Th, 226Ra, 228Ra, 210Pb and 40K in commercial samples of clay minerals used for pharmaceutical or cosmetic purposes. Two kinds of clays samples were obtained in pharmacies, named green clay and white clay. Measurement for the determination of 238U and 232Th activity concentration was made by alpha spectrometry and gamma spectrometry was used for 226Ra, 228Ra, 210Pb and 40K determination. Some physical-chemical parameters were also determined as organic carbon and pH. The average activity concentration obtained was 906±340 Bq kg-1 for 40K, 40±9 Bq kg-1 for 226Ra, 75±9 Bq kg-1 for 228Ra, 197±38 Bq kg-1 for 210Pb, 51±26 Bq kg-1 for 238U and 55±24 Bq kg-1 for 232Th, considering both kinds of clay.

  5. Killer clays! Natural antibacterial clay minerals

    USGS Publications Warehouse

    Williams, L.B.; Holland, M.; Eberl, D.D.; Brunet, T.; De Courrsou, L. B.

    2004-01-01

    The clay chemical properties that may be important in medicine were investigated. It was found that natural clay minerals can have striking and very specific effects on microbial populations. The effects can range from potentially enhanced microbial growth to complete sterilization. This paper presents evidence that natural clay minerals can be effective antimicrobial agents.

  6. Clay Mineral Preferred Orientation

    NASA Astrophysics Data System (ADS)

    Day-Stirrat, R. J.

    2014-12-01

    Anisotropy of the orientation of clay minerals, often referred to as texture, may be unique to sediments' deposition, composition, deformation or diagenetic history. The literature is rich with studies that include preferred orientation generation in fault gouge, low-grade metamorphic rocks, sediments with variable clay content and during the smectite-to-illite transformation. Untangling the interplay between many competing factors in any one geologic situation has proven a significant challenge over many years. Understanding how, where and when clay minerals develop a preferred orientation has significant implications for permeability anisotropy in shallow burial, the way mechanical properties are projected from shallower to deeper settings in basin modeling packages and the way velocity anisotropy is accounted for in seismic data processing. The assessment of the anisotropic properties of fine-grained siliciclastic rocks is gaining significant momentum in rock physics research. Therefore, a fundamental understanding of how clay minerals develop a preferred orientation in space and time is crucial to the understanding of anisotropy of physical properties. The current study brings together a wealth of data that may be used in a predictive sense to account for fabric anisotropy that may impact any number of rock properties.

  7. Mineral resource of the Month: Clay

    USGS Publications Warehouse

    Virta, Robert L.

    2010-01-01

    Clays were one of the first mineral commodities used by people. Clay pottery has been found in archeological sites that are 12,000 years old, and clay figurines have been found in sites that are even older.

  8. Mineral resource of the month: clays

    USGS Publications Warehouse

    Virta, Robert

    2004-01-01

    Clays represent one of the largest mineral commodities in the world in terms of mineral and rock production and use. Many people, however, do not recognize that clays are used in an amazingly wide variety of applications. Use continues to increase worldwide as populations and their associated needs increase. Robert Virta, clay and shale commodity specialist for the U.S. Geological Survey, has prepared the following information about clays.

  9. Clay mineralogy of weathering rinds and possible implications concerning the sources of clay minerals in soils.

    USGS Publications Warehouse

    Colman, Steven M.

    1982-01-01

    Weathering rinds on volcanic clasts in Quaternary deposits in the western US contain only very fine-grained and poorly crystalline clay minerals. Rinds were sampled from soils containing well-developed argillic B horizons in deposits approx 105 yr old or more. The clay-size fraction of the rinds is dominated by allophane and iron hydroxy-oxides, whereas the B horizons contain abundant well-crystallized clay minerals. The contrast between the clay mineralogy of the weathering rinds, in which weathering is isolated from other soil processes, and that of the associated soil matrices suggests a need to reassess assumptions concerning the rates at which clay minerals form and the sources of clay minerals in argillic B horizons. It seems that crystalline clay minerals form more slowly in weathering rinds than is generally assumed for soil environments and that the weathering of primary minerals may not be the dominant source of crystalline clay minerals in Middle to Late Pleistocene soil.-A.P.

  10. Dehydration-induced luminescence in clay minerals

    NASA Technical Reports Server (NTRS)

    Coyne, L. M.; Lahav, N.; Lawless, J. G.

    1981-01-01

    Reports of triboluminescent phenomena in organic crystalline materials prompted a search for related processes in clay minerals. The reported extensive mechanical distortion produced on freezing and drying of montmorillonite was particularly interesting because of studies of condensation reactions in a wet/dry cycled reaction sequence. The discovery of an unusual luminescent process in several clay minerals is reported and its characteristics are described.

  11. Surface geochemistry of the clay minerals

    PubMed Central

    Sposito, Garrison; Skipper, Neal T.; Sutton, Rebecca; Park, Sung-ho; Soper, Alan K.; Greathouse, Jeffery A.

    1999-01-01

    Clay minerals are layer type aluminosilicates that figure in terrestrial biogeochemical cycles, in the buffering capacity of the oceans, and in the containment of toxic waste materials. They are also used as lubricants in petroleum extraction and as industrial catalysts for the synthesis of many organic compounds. These applications derive fundamentally from the colloidal size and permanent structural charge of clay mineral particles, which endow them with significant surface reactivity. Unraveling the surface geochemistry of hydrated clay minerals is an abiding, if difficult, topic in earth sciences research. Recent experimental and computational studies that take advantage of new methodologies and basic insights derived from the study of concentrated ionic solutions have begun to clarify the structure of electrical double layers formed on hydrated clay mineral surfaces, particularly those in the interlayer region of swelling 2:1 layer type clay minerals. One emerging trend is that the coordination of interlayer cations with water molecules and clay mineral surface oxygens is governed largely by cation size and charge, similarly to a concentrated ionic solution, but the location of structural charge within a clay layer and the existence of hydrophobic patches on its surface provide important modulations. The larger the interlayer cation, the greater the influence of clay mineral structure and hydrophobicity on the configurations of adsorbed water molecules. This picture extends readily to hydrophobic molecules adsorbed within an interlayer region, with important implications for clay–hydrocarbon interactions and the design of catalysts for organic synthesis. PMID:10097044

  12. Ostwald ripening of clays and metamorphic minerals.

    PubMed

    Eberl, D D; Sacuterodonacute, J; Kralik, M; Taylor, B E; Peterman, Z E

    1990-04-27

    Analyses of particle size distributions indicate that clay minerals and other diagenetic and metamorphic minerals commonly undergo recrystallization by Ostwald ripening. The shapes of their particle size distributions can yield the rate law for this process. One consequence of Ostwald ripening is that a record of the recrystallization process is preserved in the various particle sizes. Therefore, one can determine the detailed geologic history of clays and other recrystallized minerals by separating, from a single sample, the various particle sizes for independent chemical, structural, and isotopic analyses. PMID:17815598

  13. Adsorption of nucleic Acid bases, ribose, and phosphate by some clay minerals.

    PubMed

    Hashizume, Hideo

    2015-01-01

    Besides having a large capacity for taking up organic molecules, clay minerals can catalyze a variety of organic reactions. Derived from rock weathering, clay minerals would have been abundant in the early Earth. As such, they might be expected to play a role in chemical evolution. The interactions of clay minerals with biopolymers, including RNA, have been the subject of many investigations. The behavior of RNA components at clay mineral surfaces needs to be assessed if we are to appreciate how clays might catalyze the formation of nucleosides, nucleotides and polynucleotides in the "RNA world". The adsorption of purines, pyrimidines and nucleosides from aqueous solution to clay minerals is affected by suspension pH. With montmorillonite, adsorption is also influenced by the nature of the exchangeable cations. Here, we review the interactions of some clay minerals with RNA components. PMID:25734235

  14. Adsorption of Nucleic Acid Bases, Ribose, and Phosphate by Some Clay Minerals

    PubMed Central

    Hashizume, Hideo

    2015-01-01

    Besides having a large capacity for taking up organic molecules, clay minerals can catalyze a variety of organic reactions. Derived from rock weathering, clay minerals would have been abundant in the early Earth. As such, they might be expected to play a role in chemical evolution. The interactions of clay minerals with biopolymers, including RNA, have been the subject of many investigations. The behavior of RNA components at clay mineral surfaces needs to be assessed if we are to appreciate how clays might catalyze the formation of nucleosides, nucleotides and polynucleotides in the “RNA world”. The adsorption of purines, pyrimidines and nucleosides from aqueous solution to clay minerals is affected by suspension pH. With montmorillonite, adsorption is also influenced by the nature of the exchangeable cations. Here, we review the interactions of some clay minerals with RNA components. PMID:25734235

  15. Clays and other minerals in prebiotic processes

    NASA Technical Reports Server (NTRS)

    Paecht-Horowitz, M.

    1984-01-01

    Clays and other minerals have been investigated in context with prebiotic processes, mainly in polymerization of amino acids. It was found that peptides adsorbed on the clay, prior to polymerization, influence the reaction. The ratio between the amount of the peptides adsorbed and that of the clay is important for the yield as well as for the degrees of polymerization obtained. Adsorption prior to reaction produces a certain order in the aggregates of the clay particles which might induce better reaction results. Excess of added peptides disturbs this order and causes lesser degrees of polymerization. In addition to adsorption, clays are also able to occlude between their layers substances out of the environment, up to very high concentrations.

  16. Fluxes of clay minerals in the South China Sea

    NASA Astrophysics Data System (ADS)

    Schroeder, Annette; Wiesner, Martin G.; Liu, Zhifei

    2015-11-01

    In order to assess dominant settling processes that change the composition of the detrital clay fraction during transport from neighboring estuaries to a deep sea basin, we studied relative clay mineral abundances and absolute clay mineral fluxes of clay-sized sinking particulate matter collected by eight sediment trap systems deployed from shallow to deep water depth in the South China Sea. This is the first basin-wide study on recent sedimentation processes in the western Pacific marginal seas. Annual averages of relative clay mineral abundances at the shallow traps are temporally more variable and regionally more diverse, resembling those of surrounding drainage basins. In contrast, higher fluxes of material reach the deeper traps. Their characteristics trend temporally and spatially towards uniformity and are enriched with smectite in the entire deep basin. Sinking particulate matter that reaches the shallow traps spends less time in pelagic transport and is affected by monsoonal current reversals. The enrichment in smectite in the deeper traps is a result of longer duration in transport at low velocities, which may increase the effect of differential settling during transport. The trend is caused by lateral advection driven by the cyclonic deep circulation, and this is considered as the main transport process in the northern and central deep basin. The high fluxes in the south-western deep basin could be the result of laterally advected re-suspended sediments from the neighboring shelves. The effects on the composition of the detrital clay fraction caused by oceanographic control, which indirectly include those by differential settling, mask the climatic signal from surrounding drainage basins in the deep basin sediments. This strongly affects the interpretation of the clay mineralogical record in sediments deposited under recent conditions in the South China Sea deep basin.

  17. Adsorption of polyamine on clay minerals.

    PubMed

    Blachier, C; Michot, L; Bihannic, I; Barrès, O; Jacquet, A; Mosquet, M

    2009-08-15

    This work aims at a better understanding of the interaction between a polycationic quaternary amine polymer (F25) and three different clay minerals: montmorillonite, illite, and kaolinite. For this, adsorption isotherms of F25 on the clay surfaces were measured together with the evolution of the CEC along the isotherm, which revealed that cation exchange plays an important role in the adsorption process. These first results were confirmed by XRD measurements on dried powders that are evidence in the case of montmorillonite of the presence of polymer in the interlayer spaces. In addition, the evolution of the short range structure of clay minerals suspensions on polymer adsorption was followed by WAXS experiments. Polymer intercalation was observed while the structure of the resulting stacking appeared to change slightly along the polymer adsorption isotherm. Diffuse reflectance infrared measurements revealed that significant conformational changes occur on polymer adsorption onto montmorillonite surfaces. Furthermore, adsorption above the CEC is observed which involves a charge reversal of clay mineral surfaces, the zero charge being reached for an adsorbed amount corresponding to the CEC. Finally, flocculation was discussed compared to adsorption amounts and zeta potential measurements, confirming that optimum flocculation concentration is reached for noncharged particles. PMID:19464022

  18. Lipid peroxidation induced by expandable clay minerals.

    PubMed

    Kibanova, Daria; Nieto-Camacho, Antonio; Cervini-Silva, Javiera

    2009-10-01

    Small-sized environmental particles such as 2:1 phyllosilicates induce oxidative stress, a primary indicator of cell damage and toxicity. Herein, potential hazards of clay particle uptake are addressed. This paper reports that the content and distribution of structural Fe influence the ability of expandable clay minerals to induce lipid peroxidation (LP), a major indicator of oxidative stress, in biological matrices. Three smectite clays, hectorite (SHCa-1) and two nontronites (NAu-1) and (NAu-2) containing varying total content and coordination environment of structural Fe, were selected. Screening and monitoring of LP was conducted using a thiobarbituric acid reactive substances (TBARS) assay. The higher content of TBARS in nontronites than that in SHCa-1 suspensions was explained because structural Fe contributes to LP. The observed lack of correlation between TBARS content and the extent of Fe dissolution indicated that the formation of TBARS is surface controlled. Results showing a high TBARS content in SHCa-1 but not in nontronite supematant solutions was explained because the former contains distinct, soluble chemical component(s) that could (i) induce LP by its (their) own right and (ii) whose chemical affinity for organic ligands used as inhibitors is weak. Clays serve as stronger inductors than 2,2'-azobis(2-amidinopropane) dihydrochloride (AAPH) but are much weaker than FeSO4. The outcome of this work shows that LP is clay surface-controlled and dependent on clay structural composition. PMID:19848175

  19. Radiation-induced defects in clay minerals: A review

    NASA Astrophysics Data System (ADS)

    Allard, Th.; Balan, E.; Calas, G.; Fourdrin, C.; Morichon, E.; Sorieul, S.

    2012-04-01

    Extensive information has been collected on radiation effects on clay minerals over the last 35 years, providing a wealth of information on environmental and geological processes. The fields of applications include the reconstruction of past radioelement migrations, the dating of clay minerals or the evolution of the physico-chemical properties under irradiation. The investigation of several clay minerals, namely kaolinite, dickite, montmorillonite, illite and sudoite, by Electron Paramagnetic Resonance Spectroscopy has shown the presence of defects produced by natural or artificial radiations. These defects consist mostly of electron holes located on oxygen atoms of the structure. The various radiation-induced defects are differentiated through their nature and their thermal stability. Most of them are associated with a π orbital on a Si-O bond. The most abundant defect in clay minerals is oriented perpendicular to the silicate layer. Thermal annealing indicates this defect in kaolinite (A-center) to be stable over geological periods at ambient temperature. Besides, electron or heavy ion irradiation easily leads to an amorphization in smectites, depending on the type of interlayer cation. The amorphization dose exhibits a bell-shaped variation as a function of temperature, with a decreasing part that indicates the influence of thermal dehydroxylation. Two main applications of the knowledge of radiation-induced defects in clay minerals are derived: (i) The use of defects as tracers of past radioactivity. In geological systems where the age of the clay can be constrained, ancient migrations of radioelements can be reconstructed in natural analogues of high level nuclear waste repositories. When the dose rate may be assumed constant over time, the paleodose is used to date clay populations, an approach applied to fault gouges or laterites of the Amazon basin. (ii) The influence of irradiation over physico-chemical properties of clay minerals. An environmental application concerns the performance assessment of the engineered barrier of nuclear waste disposals. In case of a leakage of transuranic elements from the radioactive waste form, alpha recoil nuclei can amorphize smectite after periods of the order of 1000 years according to a worst case scenario, whereas amorphization from ionizing radiation is unlikely. As amorphization greatly enhances the dissolution kinetics of smectite, the sensitivity of the smectites must be taken into account in the prediction of the long term behavior of engineered barriers.

  20. Mineral Acquisition from Clay by Budongo Forest Chimpanzees

    PubMed Central

    Reynolds, Vernon; Lloyd, Andrew W.; English, Christopher J.; Lyons, Peter; Dodd, Howard; Hobaiter, Catherine; Newton-Fisher, Nicholas; Mullins, Caroline; Lamon, Noemie; Schel, Anne Marijke; Fallon, Brittany

    2015-01-01

    Chimpanzees of the Sonso community, Budongo Forest, Uganda were observed eating clay and drinking clay-water from waterholes. We show that clay, clay-rich water, and clay obtained with leaf sponges, provide a range of minerals in different concentrations. The presence of aluminium in the clay consumed indicates that it takes the form of kaolinite. We discuss the contribution of clay geophagy to the mineral intake of the Sonso chimpanzees and show that clay eaten using leaf sponges is particularly rich in minerals. We show that termite mound soil, also regularly consumed, is rich in minerals. We discuss the frequency of clay and termite soil geophagy in the context of the disappearance from Budongo Forest of a formerly rich source of minerals, the decaying pith of Raphia farinifera palms. PMID:26218593

  1. Sorption Energy Maps of Clay Mineral Surfaces

    SciTech Connect

    Cygan, Randall T.; Kirkpatrick, R. James

    1999-07-19

    A molecular-level understanding of mineral-water interactions is critical for the evaluation and prediction of the sorption properties of clay minerals that may be used in various chemical and radioactive waste disposal methods. Molecular models of metal sorption incorporate empirical energy force fields, based on molecular orbital calculations and spectroscopic data, that account for Coulombic, van der Waals attractive, and short-range repulsive energies. The summation of the non-bonded energy terms at equally-spaced grid points surrounding a mineral substrate provides a three dimensional potential energy grid. The energy map can be used to determine the optimal sorption sites of metal ions on the exposed surfaces of the mineral. By using this approach, we have evaluated the crystallographic and compositional control of metal sorption on the surfaces of kaolinite and illite. Estimates of the relative sorption energy and most stable sorption sites are derived based on a rigid ion approximation.

  2. Feasibility of classification of clay minerals by using PAS

    NASA Astrophysics Data System (ADS)

    Honda, Y.; Yoshida, Y.; Akiyama, Y.; Nishijima, S.

    2015-06-01

    After the nuclear power plant disaster, the evaluation of radioactive Cs kept in soil, especially in clay minerals and the elucidation of its movement are urgent subjects to promote decontamination. It is known that the extractable level of Cs depends on the sort of clay minerals. We tried to find the characteristics of clay minerals belonging to phillosilicate group using positron annihilation spectroscopy (PAS) and the relationship between the results of PAS and the amounts of substantially extracted Cs from the clay minerals. The results showed that each clay mineral was found to be distinguishable from other clay minerals by PAS and the extraction rate of Cs was different among those clay minerals, however the direct correlation between the results of PAS and the extraction rates of Cs was not found.

  3. Prolonged triboluminescence in clays and other minerals

    NASA Technical Reports Server (NTRS)

    Lahav, N.; Coyne, L. M.; Lawless, J. G.

    1982-01-01

    Samples of various clays and minerals were ground or fractured and monitored with a liquid scintillation spectrometer in order to obtain triboluminescent decay curves. Kaolinite samples displayed several million counts/min after grinding, with a surface area emission estimated at tens of billions of photons/sq cm of surface. The photon production rates varied with the origin of the sample, and kaolinite continually yielded higher production rates than bentonite. The addition of water to the samples slightly increased the count rate of emitted light, while the addition of the fluorescent molecule substance tryptofan significantly enhanced the count rate. Freezing smears of kaolinite and montmorillonite in liquid nitrogen and in a salt ice mixture also induced triboluminescence in the montmorillonite. A possible connection between powdery triboluminescent materials formed in mining industries and respiratory disorders among miners is suggested.

  4. Diagenetic clays as pore-lining minerals in coalbed methane reservoirs

    SciTech Connect

    Fowler, K.S.; Nick, K.E.

    1996-12-31

    Cleat surfaces from Mary Lee and Black Creek coal seams in the Black Warrior Basin and Fruitland coal from the San Juan Basin show significant amounts of diagenetic quartz, illite, kaolinite, carbonate minerals, barite, gypsum and iron sulfides and sulfates. SEM, XRD, thin section and reflected light microscopy analyses were used to identify and describe diagenetic minerals and surface textures observed along permeable cleat surfaces. SEM-EDS analysis reveals a variety of pore-lining diagenetic minerals with complex crystal morphologies in permeable cleats of preserved core and mine samples. Surface textures were varied from smooth and vitreous, dull and pitted, to rough and irregular with imbedded diagenetic minerals, often clays or sulfides. Illite is the most abundant clay and occurs as surface coatings, aggregates, authigenic crystals embedded in the coal surface, or oriented subparallel to the fracture face. Kaolinite is also abundant and occurs as abraded platelets and loosely attached aggregates packed against steps, as meniscus shapes on smooth fracture faces, and as a thick crust of anhedral crystals. Chlorite, the least abundant clay, appears as sheets of small crystals. Locally abundant sulfate, sulfide and carbonate minerals are present in masses of euhedral crystals or concentrated as thick crusts. Surface irregularities sometimes control the distribution of diagenetic minerals. Coal fines of unambiguous internal origin and masses of clays are often concentrated at surface irregularities such as steps, laminations of interbedded clays, or sulfides and coal and rough areas of fractures. Their distribution suggests mobility within fractures.

  5. Diagenetic clays as pore-lining minerals in coalbed methane reservoirs

    SciTech Connect

    Fowler, K.S.; Nick, K.E. )

    1996-01-01

    Cleat surfaces from Mary Lee and Black Creek coal seams in the Black Warrior Basin and Fruitland coal from the San Juan Basin show significant amounts of diagenetic quartz, illite, kaolinite, carbonate minerals, barite, gypsum and iron sulfides and sulfates. SEM, XRD, thin section and reflected light microscopy analyses were used to identify and describe diagenetic minerals and surface textures observed along permeable cleat surfaces. SEM-EDS analysis reveals a variety of pore-lining diagenetic minerals with complex crystal morphologies in permeable cleats of preserved core and mine samples. Surface textures were varied from smooth and vitreous, dull and pitted, to rough and irregular with imbedded diagenetic minerals, often clays or sulfides. Illite is the most abundant clay and occurs as surface coatings, aggregates, authigenic crystals embedded in the coal surface, or oriented subparallel to the fracture face. Kaolinite is also abundant and occurs as abraded platelets and loosely attached aggregates packed against steps, as meniscus shapes on smooth fracture faces, and as a thick crust of anhedral crystals. Chlorite, the least abundant clay, appears as sheets of small crystals. Locally abundant sulfate, sulfide and carbonate minerals are present in masses of euhedral crystals or concentrated as thick crusts. Surface irregularities sometimes control the distribution of diagenetic minerals. Coal fines of unambiguous internal origin and masses of clays are often concentrated at surface irregularities such as steps, laminations of interbedded clays, or sulfides and coal and rough areas of fractures. Their distribution suggests mobility within fractures.

  6. Recent advances in clay mineral-containing nanocomposite hydrogels.

    PubMed

    Zhao, Li Zhi; Zhou, Chun Hui; Wang, Jing; Tong, Dong Shen; Yu, Wei Hua; Wang, Hao

    2015-12-28

    Clay mineral-containing nanocomposite hydrogels have been proven to have exceptional composition, properties, and applications, and consequently have attracted a significant amount of research effort over the past few years. The objective of this paper is to summarize and evaluate scientific advances in clay mineral-containing nanocomposite hydrogels in terms of their specific preparation, formation mechanisms, properties, and applications, and to identify the prevailing challenges and future directions in the field. The state-of-the-art of existing technologies and insights into the exfoliation of layered clay minerals, in particular montmorillonite and LAPONITE®, are discussed first. The formation and structural characteristics of polymer/clay nanocomposite hydrogels made from in situ free radical polymerization, supramolecular assembly, and freezing-thawing cycles are then examined. Studies indicate that additional hydrogen bonding, electrostatic interactions, coordination bonds, hydrophobic interaction, and even covalent bonds could occur between the clay mineral nanoplatelets and polymer chains, thereby leading to the formation of unique three-dimensional networks. Accordingly, the hydrogels exhibit exceptional optical and mechanical properties, swelling-deswelling behavior, and stimuli-responsiveness, reflecting the remarkable effects of clay minerals. With the pivotal roles of clay minerals in clay mineral-containing nanocomposite hydrogels, the nanocomposite hydrogels possess great potential as superabsorbents, drug vehicles, tissue scaffolds, wound dressing, and biosensors. Future studies should lay emphasis on the formation mechanisms with in-depth insights into interfacial interactions, the tactical functionalization of clay minerals and polymers for desired properties, and expanding of their applications. PMID:26435008

  7. Analysis of mixed-layer clay mineral structures

    USGS Publications Warehouse

    Bradley, W.F.

    1953-01-01

    Among the enormously abundant natural occurrences of clay minerals, many examples are encountered in which no single specific crystallization scheme extends through a single ultimate grain. The characterization of such assemblages becomes an analysis of the distribution of matter within such grains, rather than the simple identification of mineral species. It having become established that the particular coordination complex typified by mica is a common component of many natural subcrystalline assemblages, the opportunity is afforded to analyze scattering from random associations of these complexes with other structural units. Successful analyses have been made of mixed hydration states of montmorillonite, of montmorillonite with mica, of vermiculite with mica, and of montmorillonite with chlorite, all of which are variants of the mica complex, and of halloysite with hydrated halloysite.

  8. The systems containing clays and clay minerals from modified drug release: a review.

    PubMed

    Rodrigues, Luís Alberto de Sousa; Figueiras, Ana; Veiga, Francisco; de Freitas, Rivelilson Mendes; Nunes, Lívio César Cunha; da Silva Filho, Edson Cavalcanti; da Silva Leite, Cleide Maria

    2013-03-01

    Clays are materials commonly used in the pharmaceutical industry, either as ingredients or as active ingredients. It was observed that when they are administered concurrently, they may interact with drugs reducing their absorption. Therefore, such interactions can be used to achieve technological and biopharmaceutical advantages, regarding the control of release. This review summarizes bibliographic (articles) and technological (patents) information on the use of systems containing clays and clay minerals in modified drug delivery. In this area, formulations such natural clay, commercial clay, synthetic clay, composites clay-polymers, nanocomposites clay-polymers, films and hidrogels composites clay-polymers are used to slow/extend or vectorize the release of drugs and consequently they increase their bioavailability. Finally, this review summarizes the fields of technology and biopharmaceutical applications, where clays are applied. PMID:23253474

  9. The effect of clay minerals on diasterane/sterane ratios

    NASA Astrophysics Data System (ADS)

    van Kaam-Peters, Heidy M. E.; Kster, Jrgen; van der Gaast, Sjierk J.; Dekker, Marln; de Leeuw, Jan W.; Sinninghe Damst, Jaap S.

    1998-09-01

    To examine the effect of clay minerals on diasterane/sterane ratios, the mineral compositions of three sample sets of sedimentary rocks displaying a wide range of diasterane/sterane ratios were analysed quantitatively. Diasterane/sterane ratios do not to correlate with clay content but depend on the amount of clay relative to the amount of organic matter (clay/TOC ratios). This correlation may explain the high diasterane/sterane ratios in crude oils and extracts derived from certain carbonate source rocks. Based on the concentrations of regular and rearranged steroids in the sample sets, it is proposed that diasterenes are partly reduced to diasteranes and partly degraded during diagenesis in a ratio largely determined by the availability of clay minerals. It is suggested that the hydrogen atoms required for reduction of the diasterenes originate from the water in the interlayers of clay minerals.

  10. Clays and Clay Minerals and their environmental application in Food Technology

    NASA Astrophysics Data System (ADS)

    del Hoyo Martínez, Carmen; Cuéllar Antequera, Jorge; Sánchez Escribano, Vicente; Solange Lozano García, Marina; Cutillas Díez, Raul

    2013-04-01

    The clay materials have led to numerous applications in the field of public health (del Hoyo, 2007; Volzone, 2007) having been demonstrated its effectiveness as adsorbents of all contaminants. Some biodegradable materials are used for for adsorption of chemical contaminants: lignins (Valderrabano et al., 2008) and also clays and clay minerals, whose colloidal properties, ease of generating structural changes, abundance in nature, and low cost make them very suitable for this kind of applications. Among the strategies used at present to preserve the quality of the water and this way to diminish the environmental risk that supposes the chemical pollution, stands out the use of adsorbents of under cost, already they are natural or modified, to immobilize these compounds and to avoid the pollution of the water with the consequent reduction of environmental and economic costs Thanks to the development of the science and the technology of the nourishment in the last 50 years, there have revealed itself several new substances that can fulfill beneficial functions in the food, and these substances, named food additives, are today within reach of all. The food additives recover a very important role in the complex nourishing supply. The additives fulfill several useful functions in the food, which often we give for sat. Nevertheless the widespread use of food additives in the food production also influences the public health. The food industries, which are very important for the economy, spill residues proved from its activity that they have to be controlled to evaluate the environmental impact and to offer the necessary information about the quantitative evaluation of the chemical risk of the use of food additives for the public health. We have studied the adsorption of several contaminants by natural or modified clays, searching their interaction mechanisms and the possible recycling of these materials for environmental purposes and prevention of the health. References -del Hoyo, C. (2007). Applied Clay Science. 36, 103-121.Layered Double Hydroxides and human health: An overview. -Valderrábano, M., Rodríguez-Cruz, S., del Hoyo, C., Sánchez-Martín, M.J. (2006). 4th International Workshop "Bioavalailability of pollutants and soil remediation". 1, 5-6. Physicochemical study of the adsorption of pesticides by lignins. -Volzone, C. (2007). Applied Clay Science. 36, 191-196. Retention of pollutant gases: Comparison between clay minerals and their modified products.

  11. Impact-Induced Clay Mineral Formation and Distribution on Mars

    NASA Technical Reports Server (NTRS)

    Rivera-Valentin, E. G.; Craig, P. I.

    2015-01-01

    Clay minerals have been identified in the central peaks and ejecta blankets of impact craters on Mars. Several studies have suggested these clay minerals formed as a result of impact induced hydrothermalism either during Mars' Noachian era or more recently by the melting of subsurface ice. Examples of post-impact clay formation is found in several locations on Earth such as the Mjolnir and Woodleigh Impact Structures. Additionally, a recent study has suggested the clay minerals observed on Ceres are the result of impact-induced hydrothermal processes. Such processes may have occurred on Mars, possibly during the Noachian. Distinguishing between clay minerals formed preor post-impact can be accomplished by studying their IR spectra. In fact, showed that the IR spectra of clay minerals is greatly affected at longer wavelengths (i.e. mid-IR, 5-25 micron) by impact-induced shock deformation while the near-IR spectra (1.0-2.5 micron) remains relatively unchanged. This explains the discrepancy between NIR and MIR observations of clay minerals in martian impact craters noted. Thus, it allows us to determine whether a clay mineral formed from impact-induced hydrothermalism or were pre-existing and were altered by the impact. Here we study the role of impacts on the formation and distribution of clay minerals on Mars via a fully 3-D Monte Carlo cratering model, including impact- melt production using results from modern hydrocode simulations. We identify regions that are conducive to clay formation and the location of clay minerals post-bombardment.

  12. Clay mineral formation and transformation in rocks and soils

    USGS Publications Warehouse

    Eberl, D.D.

    1983-01-01

    Three mechanisms for clay mineral formation (inheritance, neoformation, and transformation) operating in three geological environments (weathering, sedimentary, and diagenetic-hydrothermal) yield nine possibilities for the origin of clay minerals in nature. Several of these possibilities are discussed in terms of the rock cycle. The mineralogy of clays neoformed in the weathering environment is a function of solution chemistry, with the most dilute solutions favoring formation of the least soluble clays. After erosion and transportation, these clays may be deposited on the ocean floor in a lateral sequence that depends on floccule size. Clays undergo little reaction in the ocean, except for ion exchange and the neoformation of smectite; therefore, most clays found on the ocean floor are inherited from adjacent continents. Upon burial and heating, however, dioctahedral smectite reacts in the diagenetic environment to yield mixed-layer illite-smectite, and finally illite. With uplift and weathering, the cycle begins again. Refs.

  13. Microbe-Clay Mineral Reactions and Characterization Techniques

    NASA Astrophysics Data System (ADS)

    Dong, H.; Zhang, G.; Ji, S.; Jaisi, D.; Kim, J.

    2008-12-01

    Clays and clay minerals are ubiquitous in soils, sediments, and sedimentary rocks. They play an important role in environmental processes such as nutrient cycling, plant growth, contaminant migration, organic matter maturation, and petroleum production. The changes in the oxidation state of the structural iron in clay minerals, in part, control their physical and chemical properties in natural environments, such as clay particle flocculation, dispersion, swelling, hydraulic conductivity, surface area, cation and anion exchange capacity, and reactivity towards organic and inorganic contaminants. The structural ferric iron [Fe(III)] in clay minerals can be reduced either chemically or biologically. Many different chemical reductants have been tried, but the most commonly used agent is dithionite. Biological reductants are bacteria, including dissimilatory iron reducing prokaryotes (DIRP) and sulfate-reducing bacteria (SRB). A wide variety of DIRP have been used to reduce ferric iron in clay minerals, including mesophilic, thermophilic, and hyperthermophilic prokaryotes. Multiple clay minerals have been used for microbial reduction studies, including smectite, nontronite (iron-rich smectite variety), illite, illite/smectite, chlorite, and their various mixtures. All these clay minerals are reducible by microorganisms under various conditions with smectite (nontronite) being the most reducible. The reduction extent and rate of ferric iron in clay minerals are measured by wet chemistry, and the reduced clay mineral products are typically characterized with chemical methods, X-ray diffraction, scanning and transmission electron microscopy, Mössbauer spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR), UV-vis spectroscopy, and synchrotron-based techniques (such as EXAFS). Microbially reduced smectites (nontronites) have been found to be reactive in reducing a variety of organic and inorganic contaminants. Degradable organic contaminants include pesticides, solvents, explosives, and nitroaromatic and polychlorinated compounds. Inorganic contaminants include Cr(VI), U(VI), and Tc(VII). Despite significant efforts, our understanding of mechanisms of chemical and microbial reduction of ferric iron in clay minerals is still limited. While some studies have presented evidence for a solid-state reduction mechanism, others argue that the clay mineral structure dissolves when the extent of reduction is higher (greater than 30 percent). The electron transfer process is also dependent on the reducing agent. While chemical reduction of ferric iron appears to occur at the basal surfaces, bacteria appear to attack clay minerals at the edges.

  14. Layer Charge of Clay Minerals; Selected papers from the Symposium on Current Knowledge on the Layer Charge of Clay Minerals

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This Special issue contains papers based on the contributions presented during the workshop “Current Knowledge on the Layer Charge of Clay Minerals”, held on September 18 and 19, 2004, in the Smolenice Castle, Slovakia. Layer charge is one of the most important characteristics of clay minerals as it...

  15. Clays and clay minerals in Bikaner: Sources, environment pollution and management

    NASA Astrophysics Data System (ADS)

    Gayatri, Sharma; Anu, Sharma

    2016-05-01

    Environmental pollution can also be caused by minerals which include natural as well as human activities. Rapid urbanization, consumerist life style, anthropogenic deeds are increasing environmental pollution day by day. Fluctuation in our ecosystem or polluted environment leads to many diseases and shows adverse effects on living organisms. The main aim of this paper is to highlight the environmental pollution from clays and clay minerals and their mitigation..

  16. Geochemistry of clay minerals for uranium exploration in the Grants mineral belt, New Mexico

    NASA Astrophysics Data System (ADS)

    Brookins, D. G.

    1982-03-01

    Clay mineralogy studies of ore rocks versus barren rocks in the Grants mineral belt, New Mexico, show that some combination of chlorite (rosette form), illite, mixed-layer illite-montmorillonite, (±Mg-montmorillonite) are penecontemporaneous with uranium minerals in trend ore; these same clay minerals plus kaolinite are related to the roll-type ore near the main redox front of the Grants mineral belt. Clay minerals from barren rocks are characterized by a greater abundance of Na-montmorillonite, kaolinite, and face-to-edge form chlorite. Chlorites from ore zones contain much more vanadium than do chlorites from barren rocks. Trend orr probably formed from southeasterly flowing waters following paleochannels in the Late Jurassic. These deposits are found almost entirely in reduced rocks, and organic carbon may have been an important reductant to remove U-V-U-V-Se-Mo from solution as carbonate from ore zones contains some organic carbon based on stable isotope studies. Uplift, remobilization, and reprecipitation of some of the trend ore resulted in the formation of redistributed ore, some of which possesses a roll-type geometry. Mineralization for the roll-type ore was apparently controlled by sulfide-sulfate equilibria at or near the main redox front in the Grants mineral belt. Trend and roll-type ore possess different assemblages of clay minerals and different trace element abundances. Laramide-age faults cut both trend ore and some roll-type ores. Stack ore is found in Laramide-age fault zones. Limited oxygen isotopic data from clay minerals collected from two mines at Ambrosia Lake in reduced rocks indicate probable preservation of ancient, formational waters and show no evidence of infiltration by young meteoric waters. This information, plus the pre-Laramide-age faults, suggest, but do not unequivocally prove, that the main redox front has been relatively stable since its formation, probably some time in the Cretaceous. Younger encroachment of the redox front in post-Laramide time is proposed by others, however, and the problem is unresolved. Uranium for the deposits was most likely carried in solution as an oxyion, probably as (UO2(CO3)2·2H2O2- or (UO2(HPO4)2)2-, although organic transport cannot be entirely ruled out. Oxyions of vanadium, selenium, molybdenum and possible arsenic and antimony, are interpreted from Eh-pH diagrams to have been segregated and transported with U6+ soluble species and precipitated when a chemically reducing environment was reached. The rare-earth elements are also enriched in ore zones, but is it not clear if they were transported with the U-V-Se-Mo-(As)-(Sb) suite or derived from a more local source.

  17. Clay Mineral Assemblages as Proxies for Reconstructing Messinian Paleoenvironments in the Western Mediterranean

    NASA Astrophysics Data System (ADS)

    Martinez-Ruiz, Francisca; Comas, Menchu; Vasconcelos, Crisogono

    2014-05-01

    Significant tectonic and climate changes at time of the Messinian Salinity Crisis (MSC) led to a complex sedimentation involving marked changes in sediment composition, particularly in clay mineral assemblages. One of the noticeable mineralogical changes across this time interval is the strong smectite increase in Messinian deposits in comparison to the underlying Tortonian and overlaying Pliocene sediments. As no break in the clay mineralogy is recognized in the open ocean (Chamley et al., 1978), such changes are also distinctive of the Mediterranean basins. Since the early discoveries of the giant Messinian evaporite formation (DSDP Legs 13 and 42A), a vast literature contributed, during the last decades, to the continuous debate and re-examination of the actual Messinian paleoenvironment. Drilled records in the westernmost Mediterranean (Alboran Sea) have shown significant changes in the mineralogical assemblages associated to the Messinian events. This basin is depleted of significant salt deposits. Site 976 (ODP Leg 161) recovered a 670-m-thick, middle Miocene (Serravallian) to Pleistocene/Holocene sedimentary sequence, including a thin interval of Messinian sediment, lying directly upon the metamorphic basement. Analysis of clay mineral assemblages from the sedimentary cover of Hole 976B revealed an homogeneous clay association composed of illite, smectite, chlorite and kaolinite with no major changes in clay mineral abundances except for the sediment interval dated as Messinian, which is characterized by a sharp smectite increase (Martinez-Ruiz et al., 1999). Transmission Electron Microscope analyses of clay minerals revealed that smectite composition corresponds to Al-rich beidellites, which supports the existence of such smectites in peri-Mediterranean soils. Smectite formation was favored by the climate conditions at that time, comprising progressive aridification and the alternation of wet and dry climatic episodes. Diagenesis in these smectites is negligible, further evidencing a detrital origin. However, a closer look at clay mineral associations provides an alternate understanding of clay mineral origin, including the possibility of smectite authigenesis in a Mg-rich paleoenvironment. Furthermore, fibrous clays could have originated in such environments. Relationships between Mg-rich clays and carbonates in Messinian sediments should be a next step to explore further constraints on depositional conditions. Chamley, H., Dunoyer-de-Segonzac, G., & Melieres, F. (1978). Clay minerals in Messinian sediments of the Mediterranean Sea. Initial Reports of the Deep Sea Drilling Project, Vol. 42, Part 1, pp. 389-395. Martinez-Ruiz, F., Comas, M. C., & Alonso, B. (1999). Mineral associations and geochemical indicators in Upper Miocene to Pleistocene sediments in the Alboran Basin. In: Proceedings of the Ocean Drilling Program, Scientific Reports, Vol. 161, pp. 21-37.

  18. Adsorption coefficients for TNT on soil and clay minerals

    NASA Astrophysics Data System (ADS)

    Rivera, Rosángela; Pabón, Julissa; Pérez, Omarie; Muñoz, Miguel A.; Mina, Nairmen

    2007-04-01

    To understand the fate and transport mechanisms of TNT from buried landmines is it essential to determine the adsorption process of TNT on soil and clay minerals. In this research, soil samples from horizons Ap and A from Jobos Series at Isabela, Puerto Rico were studied. The clay fractions were separated from the other soil components by centrifugation. Using the hydrometer method the particle size distribution for the soil horizons was obtained. Physical and chemical characterization studies such as cation exchange capacity (CEC), surface area, percent of organic matter and pH were performed for the soil and clay samples. A complete mineralogical characterization of clay fractions using X-ray diffraction analysis reveals the presence of kaolinite, goethite, hematite, gibbsite and quartz. In order to obtain adsorption coefficients (K d values) for the TNT-soil and TNT-clay interactions high performance liquid chromatography (HPLC) was used. The adsorption process for TNT-soil was described by the Langmuir model. A higher adsorption was observed in the Ap horizon. The Freundlich model described the adsorption process for TNT-clay interactions. The affinity and relative adsorption capacity of the clay for TNT were higher in the A horizon. These results suggest that adsorption by soil organic matter predominates over adsorption on clay minerals when significant soil organic matter content is present. It was found that, properties like cation exchange capacity and surface area are important factors in the adsorption of clayey soils.

  19. Microbial Impacts on Clay Mineral Transformation and Reactivity

    NASA Astrophysics Data System (ADS)

    Dong, H.; Jaisi, D.; Fredrickson, J.; Plymale, A.

    2006-05-01

    Clays and clay minerals are ubiquitous in soils, sedimentary rocks, and pelagic oozes. They play important roles in environmental processes such as nutrient cycling, plant growth, contaminant migration, organic matter maturation, and petroleum production. Iron is a major constituent in clay minerals, and its mobility and stability in different environmental processes is, in part, controlled by the oxidation state. Recent studies have shown that biological reduction of structural Fe(III) in clay minerals can change the physical and chemical properties of clay minerals, such as swelling, cation exchange and fixation capacity, specific surface area, color, and magnetic exchange interactions. As a result of biological reduction of Fe(III), clay minerals also undergo mineral transformations, such as dissolution of smectite and precipitation of illite, siderite and vivianite. These chemical, structural and mineralogical changes of clay minerals have a profound effect on clay mineral reactivity, such as their reactivity with organic and inorganic (i.e., heavy metals and radionuclides) contaminants. Our latest data show that biologically reduced nontronite (a smectite variety) is much more effective in reducing soluble and mobile Tc(VII) to Tc(IV) than unreduced nontronite. The reduced Tc(IV) is insoluble in groundwater and soil and thus is immobile. Biologically reduced nontronite can be prepared by microbially reducing Fe(III) in nontronite by Shewanella putrefaciens in the absence of oxygen. Approximately 30% of structurally Fe(III) can be reduced in this manner. Biogenic Fe(II) can then serve as an electron donor to reduce Tc(VII). Nearly all Fe(II) is available to reduce Tc(VII), with the rate of reduction (typically within weeks) possibly depending on the speciation of Fe(II) (surface sorbed Fe(II) vs. structural Fe(II)). Further investigations are underway to further assess the reversibility of Tc reduction upon exposure to oxygen and to elucidate Tc reduction kinetics. These preliminary results have important implications for in-situ bioremediation efforts, where either chemically or biologically reduced clay minerals can be introduced into a contaminant site for removing heavy metals and radionuclides in groundwater aquifers.

  20. Intercalation of Trichloroethene by Sediment-Associated Clay Minerals

    SciTech Connect

    Matthieu, Donald E.; Brusseau, Mark; Johnson, G. R.; Artiola, J. L.; Bowden, Mark E.; Curry, J. E.

    2013-01-01

    The objective of this research was to examine the potential for intercalation of trichloroethene (TCE) by clay minerals associated with aquifer sediments. Sediment samples were collected from a field site inTucson, AZ. Two widely used Montmorillonite specimen clays were employed as controls. X-ray diffraction, conducted with a controlled-environment chamber, was used to characterize smectite interlayer dspacing for three treatments (bulk air-dry sample, sample mixed with synthetic groundwater, sample mixed with TCE-saturated synthetic groundwater). The results show that the d-spacing measured for the samples treated with TCE-saturated synthetic groundwater are larger (*26%) than those of the untreated samples for all field samples as well as the specimen clays. These results indicate that TCE was intercalated by the clay minerals, which may have contributed to the extensive elution tailing observed in prior miscible-displacement experiments conducted with this sediment.

  1. Fluoride content of clay minerals and argillaceous earth materials

    USGS Publications Warehouse

    Thomas, J., Jr.; Glass, H.D.; White, W.A.; Trandel, R.M.

    1977-01-01

    A reliable method, utilizing a fluoride ion-selective electrode, is described for the determination of fluoride in clays and shales. Interference by aluminum and iron is minimal. The reproducibility of the method is about ??5% at different levels of fluoride concentration. Data are presented for various clay minerals and for the <2-??m fractions of marine and nonmarine clays and shales. Fluoride values range from 44 ppm (0.0044%) for nontronite from Colfax, WA, to 51,800 ppm (5.18%) for hectorite from Hector, CA. In general, clays formed under hydrothermal conditions are relatively high in fluoride content, provided the hydrothermal waters are high in fluoride content. Besides hectorite, dickite from Ouray, CO, was found to contain more than 50 times as much fluoride (6700 ppm) as highly crystalline geode kaolinite (125 ppm). The clay stratum immediately overlying a fluorite mineralized zone in southern Illinois was found to have a higher fluoride content than the same stratum in a nonmineralized zone approximately 1 mile away. Nonmarine shales in contact with Australian coals were found to be lower in fluoride content than were marine shales in contact with Illinois coals. It is believed that, in certain instances, peak shifts on DTA curves of similar clay minerals are the result of significant differences in their fluoride content. ?? 1977.

  2. Immersion Freezing of Clay Minerals and its Time Dependence

    NASA Astrophysics Data System (ADS)

    Hiranuma, N.; Moehler, O.; Bundke, U.; Cziczo, D. J.; Danielczok, A.; Ebert, M.; Garimella, S.; Hoffmann, N.; Kanji, Z. A.; Kiselev, A. A.; Raddatz, M.; Stetzer, O.

    2012-12-01

    Immersion ice nucleation efficiency of clay minerals has been investigated using the AIDA (Aerosol Interaction and Dynamics in the Atmosphere) cloud chamber. Various clay dust samples, including two illite as well as three kaolinite standards, have been examined in the temperature range between 238 K and 255 K. We observed two trends in immersion ice nucleation properties as cloud expansion conditions in the AIDA are varied. First, as previously described in the literature, the supersaturation required for the immersion freezing of clay minerals decreased with decreasing temperature and increasing inferred ice-active surface site densities. Second, the ice nucleation activity of clay minerals strongly depended on the solo-parameter, which is the rate change in temperature (i.e., dNice/dT = ∂Nice/∂t ÷ ∂T/∂t). Further time dependence of ice formation is investigated and discussed as a function of cooling rates, ice nuclei (IN), and aerosol concentrations. Ice residuals collected through a pumped counterflow virtual impactor are examined by electron microprobe analyses to seek the true chemical and physical identity of IN in clay minerals. Brief comparisons of AIDA measurement to the measurements with other ice nucleation chambers (e.g., ETH-PINC, FINCH, and commercially available DMT-SPIN) are also presented.

  3. Enchanted Clays: 44th Annual Meeting of the Clay Minerals Society (June 2007)

    SciTech Connect

    Randall T. Cygan

    2007-06-01

    “Enchanted Clays: 44th Annual Meeting of the Clay Minerals Society” was held in early June 2007 in beautiful and historic Santa Fe, New Mexico, USA. Santa Fe provided an idyllic location in the southwestern United States for the attendees to enjoy technical and social sessions while soaking up the diverse culture and wonderful climate of New Mexico—The Land of Enchantment. The meeting included a large and varied group of scientists, sharing knowledge and ideas, benefitting from technical interactions, and enjoying the wonderful historic and enchanted environs of Santa Fe. Including significant number of international scientists, the meeting was attended by approximately two hundred participants. The meeting included three days of technical sessions (oral and poster presentations), three days of field trips to clay and geological sites of northern New Mexico, and a full day workshop on the stabilization of carbon by clays. Details can be found at the meeting web site: www.sandia.gov/clay.

  4. Triazine adsorption by saponite and beidellite clay minerals.

    PubMed

    Aggarwal, Vaneet; Li, Hui; Teppen, Brian J

    2006-02-01

    We investigated the sorption of three triazine herbicides (atrazine, simazine, and metribuzin) by saponite and beidellite clay minerals saturated with K+, Cs+, Na+, and Ca2+. Saponite clay sorbed a larger fraction of each pesticide from aqueous solution than did beidellite clay. The lower cation-exchange capacity in saponite compared to that in beidellite presumably results in a less crowded interlayer, with more siloxane surface being available for adsorption. Generally, Cs-saturated clays sorbed more triazines than did clays saturated by K+, Na+, or Ca2+. We attribute this to the smaller hydrated radius of Cs+, which again increases the siloxane surface that is available for sorption. Furthermore, the relatively weak hydration of Cs+ reduces the swelling of clay interlayers, thus making sorption domains less hydrated and more receptive to hydrophobic molecules. The Cs-saponite manifested a sorption of more than 1% atrazine by weight above equilibrium concentrations of 6 mg/L, which to our knowledge is the largest sorption of neutral atrazine from water yet reported for an inorganic sorbent. Molecular dynamics simulations indicate that atrazine interacts both with clay basal planes and with multiple cations in the clay interlayer. PMID:16519299

  5. First Direct Detection of Clay Minerals on Mars

    NASA Technical Reports Server (NTRS)

    Singer, R. B.; Owensby, P. D.; Clark, R. N.

    1985-01-01

    Magnesian clays or clay-type minerals were conclusively detected in the martian regolith. Near-IR spectral observations of Mars using the Mauna Kea 2.2-m telescope show weak but definite absorption bands near microns. The absorption band positions and widths match those produced by combined OH stretch and Mg-OH lattice modes and are diagnostic of minerals with structural OH such as clays and amphiboles. Likely candidate minerals include serpentine, talc, hectorite, and sponite. There is no spectral evidence for aluminous hydroxylated minerals. No distinct band occurs at 2.55 microns, as would be expected if carbonates were responsible for the 2.35 micron absorption. High-albedo regions such as Elysium and Utopia have the strongest bands near 2.35 microns, as would be expected for heavily weathered soils. Low-albedo regions such as Iapygia show weaker but distinct bands, consistent with moderate coatings, streaks, and splotches of bright weathered material. In all areas observed, the 2.35-micron absorption is at least three times weaker than would be expected if well-crystallized clay minerals made up the bulk of bright soils on Mars.

  6. [Occurrence relationship between iron minerals and clay minerals in net-like red soils: evidence from X-ray diffraction].

    PubMed

    Yin, Ke; Hong, Han-Lie; Han, Weni; Ma, Yu-Bo; Li, Rong-Biao

    2013-04-01

    The high purity of clay minerals is a key factor to reconstruct the palaeoclimate in clay mineralogy, however, the existence of iron minerals (such as goethite and hematite) and organics lead to the intergrowth of clay minerals and other minerals, producing other mineral impurities in enriched clay minerals. Although the removal of organics in soil sediments has been fully investigated, the occurrence state of iron minerals remains controversial, hindering the preparation of high-purity clay minerals. Therefore, the occurrence relationship of iron minerals and clay minerals in Jiujiang net-like red soils of the middle to lower reaches of the Yangtze River was investigated using the sequential separation method, which provided some implications for the removal of iron minerals in soil sediments. The results indicated that goethite and hematite were mostly absorbed on the surface of hydroxy-interlayered smectite and illite in the form of films, and the rest were absorbed by kaolinite. PMID:23841442

  7. Heteroaggregation of Silver Nanoparticles with Clay Minerals in Aqueous System

    NASA Astrophysics Data System (ADS)

    Liu, J.; Burrow, E.; Hwang, Y.; Lenhart, J.

    2013-12-01

    Nanoparticles are increasingly being used in industrial processes and consumer products that exploit their beneficial properties and improve our daily lives. Nevertheless, they also attract attention when released into natural environment due to their potential for causing adverse effects. The fate and transport of nanoparticles in aqueous systems have been the focus of intense study. However, their interactions with other natural particles have received only limited attention. Clay minerals are ubiquitous in most aquatic systems and their variably charged surfaces can act as deposition sites that can alter the fate and transport of nanoparticles in natural aqueous environments. In this study, we investigated the homoaggregation of silver nanoparticles with different coating layers and their heteroaggregation behavior with clay minerals (illite, kaolinite, montmorillonite) in neutral pH solutions. Silver nanoparticles with a nominal diameter of 80 nm were synthesized with three different surface coating layers: uncoated, citrate-coated and Tween-coated. Illite (IMt-2), kaolinite (KGa-2), and montmorillonite (SWy-2) were purchased from the Clay Mineral Society (Indiana) and pretreated to obtain monocationic (Na-clay) and dicationic (Ca-clay) suspensions before the experiments. The change in hydrodynamic diameter as a function of time was monitored using dynamic light scattering (DLS) measurements in order to evaluate early stage aggregation as a function of electrolyte concentration in both the homo- and heteroaggregation scenarios. A shift in the critical coagulation concentration (CCC) values to lower electrolyte concentrations was observed in binary systems, compared to single silver nanoparticle and clay systems. The results also suggest more rapid aggregation in binary system during the early aggregation stage when compared to the single-particle systems. The behavior of citrate-coated silver nanoparticles was similar to that of the bare particles, while the Tween-coated silver nanoparticles showed high stability in both single and binary systems. There were no significant differences in early stage aggregation kinetics observed inthe Na-clay-nanoparticle or Ca-clay-nanoparticle systems, which suggested that the CCC values of the single Na- or Ca-clay suspensions depend only on the electrolyte concentration, not the original cations on the clay surface. These results provide a basic idea for understanding the heteroaggregation of different silver nanoparticles and clays, which can be utilized in further study of fate and transport of engineered nanoparticles in natural aqueous system.

  8. Removal of diphenhydramine from water by swelling clay minerals.

    PubMed

    Li, Zhaohui; Chang, Po-Hsiang; Jiang, Wei-Teh; Jean, Jiin-Shuh; Hong, Hanlie; Liao, Libing

    2011-08-01

    Frequent detection of pharmaceuticals in surface water and wastewater attracted renewed attention on studying interactions between pharmaceuticals and sludge or biosolids generated from wastewater treatment. Less attention was focused on studying interactions between pharmaceuticals and clay minerals, important soil and sediment components. This research targeted on investigating interactions between diphenhydramine (DPH), an important antihistamine drug, and a montmorillonite, a swelling clay, in aqueous solution. Stoichiometric desorption of exchangeable cations accompanying DPH adsorption confirmed that cation exchange was the most important mechanism of DPH uptake by the swelling clay. When the solution pH was below the pK(a) of DPH, its adsorption on the swelling clay was less affected by pH. Increasing solution pH above the pK(a) value resulted in a decrease in DPH adsorption by the clay. An increase in d(001) spacing at a high DPH loading level suggested interlayer adsorption, thus, intercalation of DPH. The results from this study showed that swelling clays are a good environmental sink for weak acidic drugs like DPH. In addition, the large cation exchange capacity and surface area make the clay a good candidate to remove cationic pharmaceuticals from the effluent of wastewater treatment facilities. PMID:21570085

  9. Picloram and Aminopyralid Sorption to Soil and Clay Minerals

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Aminopyralid sorption data are lacking, and these data are needed to predict off-target transport and plant available herbicide in soil solution. The objective of this research was to determine the sorption of picloram and aminopyralid to five soils and three clay minerals and determine if the pote...

  10. Role of clay minerals in the formation of atmospheric aggregates of Saharan dust

    NASA Astrophysics Data System (ADS)

    Cuadros, Javier; Diaz-Hernandez, José L.; Sanchez-Navas, Antonio; Garcia-Casco, Antonio

    2015-11-01

    Saharan dust can travel long distances in different directions across the Atlantic and Europe, sometimes in episodes of high dust concentration. In recent years it has been discovered that Saharan dust aerosols can aggregate into large, approximately spherical particles of up to 100 μm generated within raindrops that then evaporate, so that the aggregate deposition takes place most times in dry conditions. These aerosol aggregates are an interesting phenomenon resulting from the interaction of mineral aerosols and atmospheric conditions. They have been termed "iberulites" due to their discovery and description from aerosol deposits in the Iberian Peninsula. Here, these aggregates are further investigated, in particular the role of the clay minerals in the aggregation process of aerosol particles. Iberulites, and common aerosol particles for reference, were studied from the following periods or single dust events and locations: June 1998 in Tenerife, Canary Islands; June 2001 to August 2002, Granada, Spain; 13-20 August 2012, Granada; and 1-6 June 2014, Granada. Their mineralogy, chemistry and texture were analysed using X-ray diffraction, electron microprobe analysis, SEM and TEM. The mineral composition and structure of the iberulites consists of quartz, carbonate and feldspar grains surrounded by a matrix of clay minerals (illite, smectite and kaolinite) that also surrounds the entire aggregate. Minor phases, also distributed homogenously within the iberulites, are sulfates and Fe oxides. Clays are apparently more abundant in the iberulites than in the total aerosol deposit, suggesting that iberulite formation concentrates clays. Details of the structure and composition of iberulites differ from descriptions of previous samples, which indicates dependence on dust sources and atmospheric conditions, possibly including anthropic activity. Iberulites are formed by coalescence of aerosol mineral particles captured by precursor water droplets. The concentration of clays in the iberulites is suggested to be the result of higher efficiency for clay capture than for the capture of larger mineral grains. The high hygroscopicity of clay minerals probably causes retention of water in the evaporation stage and some secondary minerals (mainly gypsum) are associated with clays.

  11. Sorption of tylosin on clay minerals.

    PubMed

    Zhang, Qian; Yang, Chen; Huang, Weilin; Dang, Zhi; Shu, Xiaohua

    2013-11-01

    The equilibrium sorption of tylosin (TYL) on kaolinite and montmorillonite was measured at different solution pH using batch reactor systems. The results showed that all the sorption isotherms were nonlinear and that the nonlinearity decreased as the solution pH increased for a given clay. At a specific aqueous concentration, the single-point sorption distribution coefficient (KD) of TYL decreased rapidly as the solution pH increased. A speciation-dependent sorption model that accounted for the contributions of the cationic and neutral forms of TYL fit the data well, suggesting that the sorption may be dominated by both ion exchange and hydrophobic interactions. The isotherm data also fit well to a dual mode model that quantifies the contributions of a site-limiting Langmuir component (ion exchange) and a non-specific linear partitioning component (hydrophobic interactions). X-ray diffraction analyses revealed that the interlayers of montmorillonite were expanded due to the uptake of TYL. TYL molecules likely form a monolayer surface coverage. PMID:24007614

  12. Environmental applications of radiation-induced defects in clay minerals

    NASA Astrophysics Data System (ADS)

    Allard, T.

    2011-12-01

    Radiation effects on clay minerals have been studied over the last 35 years, providing a wealth of information on environmental and geological processes. They have been applied to the reconstruction of past radioelement migrations in the geosphere, the dating of clay minerals from soils or the evolution of the physico-chemical properties under irradiation. All known radiation-induced point defects in clay minerals are detected using Electron Paramagnetic Resonance Spectroscopy. They mostly consist in electron holes located on oxygen atoms of the structure, and can be differentiated through their nature and their thermal stability. For instance, several are associated to a π orbital on a Si-O bond. One defect, namely the A-center, is stable over geological periods at ambiant temperature. These point defects are produced mainly by ionizing radiations. By contrast to point defects, it was shown that electron or heavy ion irradiation easily produces amorphization in smectites. Two main applications of radiation-induced defects in clay minerals are derived : (i) the use of defects as tracers of past radioactivity. In geosystems where the age of the clay can be constrained, migrations of radioelements can be reconstructed in natural analogues of the far field of high level nuclear waste repositories. When the dose rate may be assumed constant over time, the paleodose is used to date clay populations, an approach applied to laterites of the Amazon basin. (ii) The influence of radiation on clay mineral properties that remains poorly documented, although it is an important issue in various domains such as the safety assessment of the high level nuclear waste repositories. In case of a leakage of transuranic elements from the radioactive wasteform, alpha recoil nuclei would amorphize smectite after a period much lower than the disposal lifetime. By contrast, amorphisation from ionizing radiation is unlikely over 1 million years. Furthermore, it was shown that amorphization greatly enhances the dissolution kinetics of smectite, a result that must be taken into account in the safety assessment of engineered barriers.

  13. Ice nucleation efficiency of clay minerals in the immersion mode

    NASA Astrophysics Data System (ADS)

    Pinti, V.; Marcolli, C.; Zobrist, B.; Hoyle, C. R.; Peter, T.

    2012-07-01

    Emulsion and bulk freezing experiments were performed to investigate immersion ice nucleation on clay minerals in pure water, using various kaolinites, montmorillonites, illites as well as natural dust from the Hoggar Mountains in the Saharan region. Differential scanning calorimeter measurements were performed on three different kaolinites (KGa-1b, KGa-2 and K-SA), two illites (Illite NX and Illite SE) and four natural and acid-treated montmorillonites (SWy-2, STx-1b, KSF and K-10). The emulsion experiments provide information on the average freezing behaviour characterized by the average nucleation sites. These experiments revealed one to sometimes two distinct heterogeneous freezing peaks, which suggest the presence of a low number of qualitatively distinct average nucleation site classes. We refer to the peak at the lowest temperature as "standard peak" and to the one occurring in only some clay mineral types at higher temperatures as "special peak". Conversely, freezing in bulk samples is not initiated by the average nucleation sites, but by a very low number of "best sites". The kaolinites and montmorillonites showed quite narrow standard peaks with onset temperatures 238 Kclay minerals strongly depend on the amount of clay mineral present per droplet and on the exact type (location of collection and pre-treatment) of the clay mineral. We suggest that apparently contradictory results obtained by different groups with different setups are indeed in good agreement when only clay minerals of the same type and amount per droplet are compared. The natural sample from the Hoggar Mountains, a region whose dusts have been shown to be composed mainly of illite, showed very similar freezing characteristics (standard and best) to the illites. Relating the concentration of best IN to the dust concentration in the atmosphere suggested that the best IN in the Hoggar sample would be common enough downwind of their source region to account for ambient IN number densities in the temperature range of 250-260 K at least during dust events.

  14. Geochemical dynamics of cesium sorption by selected clay minerals

    SciTech Connect

    Noll, M.R.

    1989-01-01

    This study focuses on the interactions of cesium with selected clay minerals. Cesium is of interest as it is a chief component of high level radioactive waste. Primarily, the thermodynamics and kinetics of Cs exchange reactions were investigated to determine the preference for Cs of a kaolinite, illite, and vermiculite. Thermodynamic studies indicated that Cs was most strongly preferred by Ca saturated clays. Of the three minerals studied, illite proved to be the most effective in adsorbing Cs as indicated by the Vanselow Selectivity Coefficients (k{sub v}). The k{sub v} values for illite ranged from 5.87 to over 10{sup 10}, depending on the mineral and saturating cation. Kinetics experiments proved to be the most interesting. On 2:1 clay minerals (illite and vermiculite), two simultaneous reactions are postulated. The first, and faster of the two reactions, is believed to correspond to Cs adsorption on surface planar sites. The second reaction may be the adsorption of Cs on interlayer and wedge exchange sites. Kaolinite only shows a single reaction since it is a 1:1 clay mineral. Rate coefficients were calculated and the first reaction was found to be on the order of one magnitude greater than the second reaction. The reactions on kaolinite were similar to this faster reaction. Desorption data indicated that the rate of desorption was one or more orders of magnitude less than the corresponding adsorption rate. It is important to note, however, that studies on the effect of temperature indicated that Arrhenius behavior is not followed in many of these experiments. It is postulated that changes in cation radius ratio, or the availability of exchange sites is causing this Anti-Arrhenius behavior. Finally, it is concluded that illite exhibits the greatest preference for the adsorption of Cs.

  15. CO2 adsorption isotherm on clay minerals and the CO2 accessibility into the clay interlayer

    NASA Astrophysics Data System (ADS)

    Gensterblum, Yves; Bertier, Pieter; Busch, Andreas; Rother, Gernot; Krooß, Bernhard

    2013-04-01

    Large-scale CO2 storage in porous rock formations at 1-3 km depth is seen as a global warming mitigation strategy. In this process, CO2 is separated from the flue gas of coal or gas power plants, compressed, and pumped into porous subsurface reservoirs with overlying caprocks (seals). Good seals are mechanically and chemically stable caprocks with low porosity and permeability. They prevent leakage of buoyant CO2 from the reservoir. Caprocks are generally comprised of thick layers of shale, and thus mainly consist of clay minerals. These clays can be affected by CO2-induced processes, such as swelling or dissolution. The interactions of CO2 with clay minerals in shales are at present poorly understood. Sorption measurements in combination scattering techniques could provide fundamental insight into the mechanisms governing CO2-clay interaction. Volumetric sorption techniques have assessed the sorption of supercritical CO2 onto coal (Gensterblum et al., 2010; Gensterblum et al., 2009), porous silica (Rother et al., 2012a) and clays as a means of exploring the potential of large-scale storage of anthropogenic CO2 in geological reservoirs (Busch et al., 2008). On different clay minerals and shales, positive values of excess sorption were measured at gas pressures up to 6 MPa, where the interfacial fluid is assumed to be denser than the bulk fluid. However, zero and negative values were obtained at higher densities, which suggests the adsorbed fluid becomes equal to and eventually less dense than the corresponding bulk fluid, or that the clay minerals expand on CO2 charging. Using a combination of neutron diffraction and excess sorption measurements, we recently deduced the interlayer density of scCO2 in Na-montmorillonite clay in its single-layer hydration state (Rother et al., 2012b), and confirmed its low density, as well as the expansion of the basal spacings. We performed neutron diffraction experiments at the FRMII diffractometer on smectite, kaolinite and illite samples. These confirmed that CO2 enters the interlayer spaces of monohydrated (D2O) smectites exchanged with Ca. The changes were proven to be fully reversible and mainly take place between 0 and 60 bar CO2. For a smectite exchanged with (CuTrien)2+ a decrease in intensity of the basal reflections with pressure was recorded, but no expansion of the basal spacing was observed. For kaolinite, similar changes in intensity upon CO2 addition were observed, but they correspond to a relative decrease of the intensity of the hk reflections. Measurements on illite yielded an unexpected increase in intensity of the basal reflections upon CO2 charging.

  16. Reversibility of soil forming clay mineral reactions induced by plant - clay interactions

    NASA Astrophysics Data System (ADS)

    Barré, P.; Velde, B.

    2012-04-01

    Recent data based upon observations of field experiments and laboratory experiments suggest that changes in phyllosilicate mineralogy, as seen by X-ray diffraction analysis, which is induced by plant action can be reversed in relatively short periods of time. Changes from diagenetic or metamorphic mineral structures (illite and chlorite) to those found in soils (mixed layered minerals in the smectite, hydroxy-interlayer mineral and illites) observed in Delaware Bay salt marsh sediments in periods of tens of years and observed under different biologic (mycorhize) actions in coniferous forests in the soil environment can be found to be reversed under other natural conditions. Reversal of this process (chloritisation of smectitic minerals in soils) has been observed in natural situations over a period of just 14 years under sequoia gigantia. Formation of smectite minerals from illite (potassic mica-like minerals) has been observed to occur under intensive agriculture conditions over periods of 80 years or so under intensive zea mais production. Laboratory experiments using rye grass show that this same process can be accomplished to a somewhat lesser extent after one growing season. However experiments using alfalfa for 30 year growing periods show that much of the illite content of a soil can be reconstituted or even increased. Observations on experiments using zea mais under various fertilizer and mycorhize treatments indicate that within a single growing season potassium can be extracted from the clay (illite layers) but at the end of the season the potassium can be restored to the clay structures and more replaced that extracted. Hence it is clear that the change in clay mineralogy normally considered to be irreversible, illite to smectite or chlorite to smectite observed in soils, is a reversible process where plant systems control the soil chemistry and the soil mineralogy. The changes in clay mineralogy concern mostly the chemical composition of the interlayer ion population of a 2:1 clay structure. However the differences in interlayer ion chemistry give us such mineral names as chloritic hydroxyinterlayered mineral (Mg, OH interlayer), illite (K interlayer), and smectite (essentially hydrated Ca interlayer ions). Extraction of these interlayer ions can be reversed by chemistry engendered by plant regimes.

  17. Geochemical study of evaporite and clay mineral-oxyhydroxide samples from the Waste Isolation Pilot Plant site

    SciTech Connect

    Brookins, D.G.

    1993-06-01

    Samples of clay minerals, insoluble oxyhydroxides, and their host evaporites from the WIPP site have been studied for their major and minor elements abundances, x-ray diffraction characteristics, K-Ar ages, and Rb-Sr ages. This study was undertaken to determine their overall geochemical characteristics and to investigate possible interactions between evaporates and insoluble constituents. The evaporite host material is water-soluble, having Cl/Br ratios typical of marine evaporites, although the Br content is low. Insoluble material (usually a mixture of clay minerals and oxyhydroxide phases) yields very high Cl/Br ratios, possibly because of Cl from admixed halide minerals. This same material yields K/Rb and Th/U ratios in the normal range for shales; suggesting little, if any, effect of evaporite-induced remobilization of U, K, or Rb in the insoluble material. The rare-earth element (REE) data also show normal REE/chondrite (REE/CHON) distribution patterns, supporting the K/Rb and Th/U data. Clay minerals yield K-Ar dates in the range 365 to 390 Ma and a Rb-Sr isochron age of 428 {+-} 7 Ma. These ages are well in excess of the 220- to 230-Ma formational age of the evaporites, and confirm the detrital origin of the clays. The ages also show that any evaporite or clay mineral reactions that might have occurred at or near the time of sedimentation and diagenesis were not sufficient to reset the K-Ar and Rb-Sr systematics of the clay minerals. Further, x-ray data indicate a normal evaporitic assemblage of clay minerals and Fe-rich oxyhydroxide phases. The clay minerals and other insoluble material appear to be resistant to the destructive effects of their entrapment in the evaporites, which suggests that these insoluble materials would be good getters for any radionuclides (hypothetically) released from the storage of radioactive wastes in the area.

  18. Role And Behaviour Of Clay Minerals In Alpine Debris Flows

    NASA Astrophysics Data System (ADS)

    Boivin, P.; Bardou, E.; Pfeiffer, H.

    2004-12-01

    The role of clay minerals is generally considered as negligible in alpine debris flow studies and experiments. This assumption is discussed on the basis of field and experimental data. In two neighbouring alpine catchments, with similar morphology and contrasted geology, the physical, mineralogical and chemical properties of the fine earth (<2mm fraction) of soils, debris flow deposits, and parent materials were compared. The clay minerals (clay and silt size) were extracted and characterized for mineralogy and cation exchange capacity (CEC). Their critical coagulation concentrations (CCC) were determined in laboratory experiments. The soil and surface solutions were sampled and monitored for chemical composition, which were compared to the experimental CCCs. The chemical equilibration time between soil solution and solid phase was tested on saturated paste extracts. It was observed that the fine earth of the debris flow deposits was not representative of the triggering materials in terms of fabric, density, particle size, particle shape and mineralogy. Results show that the particles were rounded, crushed and segregated during the flow. The parent materials were composed of platy particles with a small bulk density suggesting an edge-to edge fabric. It contained phyllosilicates of silt and clay size, coated with transformed organic matter. The deposits were composed of rounded particles with a large bulk density suggesting a close-packed fabric. Compared to the parent materials, the deposits contained a larger amount of large mono-crystalline particles of either quartz or calcite with round shape, and less small platy particles of phyllosilicates. The CEC of the fine earth and of the clay-size and silt-size particles was consequently about two times higher in the parent materials than in the deposits. This was interpreted as the results of two main phenomena, namely (i) the leaching of the suspended colloidal particles out of the deposits during the depositional stage, and (ii) the crushing of the larger non-colloidal particles during the flow. The CCCs of the extracted clay minerals were close to CCC values reported in the literature for similar minerals. The solutions reached equilibrium with the solid phases within 20min of equilibration time in the laboratory. The field solid phases and surface waters were at equilibrium with the solid phases. There concentrations were only slightly higher than the CCCs, thus allowing for flocculation of the minerals. However, it is most probable that the concentrations of the soil and surface waters drop largely below the CCC values during snow-melt or heavy rainfall. Furthermore, the CCCs were determined in the lab without shaking energy. During the flow in the field, the phyllosilicates will be more easily dispersed because additional shaking energy sharply increases the CCC.

  19. Ice nucleation efficiency of clay minerals in the immersion mode

    NASA Astrophysics Data System (ADS)

    Pinti, V.; Marcolli, C.; Zobrist, B.; Hoyle, C. R.; Peter, T.

    2012-01-01

    Emulsion and bulk freezing experiments were performed to investigate immersion ice nucleation on clay minerals in pure water, using various kaolinites, montmorillonites, illites as well as natural dust from the Hoggar Mountains in the Saharan region. DSC (differential scanning calorimeter) measurements were performed on the kaolinites KGa-1b and KGa-2 from the Clay Mineral Society and kaolinite from Sigma-Aldrich; the montmorillonites SWy-2 and STx-1b from the Clay Mineral Society and the acid treated montmorillonites KSF and K-10 from Sigma Aldrich; the illites NX and SE from Arginotec. The emulsion experiments provide information on the average freezing behaviour characterized by the average nucleation sites. These experiments revealed one to two distinct heterogeneous freezing peaks, which suggest the presence of a low number of qualitatively distinct average nucleation site classes. We refer to the peak at the lowest temperature as "standard peak" and to the one at higher temperatures as "special peak". Conversely, freezing in bulk samples is not initiated by the average nucleation sites, but by a very low number of "best sites". The kaolinites showed quite narrow standard peaks with onset temperatures 239 K < Tonstd < 242 K and best sites with averaged median freezing temperature Tmedbest = 257 K. Only the kaolinite from Sigma Aldrich featured a special peak with freezing onset at 248 K. The illites showed broad standard peaks with freezing onsets at 244 K < Tonstd < 246 K and best sites with averaged median freezing temperature Tmedbest = 262 K. Montmorillonites had standard peaks with onsets 238 K < Tonstd < 240 K and best sites with Tmedbest=257 K. SWy-2, M K10, and KSF featured special peaks with onsets at Tonspcl=247, 240, and 242 K, respectively. M K10 and KSF both from Sigma Aldrich had less intense standard peaks compared to the ones from the Clay Mineral Society suggesting that a fraction of the standard sites are lost by the acid treatment. The acid treatment had however, no evident effect on best sites. Our investigations demonstrate that immersion freezing temperatures of clay minerals strongly depend on the amount of clay mineral present per droplet and on the exact type (location of collection and pre-treatment) of the clay mineral. We suggest that apparently contradictory results obtained by different groups with different setups can indeed be brought into good agreement when only clay minerals of the same type and amount per droplet are compared. The natural sample from the Hoggar Mountains, a region whose dusts have been shown to be composed mainly of illite, showed very similar freezing characteristics to the illites with freezing peak onsets 247 K < Tonstd < 248 K for the average and Tmedbest = 261 K for the best sites. Relating the concentration of best IN to the dust concentration in the atmosphere suggested that the best IN in the Hoggar sample would be common enough downwind of their source region to account for ambient IN number densities in the temperature range of 250-260 K at least during dust events.

  20. Deposition kinetics of MS2 bacteriophages on clay mineral surfaces.

    PubMed

    Tong, Meiping; Shen, Yun; Yang, Haiyan; Kim, Hyunjung

    2012-04-01

    The deposition of bacteriophage MS2 on bare and clay-coated silica surfaces was examined in both monovalent (NaCl) and divalent (CaCl(2) and MgCl(2)) solutions under a wide range of environmentally relevant ionic strength and pH conditions by utilizing a quartz crystal microbalance with dissipation (QCM-D). Two types of clay, bentonite and kaolinite, were concerned in this study. To better understand MS2 deposition mechanisms, QCM-D data were complemented by zeta potentials measurements and Derjaguin-Landau-Verwey-Overbeek (DLVO) interaction forces calculation. In both monovalent and divalent solutions, deposition efficiencies of MS2 increased with increasing ionic strength both on bare and clay-coated surfaces, which agreed with the trends of interaction forces between MS2 and solid surface and thus was consistent with DLVO theory. The presence of divalent ions (Ca(2+) and Mg(2+)) in solutions greatly increased virus deposition on both silica and clay deposited surfaces. Coating silica surfaces with clay minerals, either kaolinite or bentonite, could significantly increase MS2 deposition. PMID:22221455

  1. [The interaction of Bradyrhizobium japonicum with clay minerals].

    PubMed

    Kurdish, I K; Drobit'ko, A V; Shevchenko, T V; Mar'iushkin, V F

    2000-01-01

    It is shown that such clay minerals as palygorskite and montmorillonite stimulate growth activity of Bradyrhizobium japonicum. The bacteria come into contact with the above minerals. Granulated preparations of rhizobia have been developed on the basis of the results obtained. These preparations are characterized by the high yield of viable cells and a possibility of long-term storage. The use of montmorillonite in production of granulated preparations provides the higher yield of viable bacteria in the preparations and stability of their composition under long-term storage. PMID:10872286

  2. Diagenesis and clay mineral formation at Gale Crater, Mars

    SciTech Connect

    Bridges, J. C.; Schwenzer, S. P.; Leveille, R.; Westall, F.; Wiens, R. C.; Mangold, N.; Bristow, T.; Edwards, P.; Berger, G.

    2015-01-18

    The Mars Science Laboratory rover Curiosity found host rocks of basaltic composition and alteration assemblages containing clay minerals at Yellowknife Bay, Gale Crater. On the basis of the observed host rock and alteration minerals, we present results of equilibrium thermochemical modeling of the Sheepbed mudstones of Yellowknife Bay in order to constrain the formation conditions of its secondary mineral assemblage. Building on conclusions from sedimentary observations by the Mars Science Laboratory team, we assume diagenetic, in situ alteration. The modeling shows that the mineral assemblage formed by the reaction of a CO₂-poor and oxidizing, dilute aqueous solution (Gale Portage Water) in an open system with the Fe-rich basaltic-composition sedimentary rocks at 10–50°C and water/rock ratio (mass of rock reacted with the starting fluid) of 100–1000, pH of ~7.5–12. Model alteration assemblages predominantly contain phyllosilicates (Fe-smectite, chlorite), the bulk composition of a mixture of which is close to that of saponite inferred from Chemistry and Mineralogy data and to that of saponite observed in the nakhlite Martian meteorites and terrestrial analogues. To match the observed clay mineral chemistry, inhomogeneous dissolution dominated by the amorphous phase and olivine is required. We therefore deduce a dissolving composition of approximately 70% amorphous material, with 20% olivine, and 10% whole rock component.

  3. Diagenesis and clay mineral formation at Gale Crater, Mars

    DOE PAGESBeta

    Bridges, J. C.; Schwenzer, S. P.; Leveille, R.; Westall, F.; Wiens, R. C.; Mangold, N.; Bristow, T.; Edwards, P.; Berger, G.

    2015-01-18

    The Mars Science Laboratory rover Curiosity found host rocks of basaltic composition and alteration assemblages containing clay minerals at Yellowknife Bay, Gale Crater. On the basis of the observed host rock and alteration minerals, we present results of equilibrium thermochemical modeling of the Sheepbed mudstones of Yellowknife Bay in order to constrain the formation conditions of its secondary mineral assemblage. Building on conclusions from sedimentary observations by the Mars Science Laboratory team, we assume diagenetic, in situ alteration. The modeling shows that the mineral assemblage formed by the reaction of a CO₂-poor and oxidizing, dilute aqueous solution (Gale Portage Water)more » in an open system with the Fe-rich basaltic-composition sedimentary rocks at 10–50°C and water/rock ratio (mass of rock reacted with the starting fluid) of 100–1000, pH of ~7.5–12. Model alteration assemblages predominantly contain phyllosilicates (Fe-smectite, chlorite), the bulk composition of a mixture of which is close to that of saponite inferred from Chemistry and Mineralogy data and to that of saponite observed in the nakhlite Martian meteorites and terrestrial analogues. To match the observed clay mineral chemistry, inhomogeneous dissolution dominated by the amorphous phase and olivine is required. We therefore deduce a dissolving composition of approximately 70% amorphous material, with 20% olivine, and 10% whole rock component.« less

  4. Diagenesis and clay mineral formation at Gale Crater, Mars

    PubMed Central

    Bridges, J C; Schwenzer, S P; Leveille, R; Westall, F; Wiens, R C; Mangold, N; Bristow, T; Edwards, P; Berger, G

    2015-01-01

    The Mars Science Laboratory rover Curiosity found host rocks of basaltic composition and alteration assemblages containing clay minerals at Yellowknife Bay, Gale Crater. On the basis of the observed host rock and alteration minerals, we present results of equilibrium thermochemical modeling of the Sheepbed mudstones of Yellowknife Bay in order to constrain the formation conditions of its secondary mineral assemblage. Building on conclusions from sedimentary observations by the Mars Science Laboratory team, we assume diagenetic, in situ alteration. The modeling shows that the mineral assemblage formed by the reaction of a CO2-poor and oxidizing, dilute aqueous solution (Gale Portage Water) in an open system with the Fe-rich basaltic-composition sedimentary rocks at 10–50°C and water/rock ratio (mass of rock reacted with the starting fluid) of 100–1000, pH of ∽7.5–12. Model alteration assemblages predominantly contain phyllosilicates (Fe-smectite, chlorite), the bulk composition of a mixture of which is close to that of saponite inferred from Chemistry and Mineralogy data and to that of saponite observed in the nakhlite Martian meteorites and terrestrial analogues. To match the observed clay mineral chemistry, inhomogeneous dissolution dominated by the amorphous phase and olivine is required. We therefore deduce a dissolving composition of approximately 70% amorphous material, with 20% olivine, and 10% whole rock component. PMID:26213668

  5. Diagenesis and clay mineral formation at Gale Crater, Mars

    NASA Astrophysics Data System (ADS)

    Bridges, J. C.; Schwenzer, S. P.; Leveille, R.; Westall, F.; Wiens, R. C.; Mangold, N.; Bristow, T.; Edwards, P.; Berger, G.

    2015-01-01

    Mars Science Laboratory rover Curiosity found host rocks of basaltic composition and alteration assemblages containing clay minerals at Yellowknife Bay, Gale Crater. On the basis of the observed host rock and alteration minerals, we present results of equilibrium thermochemical modeling of the Sheepbed mudstones of Yellowknife Bay in order to constrain the formation conditions of its secondary mineral assemblage. Building on conclusions from sedimentary observations by the Mars Science Laboratory team, we assume diagenetic, in situ alteration. The modeling shows that the mineral assemblage formed by the reaction of a CO2-poor and oxidizing, dilute aqueous solution (Gale Portage Water) in an open system with the Fe-rich basaltic-composition sedimentary rocks at 10-50°C and water/rock ratio (mass of rock reacted with the starting fluid) of 100-1000, pH of ~7.5-12. Model alteration assemblages predominantly contain phyllosilicates (Fe-smectite, chlorite), the bulk composition of a mixture of which is close to that of saponite inferred from Chemistry and Mineralogy data and to that of saponite observed in the nakhlite Martian meteorites and terrestrial analogues. To match the observed clay mineral chemistry, inhomogeneous dissolution dominated by the amorphous phase and olivine is required. We therefore deduce a dissolving composition of approximately 70% amorphous material, with 20% olivine, and 10% whole rock component.

  6. Studies of clays and clay minerals using x-ray powder diffraction and the Rietveld method

    SciTech Connect

    Bish, D.L.

    1993-09-01

    The Rietveld method was originally developed (Rietveld, 1967, 1969) to refine crystal structures using neutron powder diffraction data. Since then, the method has been increasingly used with X-ray powder diffraction data, and today it is safe to say that this is the most common application of the method. The method has been applied to numerous natural and synthetic materials, most of which do not usually form crystals large enough for study with single-crystal techniques. It is the ability to study the structures of materials for which sufficiently large single crystals do not exist that makes the method so powerful and popular. It would thus appear that the method is ideal for studying clays and clay minerals. In many cases this is true, but the assumptions implicit in the method and the disordered nature of many clay minerals can limit titsapplicability. This chapter will describe the Rietveld method, emphasizing the assumptions important for the study of disordered materials, and it will outline the potential applications of the method to these minerals. These applications include, in addition to the refinement of crystal structures, quantitative analysis of multicomponent mixtures, analysis of peak broadening, partial structure solution, and refinement of unit-cell parameters.

  7. Bioreduction of Fe-bearing clay minerals and their reactivity toward pertechnetate (Tc-99)

    SciTech Connect

    Bishop, Michael E.; Dong, Hailiang; Kukkadapu, Ravi K.; Liu, Chongxuan; Edelmann, Richard E.

    2011-07-01

    99Technetium (99Tc) is a fission product of uranium-235 and plutonium-239 and poses a high environmental hazard due to its long half-life (t1/2 = 2.13 x 105 y), abundance in nuclear wastes, and environmental mobility under oxidizing conditions [i.e., Tc(VII)]. Under reducing conditions, Tc(VII) can be reduced to insoluble Tc(IV). Ferrous iron [Fe(II)], either in aqueous form or in mineral form, has been used to reduce Tc(VII) to Tc(IV). However, the reactivity of Fe(II) from clay minerals, other than nontronite, toward immobilization of Tc(VII) and its role in retention of reduced Tc(IV) have not been investigated. In this study the reactivity of a suite of clay minerals toward Tc(VII) reduction and immobilization was evaluated. The clay minerals chosen for this study included five members in the smectite-illite (S-I) series, (montmorillonite, nontronite, rectorite, mixed layered I-S, and illite), chlorite, and palygorskite. Fe-oxides were removed from these minerals with a modified dithionite-citrate-bicarbonate (DCB) procedure. The total Fe content of these clay minerals, after Fe-oxide removal, ranged from 0.7 to 30.4% by weight, and the Fe(III)/Fe(total) ratio ranged from 44.9 to 98.5%. X-ray diffraction (XRD) and Mössbauer spectroscopy results showed that after Fe oxide removal the clay minerals were free of Fe-oxides. Scanning electron microscopy (SEM) revealed that little dissolution occurred during the DCB treatment. Bioreduction experiments were performed in bicarbonate buffer (pH-7) with Fe(III) in the clay minerals as the sole electron acceptor, lactate as the sole electron donor, and Shewanella Putrifaciens CN32 cells as mediators. In select tubes, anthraquinone-2,6-disulfate (AQDS) was added as electron shuttle to facilitate electron transfer. The extent of Fe(III) bioreduction was the highest for chlorite (~43 wt%) and the lowest for palygorskite (~4.17 wt%). In the S-I series, NAu-2 was the most reducible (~31 %) and illite the least (~0.4 %). The extent and initial rate of bioreduction were positively correlated with the percent smectite in the S-I series (i.e., layer expandability). Fe(II) in the bioreduced clay minerals subsequently was used to reduce Tc(VII) to Tc(IV) in PIPES buffer. Similar to the trend of bioreduction, in the S-I series, reduced smectite showed the highest reactivity toward Tc(VII), and reduced illite exhibited the least. The initial rate of Tc(VII) reduction, after normalization to clay and Fe(II) concentrations, was positively correlated with the percent smectite in the S-I series. Fe(II) in chlorite and palygorskite was also reactive toward Tc(VII) reduction. These data demonstrate that crystal chemical parameters (layer expandability, Fe and Fe(II) contents, and surface area etc.) play important roles in controlling the extent and rate of bioreduction and the reactivity toward Tc(VII) reduction. Reduced Tc(IV) resides within clay mineral matrix, and this association could minimize any potential of reoxidation over long term.

  8. Program and Abstracts for Clay Minerals Society 28th Annual Meeting

    NASA Technical Reports Server (NTRS)

    1991-01-01

    This volume contains abstracts that were accepted for presentation at the annual meeting. Some of the main topics covered include: (1) fundamental properties of minerals and methods of mineral analysis; (2) surface chemistry; (3) extraterrestrial clay minerals; (4) geothermometers and geochronometers; (5) smectite, vermiculite, illite, and related reactions; (6) soils and clays in environmental research; (7) kaolinite, halloysite, iron oxides, and mineral transformations; and (8) clays in lakes, basins, and reservoirs.

  9. Evidence for microbial liberation of structurally-coordinated iron in clay minerals as a nutrient source in the world ocean

    NASA Astrophysics Data System (ADS)

    Metcalfe, K. S.; Gaines, R. R.; Trang, J.; Scott, S.; Crane, E. J.; Lackey, J.; Prokopenko, M. G.; Berelson, W.

    2012-12-01

    Clay minerals are the most abundant materials found at the surface of earth and they are the primary constituents of marine sediments. Iron, a limiting nutrient in many marine settings, is a common constituent of clay minerals. Recent in vitro experimental evidence has shown that lab cultures of Fe-reducing bacteria are able to utilize structurally-bound Fe from the crystal lattice of nontronite, an uncommon and particularly Fe-rich (> 12 wt.%) smectitie. Reduction of structurally-coordinated Fe results in both the liberation of Fe(II) to solution, where it is available for other biotic processes, as well as the transformation of smectite to illite. However, it remains unclear: 1. whether Fe-reducers are able to access structurally coordinated Fe found at low wt.% in common clay minerals; and 2. if naturally occuring populations of Fe-reducers are able to reduce structurally coordinated Fe as are some lab strains. In order to address these questions, we conducted in vitro experiments using a suite of sixteen clay minerals with low (0.8 wt.%) to high (13.9 wt.%) Fe concentrations. Clays were treated with Na-dithionite solution to remove surface-bound Fe, isolating for study Fe sourced from within the clay crystal lattice. Experimental evidence clearly indicates that, under in vitro conditions, Fe(III) bound in common clay minerals is available for reduction by the lab strain Shewanella oneidensis MR-1 as well as by naturally-occuring consortia of Fe-reducers cultured from the San Pedro and Santa Monica Basins. Our findings suggest that common clay minerals may represent a large and previously unrecognized pool of bioavailable Fe in the world ocean that contributes significantly to biogeochemical cycling of Fe and C.

  10. Report on "Methodologies for Investigating Microbial-Mineral Interactions: A Clay Minerals Society Short Course"

    SciTech Connect

    Patricia A. Maurice

    2010-02-08

    A workshop entitled, “Methods of Investigating Microbial-Mineral Interactions,” was held at the Clay Minerals Society meeting at the Pacific Northwest National Laboratory in Richland, WA on June 19, 2004. The workshop was organized by Patricia A. Maurice (University of Notre Dame) and Lesley A. Warren (McMaster University, CA). Speakers included: Dr. P. Bennett, Dr. J. Fredrickson (PNNL), Dr. S. Lower (Ohio State University), Dr. P. Maurice, Dr. S. Myneni (Princeton University), Dr. E. Shock (Arizona State), Dr. M. Tien (Penn State), Dr. L. Warren, and Dr. J. Zachara (PNNL). There were approximately 75 attendees at the workshop, including more than 20 students. A workshop volume was published by the Clay Minerals Society [Methods for Study of Microbe-Mineral Interactions (2006), CMS Workshop Lectures, vol. 14
(Patricia A. Maurice and Leslie A. Warren, eds.) ISBN 978-1-881208-15-0, 166 pp.

  11. Aqueous suspensions of natural swelling clay minerals. 2. Rheological characterization.

    PubMed

    Paineau, Erwan; Michot, Laurent J; Bihannic, Isabelle; Baravian, Christophe

    2011-06-21

    We report in this article a comprehensive investigation of the viscoelastic behavior of different natural colloidal clay minerals in aqueous solution. Rheological experiments were carried out under both dynamic and steady-state conditions, allowing us to derive the elasticity and yield stress. Both parameters can be renormalized for all sizes, ionic strength, and type of clay using in a first approach only the volume of the particles. However, applying such a treatment to various clays of similar shapes and sizes yields differences that can be linked to the repulsion strength and charge location in the swelling clays. The stronger the repulsive interactions, the better the orientation of clay particles in flows. In addition, a master linear relationship between the elasticity and yield stress whose value corresponds to a critical deformation of 0.1 was evidenced. Such a relationship may be general for any colloidal suspension of anisometric particles as revealed by the analysis of various experimental data obtained on either disk-shaped or lath- and rod-shaped particles. The particle size dependence of the sol-gel transition was also investigated in detail. To understand why suspensions of larger particles gel at a higher volume fraction, we propose a very simplified view based on the statistical hydrodynamic trapping of a particle by an another one in its neighborhood upon translation and during a short period of time. We show that the key parameter describing this hydrodynamic trapping varies as the cube of the average diameter and captures most features of the sol-gel transition. Finally, we pointed out that in the high shear limit the suspension viscosity is still closely related to electrostatic interactions and follows the same trends as the viscoelastic properties. PMID:21591697

  12. Mineral carbonation of gaseous carbon dioxide using a clay-hosted cation exchange reaction.

    PubMed

    Kang, Il-Mo; Roh, Ki-Min

    2013-01-01

    The mineral carbonation method is still a challenge in practical application owing to: (1) slow reaction kinetics, (2) high reaction temperature, and (3) continuous mineral consumption. These constraints stem from the mode of supplying alkaline earth metals through mineral acidification and dissolution. Here, we attempt to mineralize gaseous carbon dioxide into calcium carbonate, using a cation exchange reaction of vermiculite (a species of expandable clay minerals). The mineralization is operated by draining NaCI solution through vermiculite powders and continuously dropping into the pool of NaOH solution with CO2 gas injected. The mineralization temperature is regulated here at 293 and 333 K for 15 min. As a result of characterization, using an X-ray powder diffractometer and a scanning electron microscopy, two types of pure CaCO3 polymorphs (vaterite and calcite) are identified as main reaction products. Their abundance and morphology are heavily dependent on the mineralization temperature. Noticeably, spindle-shaped vaterite, which is quite different from a typical vaterite morphology (polycrystalline spherulite), forms predominantly at 333 K (approximately 98 wt%). PMID:24617079

  13. Radiolysis of alanine adsorbed in a clay mineral

    SciTech Connect

    Aguilar-Ovando, Ellen Y.; Negron-Mendoza, Alicia

    2013-07-03

    Optical activity in molecules is a chemical characteristic of living beings. In this work, we examine the hypothesis of the influence of different mineral surfaces on the development of a specific chirality in organic molecules when subjected to conditions simulating the primitive Earth during the period of chemical evolution. By using X-ray diffraction techniques and HPLC/ELSD to analyze aqueous suspensions of amino acids adsorbed on minerals irradiated in different doses with a cobalt-60 gamma source, the experiments attempt to prove the hypothesis that some solid surfaces (like clays and meteorite rocks) may have a concentration capacity and protective role against external sources of ionizing radiation (specifically {gamma}-ray) for some organic compounds (like some amino acids) adsorbed on them. Preliminary results show a slight difference in the adsorption and radiolysis of the D-and L-alanine.

  14. Radiolysis of alanine adsorbed in a clay mineral

    NASA Astrophysics Data System (ADS)

    Aguilar-Ovando, Ellen Y.; Negrón-Mendoza, Alicia

    2013-07-01

    Optical activity in molecules is a chemical characteristic of living beings. In this work, we examine the hypothesis of the influence of different mineral surfaces on the development of a specific chirality in organic molecules when subjected to conditions simulating the primitive Earth during the period of chemical evolution. By using X-ray diffraction techniques and HPLC/ELSD to analyze aqueous suspensions of amino acids adsorbed on minerals irradiated in different doses with a cobalt-60 gamma source, the experiments attempt to prove the hypothesis that some solid surfaces (like clays and meteorite rocks) may have a concentration capacity and protective role against external sources of ionizing radiation (specifically γ-ray) for some organic compounds (like some amino acids) adsorbed on them. Preliminary results show a slight difference in the adsorption and radiolysis of the D-and L-alanine.

  15. Role of clay minerals in the transportation of iron

    USGS Publications Warehouse

    Carroll, D.

    1958-01-01

    The clay minerals have iron associated with them in several ways: 1. (1) as an essential constituent 2. (2) as a minor constituent within the crystal lattice where it is in isomorphous substitution and 3. (3) as iron oxide on the surface of the mineral platelets. Nontronite, "hydromica," some chlorites, vermiculite, glauconite and chamosite contain iron as an essential constituent. Kaolinite and halloysite have no site within the lattice for iron, but in certain environments iron oxide (goethite or hematite) is intimately associated as a coating on the micelles. Analyses of clay minerals show that the content of Fe2O3 varies: 29 per cent (nontronite), 7??3 per cent (griffithite), 4.5 per cent ("hydromica"), 5.5 per cent (chlorite), 4 per cent (vermiculite) and 18 per cent (glauconite). The FeO content is: 40 per cent (chamosite), 7.8 per cent (griffithite), 1-2 per cent ("hydromica"), 3 per cent (glauconite) and 2 per cent (chlorite). The iron associated with the clay minerals remains stable in the environment in which the minerals occur, but if either pH or Eh or both are changed the iron may be affected. Change of environment will cause: 1. (1) removal of iron by reduction of Fe3+ to Fe2+; 2. (2) ion-exchange reactions; 3. (3) instability of the crystal lattice. Experiments using bacterial activity to produce reducing conditions with kaolinite and halloysite coated with iron oxides and with nontronite in which ferric iron is in the octahedral position within the lattice showed that ferric oxide is removed at Eh +0??215 in fresh water and at Eh +0.098 in sea water. Hematite, goethite, and indefinite iron oxides were removed at different rates. Red ferric oxides were changed to black indefinite noncrystalline ferrous sulphide at Eh -0.020 but reverted to ferric oxide under oxidizing conditions. Nontronite turned bright green under reducing conditions and some of the ferrous iron remained within the lattice on a return to oxidizing conditions. Bacterial activity seems to be necessary for maintaining reducing conditions in the environments studied. ?? 1958.

  16. Towards an understanding of the role of clay minerals in crude oil formation, migration and accumulation

    NASA Astrophysics Data System (ADS)

    Wu, Lin Mei; Zhou, Chun Hui; Keeling, John; Tong, Dong Shen; Yu, Wei Hua

    2012-12-01

    This article reviews progress in the understanding of the role of clay minerals in crude oil formation, migration and accumulation. Clay minerals are involved in the formation of kerogen, catalytic cracking of kerogen into petroleum hydrocarbon, the migration of crude oil, and the continued change to hydrocarbon composition in underground petroleum reservoirs. In kerogen formation, clay minerals act as catalysts and sorbents to immobilize organic matter through ligand exchange, hydrophobic interactions and cation bridges by the mechanisms of Maillard reactions, polyphenol theory, selective preservation and sorptive protection. Clay minerals also serve as catalysts in acid-catalyzed cracking of kerogen into petroleum hydrocarbon through Lewis and Brnsted acid sites on the clay surface. The amount and type of clay mineral affect the composition of the petroleum. Brnsted acidity of clay minerals is affected by the presence and state of interlayer water, and displacement of this water is a probable driver in crude oil migration from source rocks. During crude oil migration and accumulation in reservoirs, the composition of petroleum is continually modified by interaction with clay minerals. The clays continue to function as sorbents and catalysts even while they are being transformed by diagenetic processes. The detail of chemical interactions and reaction mechanisms between clay minerals and crude oil formation remains to be fully explained but promises to provide insights with broader application, including catalytic conversion of biomass as a source of sustainable energy into the future.

  17. Kinetic Study of Denatonium Sorption to Smectite Clay Minerals

    PubMed Central

    Crosson, Garry S.; Sandmann, Emily

    2013-01-01

    Abstract The denatonium cation, as a benzoate salt, is the most bitter cation known to modern society and is frequently added to consumer products to reduce accidental and intentional consumption by humans and animals. Denatonium can enter the environment by accidental discharges, potentially rendering water supplies undrinkable. Interactions of denatonium with soil components (i.e., smectite minerals) ultimately control the environmental fate of denatonium, but the current literature is devoid of studies that evaluate denatonium sorption to smectite minerals. This study investigated the mechanism and kinetics of denatonium sorption to smectite clay minerals as a function of smectite type, temperature, pH and ionic strength. Uptake by synthetic mica montmorillonite (Syn-1), Wyoming montmorillonite (SWy-2), and Texas montmorillonite (STx-1b) at 305K was rapid, with equilibrium being reached within 2 min for all clays. Complete removal of denatonium was observed for STx-1b at pH 6.9, while partial removal was observed for Syn-1 and SWy-2. Kinetic behavior of SWy-2 and Syn-1 is consistent with a pseudo–second-order model at 305K. An activation energy of +25.9 kJ/mol was obtained for sorption to Syn-1 and was independent of temperature between 286K and 338K. Activation-free energy (ΔG*), activation enthalpy (ΔH*), and activation entropy (ΔS*) for Syn-1 were found to be +62.91 kJ/mol, +23.36 kJ/mol, and −0.130 kJ/(K·mol), respectively. Sorption capacities at pH 3.6, 6.9, and 8.2 were constant at 1.3×10−2 g denatonium/g clay; however, the kinetic rate constant increased by 56%, going from acidic to basic solution conditions. Distribution coefficients were negatively correlated with ionic strength, suggesting cation exchange. Collectively, results suggested that smectite minerals can serve as efficient sinks for denatonium cations. This is much-needed information for agencies developing regulations regarding denatonium usage and for water treatment professionals who may ultimately have to treat denatonium-impacted water supplies. PMID:23781128

  18. Microbial reduction of structurally-coordinated iron in common clay minerals

    NASA Astrophysics Data System (ADS)

    Gaines, R. R.; Scott, S.; Crane, E.; Lackey, J.

    2009-12-01

    Experimental evidence has demonstrated the capacity of some iron reducing bacteria to reduce structurally bound Fe(III) within the crystal lattice of iron-rich smectite clays, releasing dissolved Fe(II) to solution. Here, we present experimental data which suggest that a large pool of lattice-bound iron in marine sediments is available for microbial reduction, and that this microbially-mediated process may constitute a major flux of iron from the geosphere to the biosphere. Prior studies have demonstrated that the Fe-reducing bacterium Shewanella is capable of reducing structurally-coordinated iron from the clay mineral nontronite, a smectite that is unusually iron rich, but is rare in natural settings. Clay minerals are the most abundant materials found at Earth’s surface, but it has remained unclear whether structurally-bound iron in common clay minerals is available for biological processes. It has also remained unclear whether microbial consortia in marine sediments are capable of structural iron reduction as is the lab strain Shewanella. To investigate the potential for microbial reduction of structurally bound iron in common clay minerals, four different clay minerals with iron contents ranging from low (0.8 wt.%; smectite-illite mixed layer ICSz-1) to high (13.9 wt.%; nontronite NAu-1) were exposed to the iron reducer Shewanella oneidensis MR-1 and also to an unknown iron reducing microorganism(s) cultured from anaerobic marine sediments of the San Pedro Basin. Control samples of each mineral were exposed to microwave-killed bacterial cells. After time increments ranging from 7 to 120 days, the degree of structural Fe-reduction in each sample was assessed by measuring the concentration of Fe(II) in solution. Microbially-induced changes in mineralogy were characterized using X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. The concentration of Fe(II) in solution was observed to increase in all samples. X-ray diffraction patterns for each mineral show a pronounced decline in the crystallinity and abundance of smectite with increasing exposure time, as evidenced by broadening and collapse of the smectite 001 peak. The relative intensity of both illite and quartz peaks increased with increasing exposure time, indicating the production of these phases as expected reaction byproducts. SEM imaging and elemental mapping reveals the presence of sub-micron, highly crystalline sheet silicates that correspond with positive potassium anomalies and are interpreted as neoformed illite. Fe(II) concentration in solution and mineralogical transformations produced by iron reducing organism(s) cultured from San Pedro Basin sediments were closely comparable to those produced by Shewanella oneidensis MR-1 for each set of mineral samples. This evidence suggests that iron contained in relatively low proportions in common sheet silicates in marine sediments is available for microbial reduction, and that this process may play a significant role in the marine iron cycle.

  19. The role of clay minerals in the preservation of organic matter in sediments of qinghai lake, NW China

    USGS Publications Warehouse

    Yu, B.; Dong, H.; Jiang, H.; Lv, G.; Eberl, D.; Li, S.; Kim, J.

    2009-01-01

    The role of saline lake sediments in preserving organic matter has long been recognized. In order to further understand the preservation mechanisms, the role of clay minerals was studied. Three sediment cores, 25, 57, and 500 cm long, were collected from Qinghai Lake, NW China, and dissected into multiple subsamples. Multiple techniques were employed, including density fractionation, X-ray diffraction, scanning and transmission electron microscopy (SEM and TEM), total organic carbon (TOC) and carbon compound analyses, and surface area determination. The sediments were oxic near the water-sediment interface, but became anoxic at depth. The clay mineral content was as much as 36.8%, consisting mostly of illite, chlorite, and halloysite. The TEM observations revealed that organic matter occurred primarily as organic matter-clay mineral aggregates. The TOC and clay mineral abundances are greatest in the mid-density fraction, with a positive correlation between the TOC and mineral surface area. The TOC of the bulk sediments ranges from 1 to 3% with the non-hydrocarbon fraction being predominant, followed by bitumen, saturated hydrocarbon, aromatic hydrocarbons, and chloroform-soluble bitumen. The bimodal distribution of carbon compounds of the saturated hydrocarbon fraction suggests that organic matter in the sediments was derived from two sources: terrestrial plants and microorganisms/algae. Depthrelated systematic changes in the distribution patterns of the carbon compounds suggest that the oxidizing conditions and microbial abundance near the water-sediment interface promote degradation of labile organic matter, probably in adsorbed form. The reducing conditions and small microbial biomass deeper in the sediments favor preservation of organic matter, because of the less labile nature of organic matter, probably occurring within clay mineral-organic matter aggregates that are inaccessible to microorganisms. These results have important implications for our understanding of mechanisms of organic matter preservation in saline lake sediments.

  20. Surficial clay mineral distribution on the southwestern continental margin of India: evidence of input from the Bay of Bengal

    NASA Astrophysics Data System (ADS)

    Chauhan, Onkar S.; Gujar, A. R.

    1996-03-01

    Analyses of spatial distribution of clay minerals, sediment texture, and > 63 μm fractions of the grab samples from the S W continental margin of India exhibit: (i) higher contents of illite and chlorite on the lower slope and (ii) a well-defined no-clay zone on the entire shelf. Kaolinite and smectite are also present in significant quantities on the slope with traces of gibbsite and palygorskite in some samples. The high contents of illite and chlorite (clay minerals which are not abundant in the soils and estuarine sediments of this region) in the southern region of the study area are evidence for sediment contribution from the Bay of Bengal waters (BBW), which enter this region after the SW monsoon. Distribution trends of kaolinite, smectite, gibbsite, and laterite granules on the slope are suggestive of contribution from chemically weathered soils of Peninsular India.

  1. DFT theoretical and FT-IR spectroscopic investigations of the plasticity of clay minerals dispersions

    NASA Astrophysics Data System (ADS)

    Kasprzhitskii, A.; Lazorenko, G.; Yavna, V.; Daniel, Ph.

    2016-04-01

    Plasticity is the most important property of dispersions of clay minerals that determine the character of participation of these systems in many natural and technological processes. We report on the results of studies of hydration mechanism in typical clay minerals making part of natural dispersions of sedimentation masses by means of IR spectroscopy and theoretical density functional theory (DFT) methods. X-ray diffraction analysis of clay minerals of Millerovo mineral deposit (Russian Federation) is carried out. Regularities and peculiarities of interaction of water molecules with kaolinite basal planes (001) and (00 1 bar) are analyzed. The role of water in the formation of plasticity of clay minerals dispersions is revealed. The modes of water molecules placement and their state and structure in the system "clay mineral-water" is defined. Phase transition processes of clay minerals dispersion into plastic and liquid state and their influence on spectral characteristics of the systems are investigated. The interpretation of clay minerals phase transitions into plastic and fluid state based on the results of DFT simulation is given. The relation is established between specific variation of spectral characteristics and phase transitions of clay minerals dispersions into plastic and liquid state.

  2. Soft X-ray spectromicroscopy study of mineral-organic matter associations in pasture soil clay fractions.

    PubMed

    Chen, Chunmei; Dynes, James J; Wang, Jian; Karunakaran, Chithra; Sparks, Donald L

    2014-06-17

    There is a growing acceptance that associations with soil minerals may be the most important overarching stabilization mechanism for soil organic matter. However, direct investigation of organo-mineral associations has been hampered by a lack of methods that can simultaneously characterize organic matter (OM) and soil minerals. In this study, STXM-NEXAFS spectroscopy at the C 1s, Ca 2p, Fe 2p, Al 1s, and Si 1s edges was used to investigate C associations with Ca, Fe, Al, and Si species in soil clay fractions from an upland pasture hillslope. Bulk techniques including C and N NEXAFS, Fe K-edge EXAFS spectroscopy, and XRD were applied to provide additional information. Results demonstrated that C was associated with Ca, Fe, Al, and Si with no separate phase in soil clay particles. In soil clay particles, the pervasive C forms were aromatic C, carboxyl C, and polysaccharides with the relative abundance of carboxyl C and polysaccharides varying spatially at the submicrometer scale. Only limited regions in the soil clay particles had aliphatic C. Good C-Ca spatial correlations were found for soil clay particles with no CaCO3, suggesting a strong role of Ca in organo-mineral assemblage formation. Fe EXAFS showed that about 50% of the total Fe in soils was contained in Fe oxides, whereas Fe-bearing aluminosilicates (vermiculite and Illite) accounted for another 50%. Fe oxides in the soil were mainly crystalline goethite and hematite, with lesser amounts of poorly crystalline ferrihydrite. XRD revealed that soil clay aluminosilicates were hydroxy-interlayered vermiculite, Illite, and kaolinite. C showed similar correlation with Fe to Al and Si, implying a similar association of Fe oxides and aluminosilicates with organic matter in organo-mineral associations. These direct microscopic determinations can help improve understanding of organo-mineral interactions in soils. PMID:24837340

  3. Metachromasy as an indicator of photostabilization of methylene blue adsorbed to clays and minerals.

    PubMed

    Samuels, Maya; Mor, Omer; Rytwo, Giora

    2013-04-01

    The influence of methylene blue adsorption to different clays on its photodegradation was studied. Methylene blue in solution was decomposed by sunlight in a zero-order process. Adsorption to some clay minerals (sepiolite and vermiculite) and a zeolite (clinoptilolite) accelerated the degradation process, and converted it to a first-order reaction. On the other hand, adsorption to other clay minerals (palygorskite and montmorillonite) stabilized the dye and prevented its degradation. Interestingly, in the clay-dye complexes that exhibited stability, clear metachromasy of the adsorbed methylene blue occurred, whereas the effect was not observed in the clay-dye complexes that underwent photodegradation. PMID:23474529

  4. Determining Mineral Types and Abundances from Reflectance Measurements

    NASA Technical Reports Server (NTRS)

    Smith, M. O.; Adams, J. B.

    1985-01-01

    Mineral types and their abundances were quantitatively determined from laboratory reflectance spectra using principal components analysis (PCA). PCA reduced the measured spectral dimensionality and allowed testing the uniqueness and validity of spectral mixing models. In addition to interpreting absorption bands, in this new approach we interpreted variations in the overall spectral curves in terms of physical processes, namely changes in mixtures of minerals, in particle size and in illumination geometry. Application of this approach to reflectances of planetary surfaces allows interpretation to be extended to quantitative determinations of mineral types and abundances.

  5. Origin of clay-mineral variation in Wisconsinan age sediments from the Lake Michigan basin

    SciTech Connect

    Monaghan, G.W. ); Larson, G.J. . Dept. of Geological Sciences)

    1994-04-01

    Drift samples collected in Wisconsin and Michigan from exposures representative of the Wisconsinan stratigraphy of the Lake Michigan Lobe indicate that clay mineral and shale lithology systematically vary between successive till sheets as a result of differential erosion of two unique source beds: shale bedrock, rich in 10[angstrom] clay (illite) and pre-existing drift (particularly lacustrine clay), depleted in 10[angstrom] clay. A general increase in relative amounts of 10[angstrom] clay and shale clasts begins with early or middle Wisconsinan (Altonian) Glenn Shores till and continues through late Wisconsinan (Woodfordian) Ganges-New Berlin till and Saugatuck-Oak Creek till. Both 10[angstrom] clay and shale decrease in post Mackinaw (late Woodfordian) Interstade Ozaukee-Haven and Two Rivers tills. Clay minerals in till rich in 10[angstrom] clay (Saugatuck-Oak Creek) were derived mainly from extensive erosion and comminution of shale whereas those in tills depleted in 10[angstrom] clay (Ganges-New Berlin, Ozaukee-Haven, and Two Rivers) were eroded mainly from lacustrine clay. Because it is compositionally dissimilar to either the shale or lake clay source and relatively rich in kaolinite, clay minerals in early-middle Wisconsinan Glenn Shores till may have been derived from Sangamon saprolite eroded during an early post-Sangamon ice advance. Variations in source bed erosion and subsequent changes in till lithology result either from depletion of the source bed (Glenn Shores till) or from progressively eroding drift mantling shale outcrops (unroofing) during successive late Wisconsinan ice advances.

  6. Clay Minerals in Mawrth Vallis Region of Mars

    NASA Technical Reports Server (NTRS)

    2008-01-01

    This map showing the location of some clay minerals in of a portion of the Mawrth Vallis region of Mars covers an area about 10 kilometers (6.2 mile) wide. The map is draped over a topographical model that exaggerates the vertical dimension tenfold.

    The mineral mapping information comes from an image taken on Sept. 21, 2007, by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM). Iron-magnesium phyllosilicate is shown in red. Aluminum phyllosyllicate is shown in blue. Hydrated silica and a ferrous iron phase are shown in yellow/green.

    The topographical information comes from the Mars Orbiter Laser Altimeter instrument on NASA's Mars Global Surveyor orbiter.

    Mawrth Vallis is an outflow channel centered near 24.7 degrees north latitude, 339.5 degrees east longitude, in northern highlands of Mars.

    CRISM is one of six science instruments on the Mars Reconnaissance Orbiter. Led by The Johns Hopkins University Applied Physics Laboratory, Laurel, Md., the CRISM team includes expertise from universities, government agencies and small businesses in the United States and abroad. NASA's Jet Propulsion Laboratory, a division of the California Institute of Technology in Pasadena, manages the Mars Reconnaissance Orbiter for NASA's Science Mission Directorate, Washington. Lockheed Martin Space Systems, Denver, built the orbiter.

  7. The origin of clay minerals in the tidal flats of the German Bight

    NASA Astrophysics Data System (ADS)

    Engelhardt, H.-J.

    2003-04-01

    The investigation of transport processes of clays in the aquatic environment is important as many pollutants are adsorbed on the surface of fine-grained particles or clay-organic complexes. Suppliers are rivers draining industrial centers. The material is mixed with lithogenic grains characterized by geogenic background compositions. In the Wadden Sea tidal flats large amounts of fine size sediments are accumulated. Sources which must be taken into consideration are rivers (Elbe, Ems, Weser) and pleistocene deposits, eroded from the coast and seafloor. This study used mineral specific properties to determine the portion of the potential source materials on Wadden Sea tidal flat deposits and suspensions. The following features were measured (< 2 μm fraction): the crystallite sizes/widths of XRD peaks, chlorite compositions (cf. Schoen 1962, Amer. Min. 47) after dimethylsulfoxide treatment, the coherent domains within illites and kaolinites by IR spectrometry (cf. Flehmig 1973, N. Jb. Miner. Abh. 119), and the K/Rb-ratios of illite. In addition, K-Ar ages on pure mica concentrates (112-200 μm) were determined. According to the clay mineral abundances, the crystallite sizes, and the structural features of chlorite and kaolinite the younger glacial units (Saale, Weichsel) could be the source of the tidal flat material or alternatively a mixture of glacial and fluviatile sediments. The results correspond with K-Ar ages (tidal flats ˜400 Ma, glacial deposits and scandinavian source rocks 370-1,640 Ma, river sediments and rocks of the catchment areas 285-340 Ma). Illite is the most common clay mineral of the samples with the exception of Elsterian samples which are dominated by smectite. IR data proof that the illites of fluviatile detritus has the greatest coherent domains (>= 0.16), the samples of the tidal flats vary from 0.11 to 0.15, and the glacial sediments have the worst crystallinity (le0.11). K/Rb-ratios show a dominance of the fluviatile detritus (tidal flats ˜145, glacial deposits ˜170, fluviatile bedload ˜130). Thus, about 60% of the illites deposited in the tidal flats have a fluviatile and the remainder a pleistocene origin. Samples of cores from the southern North Sea show that the content of riverine material decreases in seaward direction. In contrast to these results, investigations of the sand fraction (quartz crystallinities, K/Rb-ratio) indicate that the coarse minerals of the tidal flats originated of pleistocene deposits.

  8. A general evaluation of the frequency distribution of clay and associated minerals in the alluvial soils of ceylon

    USGS Publications Warehouse

    Herath, J.W.; Grimshaw, R.W.

    1971-01-01

    Clay mineral analyses were made of several alluvial clay materials from Ceylon. These studies show that the soil materials can be divided into 3 clay mineral provinces on the basis of the frequency distribution of clay and associated minerals. The provinces closely follow the climatic divisions. The characteristic feature of this classification is the progressive development of gibbsite from Dry to Wet Zone areas. Gibbsite has been used as a reliable indicator mineral. ?? 1971.

  9. [Effects of temperature on organic carbon mineralization in paddy soils with different clay content].

    PubMed

    Ren, Xiu-E; Tong, Cheng-Li; Sun, Zhong-Lin; Tang, Guo-Yong; Xiao, He-Ai; Wu, Jin-Shui

    2007-10-01

    An incubation test with three kinds of paddy soil (sandy loam, clay loam, and silty clay soils) in subtropical region was conducted at 10, 15, 20, 25 and 30 degrees C to examine the response of the mineralization of soil organic carbon (SOC) to temperature change. The results showed that during the period of 160 d incubation, the accumulative mineralized amount of SOC in sandy loam, clay loam, and silty clay soils at 30 degrees C was 3.5, 5.2 and 4.7 times as much as that at 10 degrees C, respectively. The mineralization rate was lower and relatively stable at lower temperatures (< or = 20 C), but was higher at the beginning of incubation and decreased and became stable as the time prolonged at higher temperatures (> or = 25 degrees C). During incubation, the temperature coefficient (Q10) of SOC mineralization in test soils fluctuated, with an average Q10 in sandy loam, clay loam, and silty clay soils being 1.92, 2.37 and 2.32, respectively. There was a positive exponential correlation between SOC mineralization constant k and temperature (P < 0.01), and the response of SOC mineralization to temperature change was in the order of clay loam soil > silty clay soil > sandy loam soil. PMID:18163305

  10. Sm-Nd dating of Fig Tree clay minerals of the Barberton greenstone belt, South Africa

    NASA Technical Reports Server (NTRS)

    Toulkeridis, T.; Goldstein, S. L.; Clauer, N.; Kroner, A.; Lowe, D. R.

    1994-01-01

    Sm-Nd isotopic data from carbonate-derived clay minerals of the 3.22-3.25 Ga Fig Tree Group, Barberton greenstone belt, South Africa, form a linear array corresponding to an age of 3102 +/- 64 Ma, making these minerals the oldest dated clays on Earth. The obtained age is 120-160 m.y. younger than the depositional age determined by zircon geochronology. Nd model ages for the clays range from approximately 3.39 to 3.44 Ga and almost cover the age variation of the Barberton greenstone belt rocks, consistent with independent evidence that the clay minerals are derived from material of the belt. The combined isotopic and mineralogical data provide evidence for a cryptic thermal overprint in the sediments of the belt. However, the highest temperature reached by the samples since the time of clay-mineral formation was <300 degrees C, lower than virtually any known early Archean supracrustal sequence.

  11. Sm-Nd dating of Fig Tree clay minerals of the Barberton greenstone belt, South Africa.

    PubMed

    Toulkeridis, T; Goldstein, S L; Clauer, N; Kroner, A; Lowe, D R

    1994-03-01

    Sm-Nd isotopic data from carbonate-derived clay minerals of the 3.22-3.25 Ga Fig Tree Group, Barberton greenstone belt, South Africa, form a linear array corresponding to an age of 3102 +/- 64 Ma, making these minerals the oldest dated clays on Earth. The obtained age is 120-160 m.y. younger than the depositional age determined by zircon geochronology. Nd model ages for the clays range from approximately 3.39 to 3.44 Ga and almost cover the age variation of the Barberton greenstone belt rocks, consistent with independent evidence that the clay minerals are derived from material of the belt. The combined isotopic and mineralogical data provide evidence for a cryptic thermal overprint in the sediments of the belt. However, the highest temperature reached by the samples since the time of clay-mineral formation was <300 degrees C, lower than virtually any known early Archean supracrustal sequence. PMID:11540244

  12. Elemental Abundance Distributions in Basalt Clays and Meteorites: Is It a Biosignature?

    NASA Technical Reports Server (NTRS)

    Fisk, M. R.; Storrie-Lombardi, M. C.; Joseph, J.

    2005-01-01

    Volcanic glass altered by microorganisms exhibits distinctive textures differing significantly from abiotic alteration [1-4]. We have previously presented morphological evidence of bioweathering in sub-oceanic basalt glass [5] and olivine [6], and noted similar alterations in Nakhla [7]. We have also introduced an autonomous Bayesian probabilistic classification methodology to identify biotic and abiotic alteration in sub-oceanic basalts using elemental abundance data [8]. We now present data from multiple sub-oceanic sites addressing the more general question of utilizing elemental abundance distribution in clays as a valid biosignature for the exploration of putative clay alteration products in meteorites.

  13. MAX--An Interactive Computer Program for Teaching Identification of Clay Minerals by X-ray Diffraction.

    ERIC Educational Resources Information Center

    Kohut, Connie K.; And Others

    1993-01-01

    Discusses MAX, an interactive computer program for teaching identification of clay minerals based on standard x-ray diffraction characteristics. The program provides tutorial-type exercises for identification of 16 clay standards, self-evaluation exercises, diffractograms of 28 soil clay minerals, and identification of nonclay minerals. (MDH)

  14. A SEM, EDS and vibrational spectroscopic study of the clay mineral fraipontite

    NASA Astrophysics Data System (ADS)

    Theiss, Frederick L.; López, Andrés; Scholz, Ricardo; Frost, Ray L.

    2015-08-01

    The mineral fraipontite has been studied by using a combination of scanning electron microscopy with energy dispersive analysis and vibrational spectroscopy (infrared and Raman). Fraipontite is a member of the 1:1 clay minerals of the kaolinite-serpentine group. The mineral contains Zn and Cu and is of formula (Cu,Zn,Al)3(Si,Al)2O5(OH)4. Qualitative chemical analysis of fraipontite shows an aluminium silicate mineral with amounts of Cu and Zn. This kaolinite type mineral has been characterised by Raman and infrared spectroscopy; in this way aspects about the molecular structure of fraipontite clay are elucidated.

  15. Formation of replicating saponite from a gel in the presence of oxalate: implications for the formation of clay minerals in carbonaceous chondrites and the origin of life

    USGS Publications Warehouse

    Schumann, Dirk; Hartman, Hyman; Eberl, Dennis D.; Sears, S. Kelly; Hesse, Reinhard; Vali, Hojatollah

    2012-01-01

    The potential role of clay minerals in the abiotic origin of life has been the subject of ongoing debate for the past several decades. At issue are the clay minerals found in a class of meteorites known as carbonaceous chondrites. These clay minerals are the product of aqueous alteration of anhydrous mineral phases, such as olivine and orthopyroxene, that are often present in the chondrules. Moreover, there is a strong correlation in the occurrence of clay minerals and the presence of polar organic molecules. It has been shown in laboratory experiments at low temperature and ambient pressure that polar organic molecules, such as the oxalate found in meteorites, can catalyze the crystallization of clay minerals. In this study, we show that oxalate is a robust catalyst in the crystallization of saponite, an Al- and Mg-rich, trioctahedral 2:1 layer silicate, from a silicate gel at 60°C and ambient pressure. High-resolution transmission electron microscopy analysis of the saponite treated with octadecylammonium (n(C)=18) cations revealed the presence of 2:1 layer structures that have variable interlayer charge. The crystallization of these differently charged 2:1 layer silicates most likely occurred independently. The fact that 2:1 layer silicates with variable charge formed in the same gel has implications for our understanding of the origin of life, as these 2:1 clay minerals most likely replicate by a mechanism of template-catalyzed polymerization and transmit the charge distribution from layer to layer. If polar organic molecules like oxalate can catalyze the formation of clay-mineral crystals, which in turn promote clay microenvironments and provide abundant adsorption sites for other organic molecules present in solution, the interaction among these adsorbed molecules could lead to the polymerization of more complex organic molecules like RNA from nucleotides on early Earth.

  16. [Species Determination and Spectral Characteristics of Swelling Clay Minerals in the Pliocene Sandstones in Xinghai, Qinghai].

    PubMed

    Wang, Chao-wen; Chen, Jiang-jun; Fang, Qian; Yin, Ke; Hong, Han-lie

    2015-10-01

    X-ray diffraction (XRD) and Fourier infrared absorption spectroscopy (FTIR) were conducted to deepen our research on specific species and spectral characteristics of swelling clay minerals in the Pliocene sandstones in Xinghai, Qinghai province. XRD results show that swelling clay minerals are dominant clay minerals in the sandstones, which can be up to 97% in percentage. XRD patterns show 060 reflections of the samples occur both remarkably at 1.534 Å and 1.498 Å, indicating the samples contain physical mixtures of trioctahedral and dioctahedral swelling clay minerals, respectively. Further treatment of Li-300 degrees C heat and glycerol saturation shows the swelling clay minerals collapse to 9.3-9.9 Å with a partial expansion to -18 Å. This indicates the swelling clay minerals dominate montmorillonite and contain minor saponite. The montmorillonite shows no swelling after Li-300 degrees C heat and glycerol saturation because of Li+ inserting into the octahedral layers, which balances the layer charge caused by the substitution of Mg to Al. FTIR results show the samples are composed of a kind of phyllosilicate with absorbed and structural water, which is in agreement with the results of XRD. Absorbed peaks at 913, 842, 880 cm(-1), corresponding to OH associated with Al-Al, Al-Mg, and Al-Fe pairs, further indicates the minerals are dominant dioctahedron in structure. Meanwhile, absorbed peaks at 625 and 519 cm(-1), corresponding to coupled Si-O and Al-O-Si deformation, indicates parts of Si is replaced by Al in tetrahedron. The spectral characteristics of the samples are against the presence of beidellite and nontronite based on the results of XRD and FTIR, while demonstrating an,existence of montmorillonite. This study, to distinguish the specific species of swelling clay species in clay minerals, would be of great importance when using clay mineralogy to interpret provenance and climatic information. PMID:26904841

  17. Clays as mineral dust aerosol: An integrated approach to studying climate, atmospheric chemistry, and biogeochemical effects of atmospheric clay minerals in an undergraduate research laboratory

    NASA Astrophysics Data System (ADS)

    Hatch, C. D.; Crane, C. C.; Harris, K. J.; Thompson, C. E.; Miles, M. K.; Weingold, R. M.; Bucuti, T.

    2011-12-01

    Entrained mineral dust aerosol accounts for 45% of the global annual atmospheric aerosol load and can have a significant influence on important environmental issues, including climate, atmospheric chemistry, cloud formation, biogeochemical processes, visibility, and human health. 70% of all mineral aerosol mass originating from Africa consists of layered aluminosilicates, including illite, kaolinite, and montmorillonite clays. Clay minerals are a largely neglected component of mineral aerosol, yet they have unique physiochemical properties, including a high reactive surface area, large cation exchange capacities, small particle sizes, and a relatively large capacity to take up adsorbed water, resulting in expansion of clay layers (and a larger reactive surface area for heterogeneous interactions) in some cases. An integrated laboratory research approach has been implemented at Hendrix College, a Primarily Undergraduate Institution, in which undergraduate students are involved in independent and interdisciplinary research projects that relate the chemical aging processes (heterogeneous chemistry) of clay minerals as a major component of mineral aerosol to their effects on climate (water adsorption), atmospheric chemistry (trace gas uptake), and biogeochemistry (iron dissolution and phytoplankton biomarker studies). Preliminary results and future directions will be reported.

  18. Lithium, a preliminary survey of its mineral occurrence in flint clay and related rock types in the United States

    USGS Publications Warehouse

    Tourtelot, H.A.; Brenner-Tourtelot, E. F.

    1978-01-01

    Maximum concentrations of lithium found in samples of flint clay and associated rocks of Pennsylvanian age in different States, in parts per million (ppm), are: Missouri, 5100; Pennsylvania-Maryland, 2100; Kentucky, 890; Ohio, 660; Alabama, 750; and Illinois, 160. Lithium-bearing kaolin deposits are distributed in the Coastal Plain province from New Jersey to Texas, and one occurs in Idaho; maximum lithium concentrations in samples from these deposits range from 64 to 180 ppm. The maximum concentration found in the Arkansas bauxite region is 460 ppm and that in flint clay in Colorado is 370 ppm. Samples from areas other than Pennsylvania, Maryland, Kentucky and Missouri are relatively few in number, represent mostly commercially valuable clays, and represent only a part of the refractory clay deposits in the United States. Data are not available on the clays associated with these deposits that may be unusable because they contain too much lithium as well as other deleterious elements. In both Pennsylvania and Missouri, lithium contents vary regionally between districts and locally between deposits. In samples containing more than 2000 ppm lithium, the lithium occurs in a dioctahedral chlorite mineral very similar to cookeite, which previously has not been recognized in sedimentary clays. The associated clays consist chiefly of well-crystallized kaolinite. The dioctahedral chlorite, however, seems to be most abundant where diaspore and boehmite occur along with the kaolinite. Barium, chromium, copper, phosphorus and strontium are present in some samples in amounts of several hundred pans per million or more, and may contribute to the failure of some clays to perform satisfactorily in firing tests. Lithium-rich clays could serve as a significant lithium resource in the very distant future. Clays that contain as much as 1% lithium may be common enough in Missouri or in Pennsylvania to be produced as a by-product to help support benefication costs for refractory clays. Sufficient amounts of lithium-rich clay may be found in deposits that have been explored, found unsatisfactory for normal refractory uses, and not developed. The lithium-rich clay in some deposits presently being worked may be worth stockpiling for eventual use. ?? 1978.

  19. Sorption-desorption behavior of PCP on soil organic matter and clay minerals.

    PubMed

    Pu, Xunchi; Cutright, Teresa J

    2006-08-01

    Pentachlorophenol (PCP) contamination is a severe environmental problem due to its widespread occurrence, toxicity and recalcitrance. In order to gain a better understanding of the fate of PCP in soils, the role of the soil organic matter (SOM) and clay minerals in the PCP sorption-desorption was studied on two bulk field soils, two subsoils (i.e., SOM or clay-removed soil) and two artificial soils. The two field soils used were a silty loam from New Mexico (NM) containing 10% clay and a sandy-clay-loam from Colombia (CO) South America comprised of 18% clay minerals. The bulk CO soil containing kaolinite sorbed significantly less PCP than the NM soil. All soils depicted an apparent hysteresis during sorption. The CO bulk and subsoils desorbed 14-20% and 15-26% of the sorbed PCP respectively whereas the NM bulk and subsoils desorbed only 4-12% and 5-16%, respectively. Experiments conducted with pure clay and artificial soils indicated that the expandable clay minerals were key sorbent material. Additional studies to investigate the interaction between SOM and clay minerals are needed to fully understand sorptive phenomena. PMID:16473390

  20. Determination of the composition of the organic matter chemically stabilized by agricultural soil clay minerals: Spectroscopy and Density Fractionation

    NASA Astrophysics Data System (ADS)

    Oufqir, Sofia; Bloom, Paul; Toner, Brandy; Hatcher, Patrick

    2014-05-01

    The interactions between soil organic matter and clay minerals are considered important processes because of their ability to sequester C in soil for long periods of time, and hence control C in the global C cycle when present. However, differing results have been reported regarding the composition of the soil organic matter - aromatic fractions versus aliphatic fractions - associated with clay minerals. To clarify this critical issue and better understand the C sequestration process in soils, we aimed to determine the nature of the chemically bound natural organic matter on clay surfaces, and to probe the speciation and spatial distribution of C in the soil clay nanoparticles using direct spectroscopic measurements namely solid-state CP-MAS and DP-MAS 13C NMR spectroscopy, x-ray diffraction spectroscopy (XRD), and scanning transmission x-ray microscopy (STXM). We tested the hypotheses that peptides and polysaccharides are stabilized by the smectite-illite clay while the lipids and black carbon are a separate phase; and that they are evenly distributed on clay surfaces. A soil clay fraction (5.5% organic C) was isolated from the surface of a prairie soil (Mollisol) in southwestern Minnesota, characterized by a pH 6.0, 32.5% clay content, and 3.7% organic carbon, using a sonication-sedimentation-siphoning process in distilled water. Then was subjected to density separation combined with low energy ultrasonic dispersion to separate the free organic and black C (light fraction) from the chemically bound C (heavy fraction). The XRD results indicated a dominance of interstratified smectite-illite clays in soil. The 13C-NMR spectra of the soil clay fraction suggested that polysaccharides and polypeptides are the prevailing components of the organic matter associated with the mineral clay, with only a minor component of aromatic C. The light fraction has strong alkyl C-H bands characteristic of fatty acids plus strong C-O bands characteristic of polysaccharides, including the anomeric C band centered at 105 ppm. The aromatic band at 130 ppm and the phenolic C-O band at 150 pm are strong as well indicating the presence of black carbon and lignin-derived components, contrary to the heavy fraction where they are almost absent. STXM results indicated that the proteins are abundant in the soil clay fraction, separate from lipids, and partially associated with saccharides. The black carbon constitutes a separate phase, but is amply present with lipids and lignin-derived compounds in the light fraction. We conclude that (1) the smectite-illite sheets in our soils preferentially retain peptides, and polysaccharides favoring the protection of these normally readily biodegradable fractions relative to the lignin-derived phenolic components; (2) the black carbon constitutes a major component of the light fraction, and is partially attached to the organic matter bonded with the smectitic clays; and (3) the lipids are associated with soil clay fraction as a separate phase, but are not bound to clay minerals.

  1. Clay Minerals as Solid Acids and Their Catalytic Properties.

    ERIC Educational Resources Information Center

    Helsen, J.

    1982-01-01

    Discusses catalytic properties of clays, attributed to acidity of the clay surface. The formation of carbonium ions on montmorillonite is used as a demonstration of the presence of surface acidity, the enhanced dissociation of water molecules when polarized by cations, and the way the surface can interact with organic substances. (Author/JN)

  2. Correlation of the Abundance of Betaproteobacteria on Mineral Surfaces with Mineral Weathering in Forest Soils

    PubMed Central

    Lepleux, C.; Turpault, M. P.; Oger, P.; Frey-Klett, P.

    2012-01-01

    Pyrosequencing-based analysis of 16S rRNA gene sequences revealed a significant correlation between apatite dissolution and the abundance of betaproteobacteria on apatite surfaces, suggesting a role for the bacteria belonging to this phylum in mineral weathering. Notably, the cultivation-dependent approach demonstrated that the most efficient mineral-weathering bacteria belonged to the betaproteobacterial genus Burhkolderia. PMID:22798365

  3. Evaluation of the medicinal use of clay minerals as antibacterial agents

    PubMed Central

    Williams, Lynda B.; Haydel, Shelley E.

    2010-01-01

    Natural clays have been used to heal skin infections since the earliest recorded history. Recently our attention was drawn to a clinical use of French green clay (rich in Fe-smectite) for healing Buruli ulcer, a necrotizing fasciitis (‘flesh-eating’ infection) caused by Mycobacterium ulcerans. These clays and others like them are interesting as they may reveal an antibacterial mechanism that could provide an inexpensive treatment for this and other skin infections, especially in global areas with limited hospitals and medical resources. Microbiological testing of two French green clays, and other clays used traditionally for healing, identified three samples that were effective at killing a broad-spectrum of human pathogens. A clear distinction must be made between ‘healing clays’ and those we have identified as antibacterial clays. The highly adsorptive properties of many clays may contribute to healing a variety of ailments, although they are not antibacterial. The antibacterial process displayed by the three identified clays is unknown. Therefore, we have investigated the mineralogical and chemical compositions of the antibacterial clays for comparison with non-antibacterial clays in an attempt to elucidate differences that may lead to identification of the antibacterial mechanism(s). The two French green clays used to treat Buruli ulcer, while similar in mineralogy, crystal size, and major element chemistry, have opposite effects on the bacterial populations tested. One clay deposit promoted bacterial growth whereas another killed the bacteria. The reasons for the difference in antibacterial properties thus far show that the bactericidal mechanism is not physical (e.g., an attraction between clay and bacteria), but by a chemical transfer or reaction. The chemical variables are still under investigation. Cation exchange experiments showed that the antibacterial component of the clay can be removed, implicating exchangeable cations in the antibacterial process. Furthermore, aqueous leachates of the antibacterial clays effectively kill the bacteria. Progressively heating the clay leads first to dehydration (200°C), then dehydroxylation (550°C or more), and finally to destruction of the clay mineral structure by (~900°C). By identifying the elements lost after each heating step, and testing the bactericidal effect of the heated product, we eliminated many toxins from consideration (e.g., microbes, organic compounds, volatile elements) and identified several redox-sensitive refractory metals that are common among antibacterial clays. We conclude that the pH and oxidation state buffered by the clay mineral surfaces is key to controlling the solution chemistry and redox related reactions occurring at the bacterial cell wall. PMID:20640226

  4. Enhanced cellular preservation by clay minerals in 1 billion-year-old lakes.

    PubMed

    Wacey, David; Saunders, Martin; Roberts, Malcolm; Menon, Sarath; Green, Leonard; Kong, Charlie; Culwick, Timothy; Strother, Paul; Brasier, Martin D

    2014-01-01

    Organic-walled microfossils provide the best insights into the composition and evolution of the biosphere through the first 80 percent of Earth history. The mechanism of microfossil preservation affects the quality of biological information retained and informs understanding of early Earth palaeo-environments. We here show that 1 billion-year-old microfossils from the non-marine Torridon Group are remarkably preserved by a combination of clay minerals and phosphate, with clay minerals providing the highest fidelity of preservation. Fe-rich clay mostly occurs in narrow zones in contact with cellular material and is interpreted as an early microbially-mediated phase enclosing and replacing the most labile biological material. K-rich clay occurs within and exterior to cell envelopes, forming where the supply of Fe had been exhausted. Clay minerals inter-finger with calcium phosphate that co-precipitated with the clays in the sub-oxic zone of the lake sediments. This type of preservation was favoured in sulfate-poor environments where Fe-silicate precipitation could outcompete Fe-sulfide formation. This work shows that clay minerals can provide an exceptionally high fidelity of microfossil preservation and extends the known geological range of this fossilization style by almost 500 Ma. It also suggests that the best-preserved microfossils of this time may be found in low-sulfate environments. PMID:25068404

  5. Elastic Properties of Clay Minerals Determined by Atomic Force Acoustic Microscopy Technique

    NASA Astrophysics Data System (ADS)

    Kopycinska-Müller, M.; Prasad, M.; Rabe, U.; Arnold, W.

    Seismic wave propagation in geological formations is altered by the presence of clay minerals. Knowledge about the elastic properties of clay is therefore essential for the interpretation and modeling of the seismic response of clay-bearing formations. However, due to the layered structure of clay, it is very difficult to investigate its elastic properties. We measured elastic properties of clay using atomic force acoustic microscopy (AFAM). The forces applied during the experiments were not higher than 50 nN. The adhesion forces were measured from the pull-off forces and included into our calculations by means of the Derjaguin-Mueller-Toporov model for contact mechanics. The obtained values of the elastic modulus for clay varied from 10 to 17 GPa depending on various parameters that describe the dynamics of a vibrating beam

  6. The possible role of nannobacteria (dwarf bacteria) in clay-mineral diagenesis and the importance of careful sample preparation in high-magnification SEM study

    SciTech Connect

    Folk, R.L.; Lynch, F.L.

    1997-05-01

    Bacterial textures are present on clay minerals in Oligocene Frio Formation sandstones from the subsurface of the Corpus Christi area, Texas. In shallower samples, beads 0.05--0.1 {micro}m in diameter rim the clay flakes; at greater depth these beads become more abundant and eventually are perched on the ends of clay filaments of the same diameter. The authors believe that the beads are nannobacteria (dwarf forms) that have precipitated or transformed the clay minerals during burial of the sediments. Rosettes of chlorite also contain, after HCl etching, rows of 0.1 {micro}m bodies. In contrast, kaolinite shows no evidence of bacterial precipitation. The authors review other examples of bacterially precipitated clay minerals. A danger present in interpretation of earlier work (and much work of others) is the development of nannobacteria-looking artifacts caused by gold coating times in excess of one minute; the authors strongly recommend a 30-second coating time. Bacterial growth of clay minerals may be a very important process both in the surface and subsurface.

  7. Potential bioavailability of mercury in humus-coated clay minerals.

    PubMed

    Zhu, Daiwen; Zhong, Huan

    2015-10-01

    It is well-known that both clay and organic matter in soils play a key role in mercury biogeochemistry, while their combined effect is less studied. In this study, kaolinite, vermiculite, and montmorillonite were coated or not with humus, and spiked with inorganic mercury (IHg) or methylmercury (MeHg). The potential bioavailability of mercury to plants or deposit-feeders was assessed by CaCl2 or bovine serum albumin (BSA) extraction. For uncoated clay, IHg or MeHg extraction was generally lower in montmorillonite, due to its greater number of functional groups. Humus coating increased partitioning of IHg (0.5%-13.7%) and MeHg (0.8%-52.9%) in clay, because clay-sorbed humus provided more strong binding sites for mercury. Furthermore, humus coating led to a decrease in IHg (3.0%-59.8% for CaCl2 and 2.1%-5.0% for BSA) and MeHg (8.9%-74.6% for CaCl2 and 0.5%-8.2% for BSA) extraction, due to strong binding between mercury and clay-sorbed humus. Among various humus-coated clay particles, mercury extraction by CaCl2 (mainly through cation exchange) was lowest in humus-coated vermiculite, explained by the strong binding between humus and vermiculite. The inhibitory effect of humus on mercury bioavailability was also evidenced by the negative relationship between mercury extraction by CaCl2 and mercury in the organo-complexed fraction. In contrast, extraction of mercury by BSA (principally through complexation) was lowest in humus-coated montmorillonite. This was because BSA itself could be extensively sorbed onto montmorillonite. Results suggested that humus-coated clay could substantially decrease the potential bioavailability of mercury in soils, which should be considered when assessing risk in mercury-contaminated soils. PMID:26456605

  8. Effect of cyclodextrins on surface and pore properties of soil clay minerals.

    PubMed

    Jozefaciuk, G; Muranyi, A; Fenyvesi, E

    2001-12-15

    Although cyclodextrins are increasingly used in soil decontamination, little is known about their effects on soil physicochemical properties. In this work, the surface and pore properties of randomly methylated beta-cyclodextrin (RAMEB) and three typical clay minerals were characterized, and the effects of RAMEB concentrations on clay minerals were studied using water vapor adsorption-desorption and mercury intrusion porosimetry techniques. As compared to clay minerals, for pure RAMEB very large surface area and volume of nanometer-size pores (micropores) were determined. Energy of interaction with water vapor, volume of micrometer-size pores (mesopores), and fractal dimensions in both pore size ranges of RAMEB were lower than those of the minerals. When increasing amounts of RAMEB were added to the minerals, the surface area and micropore volume decreased and adsorption energy increased. The volume of mesopores decreased after RAMEB treatments for bentonite and kaolin and increased for illite. As deduced from the fractal dimensions increase, the pore structure of the minerals became more complex with RAMEB addition. The observed changes were in general contrary to these expected when RAMEB and minerals coexist as separate, nonreactive phases and suggested strong interaction of RAMEB with clay minerals. PMID:11775177

  9. MODELING OF CATION BINDING IN HYDRATED 2:1 CLAY MINERALS

    EPA Science Inventory

    Hydrated 2:1 clay minerals are high-surface area, layered silicates that play a unique role in determining the fate of ionic pollutants in the environment. These minerals, including smectites and vermiculites, make up a major component of many soils. Ionic pollutants, including r...

  10. [Analysis of XRD spectral characteristics of soil clay mineral in two typical cultivated soils].

    PubMed

    Zhang, Zhi-Dan; Luo, Xiang-Li; Jiang, Hai-Chao; Li, Qiao; Shen, Cong-Ying; Liu, Hang; Zhou, Ya-Juan; Zhao, Lan-Po; Wang, Ji-Hong

    2014-07-01

    The present paper took black soil and chernozem, the typical cultivated soil in major grain producing area of Northeast, as the study object, and determinated the soil particle composition characteristics of two cultivated soils under the same climate and location. Then XRD was used to study the composition and difference of clay mineral in two kinds of soil and the evolutionary mechanism was explored. The results showed that the two kinds of soil particles were composed mainly of the sand, followed by clay and silt. When the particle accumulation rate reached 50%, the central particle size was in the 15-130 microm interval. Except for black soil profile of Shengli Xiang, the content of clay showed converse sequence to the central particle in two soils. Clay accumulated under upper layer (18.82%) in black soil profile while under caliche layer (17.41%) in chernozem profile. Clay content was the least in parent material horizon except in black profile of Quanyanling. Analysis of clay XRD atlas showed that the difference lied in not only the strength of diffraction peak, but also in the mineral composition. The main contents of black soil and chernozem were both 2 : 1 clay, the composition of black soil was smectite/illite mixed layer-illite-vermiculite and that of chernozem was S/I mixture-illite-montmorillonite, and both of them contained little kaolinite, chlorite, quartz and other primary mineral. This paper used XRD to determine the characteristics of clay minerals comprehensively, and analyzed two kinds of typical cultivated soil comparatively, and it was a new perspective of soil minerals study. PMID:25269317

  11. Kinetic study of aluminum adsorption by aluminosilicate clay minerals

    SciTech Connect

    Walker, W.J.; Cronan, C.S.; Patterson, H.H.

    1988-01-01

    The adsorption kinetics of Al/sup 3 +/ by montmorillonite, kaolinite, and vermiculite were investigated as a function of the initial Al concentration, the surface area of the clay, and H/sup +/ concentration, at 25/sup 0/, 18/sup 0/, and 10/sup 0/C. In order to minimize complicated side reactions the pH range was kept between 3.0 and 4.1. Results showed that the adsorption rate was first order with respect to both the initial Al concentration and the clay surface area. Changes in pH within this narrow range had virtually no effect on adsorption rate. This zero order reaction dependence suggested that the H/sup +/, compared to Al, has a weak affinity for the surface. The rates of adsorption decreased in the order of montmorillonite > kaolinite > vermiculite when compared on the basis of equal surface areas, but changed to kaolinite > montmorillonite > vermiculite when the clays were compared on an equal exchange capacity basis. The calculated apparent activation energies were < 32 kJ mol/sup -1/, indicating that over the temperature range of the study the adsorption process is only marginally temperature sensitive. The mechanism is governed by a simple electrostatic cation exchange involving outer sphere complexes between adsorbed Al and the clay surface. Vermiculite, may have a second reaction step governed by both electrostatic attraction and internal ion diffusion. Equilibrium constants for the formation of an adsorbed Al clay complex were also estimated and are 10/sup 5.34/, 10/sup 5.18/, and 10/sup 4.94/ for kaolinite, montmorillonite, and vermiculite, respectively, suggesting that these clays could play a significant role in controlling soil solutions Al concentrations.

  12. Clay-mineral suites, sources, and inferred dispersal routes: Southern California continental shelf.

    PubMed

    Hein, James R; Dowling, Jennifer S; Schuetze, Anthony; Lee, Homa J

    2003-01-01

    Clay mineralogy is useful in determining the distribution, sources, and dispersal routes of fine-grained sediments. In addition, clay minerals, especially smectite, may control the degree to which contaminants are adsorbed by the sediment. We analyzed 250 shelf sediment samples, 24 river-suspended-sediment samples, and 12 river-bed samples for clay-mineral contents in the Southern California Borderland from Point Conception to the Mexico border. In addition, six samples were analyzed from the Palos Verdes Headland in order to characterize the clay minerals contributed to the offshore from that point source. The <2 microm-size fraction was isolated, Mg-saturated, and glycolated before analysis by X-ray diffraction. Semi-quantitative percentages of smectite, illite, and kaolinite plus chlorite were calculated using peak areas and standard weighting factors. Most fine-grained sediment is supplied to the shelf by rivers during major winter storms, especially during El Niño years. The largest sediment fluxes to the region are from the Santa Ynez and Santa Clara Rivers, which drain the Transverse Ranges. The mean clay-mineral suite for the entire shelf sediment data set (26% smectite, 50% illite, 24% kaolinite+chlorite) is closely comparable to that for the mean of all the rivers (31% smectite, 49% illite, 20% kaolinite+chlorite), indicating that the main source of shelf fine-grained sediments is the adjacent rivers. However, regional variations do exist and the shelf is divided into four provinces with characteristic clay-mineral suites. The means of the clay-mineral suites of the two southernmost provinces are within analytical error of the mineral suites of adjacent rivers. The next province to the north includes Santa Monica Bay and has a suite of clay minerals derived from mixing of fine-grained sediments from several sources, both from the north and south. The northernmost province clay-mineral suite matches moderately well that of the adjacent rivers, but does indicate some mixing from sources in adjacent provinces. PMID:12648951

  13. Clay-mineral suites, sources, and inferred dispersal routes: Southern California continental shelf

    USGS Publications Warehouse

    Hein, J.R.; Dowling, J.S.; Schuetze, A.; Lee, H.J.

    2003-01-01

    Clay mineralogy is useful in determining the distribution, sources, and dispersal routes of fine-grained sediments. In addition, clay minerals, especially smectite, may control the degree to which contaminants are adsorbed by the sediment. We analyzed 250 shelf sediment samples, 24 river-suspended-sediment samples, and 12 river-bed samples for clay-mineral contents in the Southern California Borderland from Point Conception to the Mexico border. In addition, six samples were analyzed from the Palos Verdes Headland in order to characterize the clay minerals contributed to the offshore from that point source. The <2 ??m-size fraction was isolated, Mg-saturated, and glycolated before analysis by X-ray diffraction. Semi-quantitative percentages of smectite, illite, and kaolinite plus chlorite were calculated using peak areas and standard weighting factors. Most fine-grained sediment is supplied to the shelf by rivers during major winter storms, especially during El Nin??o years. The largest sediment fluxes to the region are from the Santa Ynez and Santa Clara Rivers, which drain the Transverse Ranges. The mean clay-mineral suite for the entire shelf sediment data set (26% smectite, 50% illite, 24% kaolinite+chlorite) is closely comparable to that for the mean of all the rivers (31% smectite, 49% illite, 20% kaolinite+chlorite), indicating that the main source of shelf fine-grained sediments is the adjacent rivers. However, regional variations do exist and the shelf is divided into four provinces with characteristic clay-mineral suites. The means of the clay-mineral suites of the two southernmost provinces are within analytical error of the mineral suites of adjacent rivers. The next province to the north includes Santa Monica Bay and has a suite of clay minerals derived from mixing of fine-grained sediments from several sources, both from the north and south. The northernmost province clay-mineral suite matches moderately well that of the adjacent rivers, but does indicate some mixing from sources in adjacent provinces.

  14. ATTENUATION OF POLLUTANTS IN MUNICIPAL LANDFILL LEACHATE BY CLAY MINERALS

    EPA Science Inventory

    The first part of this project was a laboratory column study of attenuation of pollutants in municipal solid waste landfill leachate by mixtures of sand and calcium-saturated clays. K, NH4, Mg, Si, and Fe were moderately attenuated; and the heavy metals Pb, Cd, Hg, and Zn were st...

  15. Measurement of clay surface areas by polyvinylpyrrolidone (PVP) sorption and its use for quantifying illite and smectite abundance

    USGS Publications Warehouse

    Blum, A.E.; Eberl, D.D.

    2004-01-01

    A new method has been developed for quantifying smectite abundance by sorbing polyvinylpyrrolidone (PVP) on smectite particles dispersed in aqueous solution. The sorption density of PVP-55K on a wide range of smectites, illites and kaolinites is ???0.99 mg/m2, which corresponds to ???0.72 g of PVP-55K per gram of montmorillonite. Polyvinylpyrrolidone sorption on smectites is independent of layer charge and solution pH. PVP sorption on Si02, Fe 2O3 and ZnO normalized to the BET surface area is similar to the sorption densities on smectites. ??-Al 2O3, amorphous Al(OH)3 and gibbsite have no PVP sorption over a wide range of pH, and sorption of PVP by organics is minimal. The insensitivity of PVP sorption densities to mineral layer charge, solution pH and mineral surface charge indicates that PVP sorption is not localized at charged sites, but is controlled by more broadly distributed sorption mechanisms such as Van der Waals' interactions and/or hydrogen bonding. Smectites have very large surface areas when dispersed as single unit-cell-thick particles (???725 m2/g) and usually dominate the total surface areas of natural samples in which smectites are present. In this case, smectite abundance is directly proportional to PVP sorption. In some cases, however, the accurate quantification of smectite abundance by PVP sorption may require minor corrections for PVP uptake by other phases, principally illite and kaolinite. Quantitative XRD can be combined with PVP uptake measurements to uniquely determine the smectite concentration in such sample. ?? 2004, The Clay Minerals Society.

  16. Estimation of the standard molal heat capacities, entropies and volumes of 2:1 clay minerals

    NASA Astrophysics Data System (ADS)

    Ransom, Barbara; Helgeson, Harold C.

    1994-11-01

    The dearth of accurate values of the thermodynamic properties of 2:1 clay minerals severely hampers interpretation of their phase relations, the design of critical laboratory experiments and geologically realistic computer calculations of mass transfer in weathering, diagenetic and hydrothermal systems. Algorithms and strategies are described below for estimating to within 2% the standard molal heat capacities, entropies, and volumes of illites, smectites and other 2:1 clay minerals. These techniques can also be used to estimate standard molal thermodynamic properties of fictive endmembers of clay mineral solid solutions. Because 2:1 clay minerals like smectite and vermiculite are always hydrated to some extent in nature, contribution of interlayer H 2O to their thermodynamic properties is considered explicitly in the estimation of the standard molal heat capacities, entropies, and volumes of these minerals. Owing to the lack of accurate calorimetric data from which reliable values of the standard molal heat capacity and entropy of interlayer H 2O can be retrieved, these properties were taken in a first approximation to be equal to those of zeolitic H 2O in analcite. The resulting thermodynamic contributions per mole of interlayer H 2O to the standard molal heat capacity, entropy, and volume of hydrous clay minerals at 1 bar and 25°C are 11.46 cal mol -1, 13.15 cal mol -1 K -1 and 17.22 cm 3 mol, respectively. Estimated standard molal heat capacities, entropies and volumes are given for a suite of smectites and illites commonly used in models of clay mineral and shale diagenesis.

  17. Characterization of Clay Minerals and Kerogen in Alberta Oil Sands Geological End Members

    NASA Astrophysics Data System (ADS)

    Zheng, Limin

    The high degree of variability of oil sands ores can be attributed to a mixture of different geological end members, i.e., estuarine sand, estuarine clay, marine sand and marine clay. This study focused on the mineralogy, especially of clay minerals, and toluene insoluble organic matter, referred to as kerogen, in different oil sands end members. Clays and kerogens will likely have a significant impact on solvent recovery from the gangue following non-aqueous bitumen extraction. The bitumen-free solids were subjected to mineralogical and geochemical analysis. Kerogens were isolated and analyzed by various characterization methods. The types of clays were identified in oriented samples by X-ray diffraction analysis. The nitrogen to carbon ratio in the isolated kerogens is found to be higher than in bitumen. There are more type III kerogens in estuarine samples and more type II kerogens in marine samples.

  18. Reliable Quantitative Mineral Abundances of the Martian Surface using THEMIS

    NASA Astrophysics Data System (ADS)

    Smith, R. J.; Huang, J.; Ryan, A. J.; Christensen, P. R.

    2013-12-01

    The following presents a proof of concept that given quality data, Thermal Emission Imaging System (THEMIS) data can be used to derive reliable quantitative mineral abundances of the Martian surface using a limited mineral library. The THEMIS instrument aboard the Mars Odyssey spacecraft is a multispectral thermal infrared imager with a spatial resolution of 100 m/pixel. The relatively high spatial resolution along with global coverage makes THEMIS datasets powerful tools for comprehensive fine scale petrologic analyses. However, the spectral resolution of THEMIS is limited to 8 surface sensitive bands between 6.8 and 14.0 μm with an average bandwidth of ~ 1 μm, which complicates atmosphere-surface separation and spectral analysis. This study utilizes the atmospheric correction methods of both Bandfield et al. [2004] and Ryan et al. [2013] joined with the iterative linear deconvolution technique pioneered by Huang et al. [in review] in order to derive fine-scale quantitative mineral abundances of the Martian surface. In general, it can be assumed that surface emissivity combines in a linear fashion in the thermal infrared (TIR) wavelengths such that the emitted energy is proportional to the areal percentage of the minerals present. TIR spectra are unmixed using a set of linear equations involving an endmember library of lab measured mineral spectra. The number of endmembers allowed in a spectral library are restricted to a quantity of n-1 (where n = the number of spectral bands of an instrument), preserving one band for blackbody. Spectral analysis of THEMIS data is thus allowed only seven endmembers. This study attempts to prove that this limitation does not prohibit the derivation of meaningful spectral analyses from THEMIS data. Our study selects THEMIS stamps from a region of Mars that is well characterized in the TIR by the higher spectral resolution, lower spatial resolution Thermal Emission Spectrometer (TES) instrument (143 bands at 10 cm-1 sampling and 3x5 km pixel). Multiple atmospheric corrections are performed for one image using the methods of Bandfield et al. [2004] and Ryan et al. [2013]. 7x7 pixel areas were selected, averaged, and compared using each atmospherically corrected image to ensure consistency. Corrections that provided reliable data were then used for spectral analyses. Linear deconvolution is performed using an iterative spectral analysis method [Huang et al. in review] that takes an endmember spectral library, and creates mineral combinations based on prescribed mineral group selections. The script then performs a spectral mixture analysis on each surface spectrum using all possible mineral combinations, and reports the best modeled fit to the measured spectrum. Here we present initial results from Syrtis Planum where multiple atmospherically corrected THEMIS images were deconvolved to produce similar spectral analysis results, within the detection limit of the instrument. THEMIS mineral abundances are comparable to TES-derived abundances. References: Bandfield, JL et al. [2004], JGR 109, E10008 Huang, J et al., JGR, in review Ryan, AJ et al. [2013], AGU Fall Meeting

  19. Bioremediation of PAHs and VOCs: Advances in clay mineral-microbial interaction.

    PubMed

    Biswas, Bhabananda; Sarkar, Binoy; Rusmin, Ruhaida; Naidu, Ravi

    2015-12-01

    Bioremediation is an effective strategy for cleaning up organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs). Advanced bioremediation implies that biotic agents are more efficient in degrading the contaminants completely. Bioremediation by microbial degradation is often employed and to make this process efficient, natural and cost-effective materials can serve as supportive matrices. Clay/modified clay minerals are effective adsorbents of PAHs/VOCs, and readily available substrate and habitat for microorganisms in the natural soil and sediment. However, the mechanism underpinning clay-mediated biodegradation of organic compounds is often unclear, and this requires critical investigation. This review describes the role of clay/modified clay minerals in hydrocarbon bioremediation through interaction with microbial agents in specific scenarios. The vision is on a faster, more efficient and cost-effective bioremediation technique using clay-based products. This review also proposes future research directions in the field of clay modulated microbial degradation of hydrocarbons. PMID:26408945

  20. Atom exchange between aqueous Fe(II) and structural Fe in clay minerals.

    PubMed

    Neumann, Anke; Wu, Lingling; Li, Weiqiang; Beard, Brian L; Johnson, Clark M; Rosso, Kevin M; Frierdich, Andrew J; Scherer, Michelle M

    2015-03-01

    Due to their stability toward reductive dissolution, Fe-bearing clay minerals are viewed as a renewable source of Fe redox activity in diverse environments. Recent findings of interfacial electron transfer between aqueous Fe(II) and structural Fe in clay minerals and electron conduction in octahedral sheets of nontronite, however, raise the question whether Fe interaction with clay minerals is more dynamic than previously thought. Here, we use an enriched isotope tracer approach to simultaneously trace Fe atom movement from the aqueous phase to the solid ((57)Fe) and from the solid into the aqueous phase ((56)Fe). Over 6 months, we observed a significant decrease in aqueous (57)Fe isotope fraction, with a fast initial decrease which slowed after 3 days and stabilized after about 50 days. For the aqueous (56)Fe isotope fraction, we observed a similar but opposite trend, indicating that Fe atom movement had occurred in both directions: from the aqueous phase into the solid and from the solid into aqueous phase. We calculated that 5-20% of structural Fe in clay minerals NAu-1, NAu-2, and SWa-1 exchanged with aqueous Fe(II), which significantly exceeds the Fe atom layer exposed directly to solution. Calculations based on electron-hopping rates in nontronite suggest that the bulk conduction mechanism previously demonstrated for hematite1 and suggested as an explanation for the significant Fe atom exchange observed in goethite2 may be a plausible mechanism for Fe atom exchange in Fe-bearing clay minerals. Our finding of 5-20% Fe atom exchange in clay minerals indicates that we need to rethink how Fe mobility affects the macroscopic properties of Fe-bearing phyllosilicates and its role in Fe biogeochemical cycling, as well as its use in a variety of engineered applications, such as landfill liners and nuclear repositories. PMID:25671351

  1. Reduction And Immobilization Of Hexavalent Chromium By Microbially Reduced Fe-bearing Clay Minerals

    SciTech Connect

    Bishop, Michael E.; Glasser, Paul; Dong, Hailiang; Arey, Bruce W.; Kovarik, Libor

    2014-05-15

    Hexavalent chromium (Cr6+) is a major contaminant in the environment. As a redox-sensitive element, the fate and toxicity of chromium is controlled by reduction-oxidation (redox) reactions. Previous research has shown the ability of structural Fe(II) in naturally present and chemically reduced clay minerals to reduce Cr6+ to Cr(III) as a way of immobilization and detoxification. However, it is still poorly known whether or not structural Fe(II) in biologically reduced clay minerals exhibits a similar reactivity and if so, what the kinetics and mechanisms of Cr6+ reduction are. The objective of this study was to determine the kinetics and possible mechanisms of Cr6+ reduction by structural Fe(II) in microbially reduced clay minerals and the nature of reduced Cr(III). Structural Fe(III) in nontronite (NAu-2), montmorillonite (SWy-2), chlorite (CCa-2), and clay-rich sediments from the Ringold Formation of the Hanford site of Washington State, USA was first bioreduced to Fe(II) by an iron-reducing bacterium Geobacter sulfurreducens with acetate as the sole electron donor and anthraquinone-2,6-disulfate (AQDS) as electron shuttle in synthetic groundwater (pH 7). Biogenic Fe(II) was then used to reduce aqueous Cr6+ at three different temperatures, 10°, 20°, and 30°C, in order to determine the temperature dependence of the redox reaction between Cr6+ and clay-Fe(II). The results showed that nontronite and montmorillonite were most effective in reducing aqueous Cr6+ at all three temperatures. In contrast, most Fe(II) in chlorite was not reactive towards Cr6+ reduction at 10°C, though at 30°C there was some reduction. For all the clay minerals, the ratio of total Fe(II) oxidized to Cr6+ reduced was close to the expected stoichiometric value of 3. Characterization of the Cr-clay reaction product with scanning electron microscopy with focused ion beam and transmission electron microscopy with electron energy loss spectroscopy revealed that reduced chromium was possibly in the form of sub-nanometer Cr2O3 in association with residual clay minerals as micro-aggregates. This textural association was expected to minimize the chance of Cr(III) reoxidation upon exposure to oxidants. These results are important for our understanding of how various clay minerals may be used to reductively immobilize the heavy metal contaminant Cr in the environment.

  2. Reduction and immobilization of hexavalent chromium by microbially reduced Fe-bearing clay minerals

    NASA Astrophysics Data System (ADS)

    Bishop, Michael E.; Glasser, Paul; Dong, Hailiang; Arey, Bruce; Kovarik, Libor

    2014-05-01

    Hexavalent chromium (Cr6+) is a major contaminant in the environment. As a redox-sensitive element, the fate and toxicity of chromium is controlled by reduction-oxidation (redox) reactions. Previous research has shown the ability of structural Fe(II) in naturally present and chemically reduced clay minerals to reduce Cr6+ to Cr(III) as a way of immobilization and detoxification. However, it is still poorly known whether or not structural Fe(II) in biologically reduced clay minerals exhibits a similar reactivity and if so, what the kinetics and mechanisms of Cr6+ reduction are. The objective of this study was to determine the kinetics and possible mechanisms of Cr6+ reduction by structural Fe(II) in microbially reduced clay minerals and the nature of reduced Cr(III). Structural Fe(III) in nontronite (NAu-2), montmorillonite (SWy-2), chlorite (CCa-2), and clay-rich sediments from the Ringold Formation of the Hanford site of Washington State, USA was first bioreduced to Fe(II) by an iron-reducing bacterium Geobacter sulfurreducens with acetate as the sole electron donor and anthraquinone-2,6-disulfonate (AQDS) as electron shuttle in synthetic groundwater (pH 7). Biogenic Fe(II) was then used to reduce aqueous Cr6+ at three different temperatures, 10, 20, and 30 °C, in order to determine the temperature dependence of the redox reaction between Cr6+ and clay-Fe(II). The results showed that nontronite and montmorillonite were most effective in reducing aqueous Cr6+ at all three temperatures. In contrast, most Fe(II) in chlorite was not reactive towards Cr6+ reduction at 10 °C, though at 30 °C there was some reduction. For all the clay minerals, the ratio of total Fe(II) oxidized to Cr6+ reduced was close to the expected stoichiometric value of 3. Characterization of the Cr-clay reaction product with scanning electron microscopy with focused ion beam and transmission electron microscopy with electron energy loss spectroscopy revealed that reduced chromium was possibly in the form of sub-nanometer Cr2O3 in association with residual clay minerals as micro-aggregates. This textural association was expected to minimize the chance of Cr(III) reoxidation upon exposure to oxidants. These results are important for our understanding of how various clay minerals may be used to reductively immobilize the heavy metal contaminant Cr in the environment.

  3. Implications of Clay Mineral-RNA Interactions for the Origin of Life

    NASA Astrophysics Data System (ADS)

    Stephenson, J. D.; Ditzler, M. A.

    2014-12-01

    Due to its ability to both store information and catalyze reactions, RNA is considered by many to have been the dominant biopolymer at the origin of life. We are screening a large, random RNA population for catalytic activity in the presence and absence of prebiotically relevant clay minerals, to investigate the effect of RNA-clay mineral interactions on RNA function. There is an extensive precedent for screening RNA populations for enzymatic functions such as ligation, cleavage and binding in the laboratory. While several environmental parameters have been explored, previous screens have not considered geological interactions. This is surprising as the role of clay minerals has featured prominently in many origin of life theories. Recent empirical evidence demonstrating that clay minerals can adsorb and protect RNA molecules as well as catalyze RNA polymerization has specifically reinvigorated the proposed importance of clay mineral-RNA interactions. Although the identity of the first true biomolecules remains uncertain, interaction between emerging life and its geological environment appears inevitable. We therefore consider understanding the effect of geological-biological interactions to be of crucial importance when considering the earliest biopolymers at the origin of life. Our screens are from a random population of 10^14 unique random RNA sequences and are conducted with and without montmorillonite clay. We are screening for the ability of sequences to self cleave, one of the most basic enzymatic functions considered important to the earliest biopolymers. Our RNA function screens will therefore illuminate the effect of geological interactions at a crucial stage of early evolution.

  4. Experimental Constraints on Microbial Liberation of Structural Iron from Common Clay Minerals in Marine Sediments

    NASA Astrophysics Data System (ADS)

    Metcalfe, K. S.; Gaines, R. R.; Trang, J.; Scott, S. W.; Crane, E. J.; Lackey, J.; Prokopenko, M. G.; Berelson, W.

    2013-12-01

    Iron is a limiting nutrient in many marine settings. The marine Fe-cycle is complex because Fe may be used as an electron donor or acceptor and cycled many times before ultimate burial in sediments. Thus, the availability of iron plays a large role in the marine carbon cycle, influencing not only the extent of primary productivity but also the oxidation of organic matter in sediments. The primary constituents of marine sediments are clay minerals, which commonly contain lattice-bound Fe in octahedral sites. In marine settings, the pool of Fe bound within silicate mineral lattices has long been considered reactive only over long timescales, and thus non-bioavailable. In vitro experimental evidence has shown that lab cultures of Fe-reducing bacteria are able to utilize structurally-bound Fe (III) from the crystal lattice of nontronite, an uncommon but particularly Fe-rich (> 12 wt.%) smectite. Importantly, this process is capable of liberating Fe (II) to solution, where it is available to biotic processes as an electron donor. In order to constrain the capacity of naturally-occurring marine bacteria to liberate structurally-coordinated Fe from the lattices of common clay minerals, we exposed a suite of 16 different clay minerals (0.8-13.9 wt.% Fe) to lab cultures of known Fe-reducer S. onenidensis MR-1 and to a natural consortium of Fe-reducing microbes from the San Pedro and Santa Monica Basins over timescales ranging from 7-120 days. Clay minerals were treated with Na-dithionite to extract surface-bound Fe prior to exposure. Crystallographic data and direct measurements of Fe in solution demonstrate the release of structural Fe from all clay minerals analyzed. Neoformation of illite and amorphous quartz were observed. The array of clay minerals and microbes used in this experiment complement past findings and suggest that common clay minerals may represent a large and previously unrecognized pool of bioavailable Fe in the world ocean that contributes significantly to biogeochemical cycling of Fe and C.

  5. Chemistry and mineralogy of clay minerals in Asian and Saharan dusts and the implications for iron availability

    NASA Astrophysics Data System (ADS)

    Jeong, G. Y.; Achterberg, E. P.

    2014-06-01

    Mineral dust supplied to remote ocean regions stimulates phytoplankton growth through delivery of micronutrients, notably iron (Fe). Although attention is usually paid to Fe (hydr)oxides as major sources of available Fe, Fe-bearing clay minerals are typically the dominant phase in mineral dust. The mineralogy and chemistry of clay minerals in dust particles, however, are largely unknown. We conducted microscopic identification and chemical analysis of the clay minerals in Asian and Saharan dust particles. Cross-sectional slices of dust particles were prepared by focused ion beam (FIB) techniques and analyzed by transmission electron microscopy (TEM) combined with energy dispersive X-ray spectroscopy (EDXS). TEM images of FIB slices revealed that clay minerals occurred as either nano-thin platelets or relatively thick plates. The nano-thin platelets included illite, smectite, illite-smectite mixed layers and their nanoscale mixtures (illite-smectite series clay minerals, ISCMs) which could not be resolved with an electron microbeam. EDXS chemical analysis of the clay mineral grains revealed that the average Fe content was 5.8% in nano-thin ISCM platelets assuming 14% H2O, while the Fe content of illite and chlorite was 2.8 and 14.8%, respectively. In addition, TEM and EDXS analyses were performed on clay mineral grains dispersed and loaded on microgrids. The average Fe content of clay mineral grains was 6.7 and 5.4% in Asian and Saharan dusts, respectively. A comparative X-ray diffraction analysis of bulk dusts showed that Saharan dust was more enriched in clay minerals than in Asian dust, while Asian dust was more enriched in chlorite. The average Fe / Si, Al / Si and Fe / Al molar ratios of the clay minerals, compared to previously reported chemistries of mineral dusts and leached solutions, indicated that dissolved Fe originated from clay minerals. Clay minerals, in particular nanocrystalline ISCMs and Fe-rich chlorite are important sources of available Fe in remote marine ecosystems. Further detailed analyses of the mineralogy and chemistry of clay minerals in global aerosols are required to determine the inputs of Fe available to surface ocean microbial communities.

  6. Effect of purity on adsorption capacities of a Mars-like clay mineral at different pressures

    NASA Technical Reports Server (NTRS)

    Jenkins, Traci; Mcdoniel, Bridgett; Bustin, Roberta; Allton, Judith H.

    1992-01-01

    There has been considerable interest in adsorption of carbon dioxide on Marslike clay minerals. Some estimates of the carbon dioxide reservoir capacity of the martian regolith were calculated from the amount of carbon dioxide adsorbed on the ironrich smectite nontronite under martian conditions. The adsorption capacity of pure nontronite could place upper limits on the regolith carbon dioxide reservoir, both at present martian atmospheric pressure and at the postulated higher pressures required to permit liquid water on the surface. Adsorption of carbon dioxide on a Clay Mineral Society standard containing nontronite was studied over a wide range of pressures in the absence of water. Similar experiments were conducted on the pure nontronite extracted from the natural sample. Heating curves were obtained to help characterize and determine the purity of the clay sample.

  7. Investigating the behaviour of Mg isotopes during the formation of clay minerals

    NASA Astrophysics Data System (ADS)

    Wimpenny, Joshua; Colla, Christopher A.; Yin, Qing-Zhu; Rustad, James R.; Casey, William H.

    2014-03-01

    We present elemental and isotopic data detailing how the Mg isotope system behaves in natural and experimentally synthesized clay minerals. We show that the bulk Mg isotopic composition (δ26Mg) of a set of natural illite, montmorillonite and kaolinite spans a 2‰ range, and that their isotopic composition depends strongly on a balance between the relative proportions of structural and exchangeable Mg. After acid leaching, these natural clays become relatively enriched in isotopically heavy Mg by between 0.2‰ and 1.6‰. Results of exchange experiments indicate that the Mg that has adsorbed to interlayer spaces and surface charged sites is relatively enriched in isotopically light Mg compared to the residual clay. The isotopic composition of this exchangeable Mg (-1.49‰ to -2.03‰) is characteristic of the isotopic composition of Mg found in many natural waters. Further experiments with an isotopically characterized MgCl2 solution shows that the clay minerals adsorb this exchangeable Mg with little or no isotopic fractionation, although we cannot discount the possibility that the uptake of exchangeable Mg does so with a slight preference for 24Mg. To characterize the behaviour of Mg isotopes during clay mineral formation we synthesized brucite (Mg(OH)2), which we consider to be a good analogue for the incorporation of Mg into the octahedral sheet of Mg-rich clay minerals or into the brucitic layer of clays such as chlorite. In our experiment the brucite mineral becomes enriched in the heavy isotopes of Mg while the corresponding solution is always relatively enriched in isotopically light Mg. The system reaches a steady state after 10 days with a final fractionation factor (αsolid-solution) of 1.0005 at near-neutral pH. This result is consistent with the general consensus that secondary clay minerals preferentially take up isotopically heavy Mg during their formation. However our results also show that exchangeable Mg is an important component within bulk clay minerals and can have an important influence over the bulk clay δ26Mg value. Modeling shows that in certain soils or sediments where the percentage of exchangeable Mg is >30% and the isotopic composition of the exchangeable Mg is around -2‰, the generation of bulk δ26Mg values of <-0.5‰ is likely. On a broader scale, Mg-rich minerals such as smectite and illite are likely to impart a stronger control over the Mg budget in clay rich sediments, and their high structural Mg component is likely to result in bulk sediment δ26Mg values that are closer in composition to the UCC. Despite this, results of modeling, together with experimental observation suggests that the uptake of exchangeable Mg into these clay rich sediments could cause a decrease in the bulk δ26Mg value by up to ˜0.3-0.4‰. This should be accounted for when assessing the δ26Mg value of sediments on a crustal scale.

  8. Heterogeneous uptake of the C1 to C4 organic acids on a swelling clay mineral

    NASA Astrophysics Data System (ADS)

    Hatch, C. D.; Gough, R. V.; Tolbert, M. A.

    2007-08-01

    Mineral aerosol is of interest due to its physiochemical impacts on the Earth's atmosphere. However, adsorbed organics could influence the chemical and physical properties of atmospheric mineral particles and alter their impact on the biosphere and climate. In this work, the heterogeneous uptake of a series of small organic acids on the swelling clay, Na-montmorillonite, was studied at 212 K as a function of relative humidity (RH), organic acid pressure and clay mass. A high vacuum chamber equipped with a quadrupole mass spectrometer and a transmission Fourier transform infrared spectrometer was used to detect the gas and condensed phases, respectively. Our results show that while the initial uptake efficiency was found to be independent of organic acid pressure, it increased linearly with increasing clay mass. Thus, the small masses studied allow access to the entire surface area of the clay sample with minimal effects due to surface saturation. Additionally, results from this study show that the initial uptake efficiency for butanoic (butyric) acid on the clay increases by an order of magnitude as the RH is raised from 0% to 45% RH at 212 K while the initial uptake efficiency of formic, acetic and propanoic (propionic) acids increases only slightly at higher humidities. However, the initial uptake efficiency decreases significantly in a short amount of time due to surface saturation effects. Thus, although the initial uptake efficiencies are appropriate for initial times, the fact that the uptake efficiency will decrease over time as the surface saturates should be considered in atmospheric models. Surface saturation results in sub-monolayer coverage of organic acid on montmorillonite under dry conditions and relevant organic acid pressures that increases with increasing humidity for all organic acids studied. Additionally, the presence of large organic acids may slightly enhance the water content of the clay above 45% RH. Our results indicate that heterogeneous uptake of organic acids on swelling clay minerals provides an important irreversible heterogeneous sink for these species.

  9. Modeling selenate adsorption behavior on oxides, clay minerals, and soils using the triple layer model

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Selenate adsorption behavior was investigated on amorphous aluminum oxide, amorphous iron oxide, goethite, clay minerals: kaolinites, montmorillonites, illite, and 18 soil samples from Hawaii, and the Southwestern and the Midwestern regions of the US as a function of solution pH. Selenate adsorpti...

  10. FINAL REPORT. MODELING OF CATION BINDING IN HYDRATED 2:1 CLAY MINERALS

    EPA Science Inventory

    Hydrated 2:1 clay minerals are high surface area, layered silicates that play a unique rolein determining the fate of radionuclides in the environment. This project consisted of developing and implementing computer simulation methods for molecular characterization of the swellin...

  11. Modeling selenite adsorption envelopes on oxides, clay minerals, and soils using the triple layer model

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Selenite adsorption behavior was investigated on amorphous aluminum and iron oxides, clay minerals: kaolinite, montmorillonite, and illite, and 45 surface and subsurface soil samples from the Southwestern and Midwestern regions of the USA as a function of solution pH. Selenite adsorption decreased ...

  12. Clay minerals in primitive meteorites and interplanetary dust 1

    NASA Technical Reports Server (NTRS)

    Zolensky, M. E.; Keller, L. P.

    1991-01-01

    Many meteorites and interplanetary dust particles (IDPs) with primitive compositions contain significant amounts of phyllosilicate minerals, which are generally interpreted as evidence of protoplanetary aqueous alteration at an early period of the solar system. These meteorites are chondrites (near solar composition) of the carbonaceous and ordinary varieties. The former are subdivided (according to bulk composition and petrology) into CI, CM, CV, CO, CR, and ungrouped classes. IDPs are extraterrestrial particulates, collected in stratosphere, which have chemical compositions indicative of a primitive origin; they are typically distinct from the primitive meteorites. Characterization of phyllosilicates in these materials is a high priority because of the important physico-chemical information they hold. The most common phyllosilicates present in chondritic extraterrestrial materials are serpentine-group minerals, smectites, and micas. We discuss these phyllosilicates and describe the interpretation of their occurrence in meteorites and IDPs and what this indicates about history of their parent bodies, which are probably the hydrous asteroids.

  13. Clay minerals in basin of Mexico lacustrine sediments and their influence on ion mobility in groundwater

    NASA Astrophysics Data System (ADS)

    Warren, C. J.; Rudolph, D. L.

    1997-09-01

    Semiconfined aquifers used as the principal water supply within the Basin of Mexico are overlain by lacustrine deposits that provide a degree of protection from contamination associated with metropolitan Mexico City. Solute transport behavior and the nature of chemical interactions with mineral components in these sediments is poorly understood. The objectives of this paper were to identify the clay mineral phases of the lacustrine sediments and to determine the significance of the exchange properties of the day minerals on contaminant transport processes. Samples obtained from two cores were separated into sand, silt, and clay-size fractions. The clay-size fraction was analyzed by X-ray diffraction and Fourier transform infrared spectroscopy and for specific surface area and pH-dependent cation and anion exchange capacity. The clay-sized fraction averaged 56% of the sediment. Analyses indicated that the clay was predominantly composed of a Si-rich allophane with approximately 30% montmorillonite. Halloysite was also present to a depth of about 1.5 m, but was absent deeper in the sediment. Kaolinite and illite, reported in previous studies, and imogolite were not found in the samples. Solute transport in the sediment was modeled to demonstrate the impact of exchange properties imparted by the allophane compared to other possible clay mineral assemblages. The predominance of allophane in the Basin of Mexico sediments is responsible for many of the fundamental characteristics of the material including: high porosity (0.8-0.9), high water content (200-400%), and an extremely high and pH-dependent cation exchange capacity. The pH of the pore water within the lacustrine sediments of the Basin of Mexico is typically between 6.5 and 12. Measured cation exchange values ranged from ≈ 450 meq kg -1 at pH 6.5 to ≈ 650 meq kg -1 at pH 12 which could produce variable cation mobility in the semiconfining aquitard. The simulations illustrated that allophane is very effective for retarding the leaching of cationic metals compared to other possible clay mineral suites, particularly at high pH values. Simulation of long-term infiltration indicated that trace metals will become concentrated in the clay matrix adjacent to fracture faces in the sediment near ground surface. As such, the aquitard behaves as an efficient barrier to the infiltration of cationic metals into the underlying aquifer.

  14. Is the geological concept of clay minerals appropriate for soil science? A literature-based and philosophical analysis

    NASA Astrophysics Data System (ADS)

    Churchman, G. Jock

    Data in the literature for soils that are dominated by each of the main types of clay minerals were examined and compared with those for reference clay minerals of the same types to determine the extent to which the nature and properties of clay-size minerals in soils could be explained by those of clay minerals with the same name from non-soil, ‘geological’ environments. Published information on soils from Australia, New Zealand and Iran was sourced for this study. The clay fractions of each of the soils are dominated by either one of the common phyllosilicates: kaolinite, halloysite, illite/mica, vermiculite, smectite, and palygorskite, or by the nanocrystalline mineral, allophane. Data for samples of kaolinite that had been extracted from soils from several countries (Australia, Thailand, Indonesia and Brazil) and purified before characterization have also been examined. In soils, each dominant clay mineral is generally associated with other materials, including iron oxides, other phyllosilicates and/or nanocrystalline minerals and organic matter. As the most studied example of an extracted phyllosilicate, kaolinite shows a wide range of properties in different soils, but a narrower range of properties within a particular locality. However, almost all of the soil kaolinites studied have larger specific surface areas and higher cation exchange capacities than reference kaolinites. The literature also reveals that, among phyllosilicates in soils, illites have a wide range of potassium contents, expandable minerals (vermiculites and smectites) may be interlayered by hydroxy-Al species particularly, and smectitic layers often occur interstratified with other layers, including those of illite, kaolinite and halloysite. The variability of soil phyllosilicates and their common association with other, often poorly crystallized but highly reactive minerals and compounds can be explained by their formation in the highly heterogeneous and dynamic soil environment. Phyllosilicates from non-soil or geological sources are poor models for the representation of secondary clay-size minerals in soils. In philosophical terms, the reduction of soil mineralogy to mineralogy as it is practiced within geology is misleading because of the differences between the minerals formed in soil and geological environments. In other words, clay minerals as they are defined as mineralogical entities for geology are of a different ‘kind’ to clay minerals in soils and cannot serve as ‘types’ or ‘stereotypes’ to enable explanation of the contribution of secondary clay-size minerals to soil properties or behavior. It is more useful to view clay minerals in soils as secondary inorganic compounds of clay-size than to follow their definition for non-soil purposes as plastic phyllosilicate minerals.

  15. Cesium adsorption/desorption behavior of clay minerals considering actual contamination conditions in Fukushima.

    PubMed

    Mukai, Hiroki; Hirose, Atsushi; Motai, Satoko; Kikuchi, Ryosuke; Tanoi, Keitaro; Nakanishi, Tomoko M; Yaita, Tsuyoshi; Kogure, Toshihiro

    2016-01-01

    Cesium adsorption/desorption experiments for various clay minerals, considering actual contamination conditions in Fukushima, were conducted using the (137)Cs radioisotope and an autoradiography using imaging plates (IPs). A 50 μl solution containing 0.185 ~ 1.85 Bq of (137)Cs (10(-11) ~ 10(-9 )molL(-1) of (137)Cs) was dropped onto a substrate where various mineral particles were arranged. It was found that partially-vermiculitized biotite, which is termed "weathered biotite" (WB) in this study, from Fukushima sorbed (137)Cs far more than the other clay minerals (fresh biotite, illite, smectite, kaolinite, halloysite, allophane, imogolite) on the same substrate. When WB was absent on the substrate, the amount of (137)Cs sorbed to the other clay minerals was considerably increased, implying that selective sorption to WB caused depletion of radiocesium in the solution and less sorption to the coexisting minerals. Cs-sorption to WB continued for about one day, whereas that to ferruginous smectite was completed within one hour. The sorbed (137)Cs in WB was hardly leached with hydrochloric acid at pH 1, particularly in samples with a longer sorption time. The presence/absence of WB sorbing radiocesium is a key factor affecting the dynamics and fate of radiocesium in Fukushima. PMID:26868138

  16. Cesium adsorption/desorption behavior of clay minerals considering actual contamination conditions in Fukushima

    NASA Astrophysics Data System (ADS)

    Mukai, Hiroki; Hirose, Atsushi; Motai, Satoko; Kikuchi, Ryosuke; Tanoi, Keitaro; Nakanishi, Tomoko M.; Yaita, Tsuyoshi; Kogure, Toshihiro

    2016-02-01

    Cesium adsorption/desorption experiments for various clay minerals, considering actual contamination conditions in Fukushima, were conducted using the 137Cs radioisotope and an autoradiography using imaging plates (IPs). A 50 μl solution containing 0.185 ~ 1.85 Bq of 137Cs (10-11 ~ 10-9 molL-1 of 137Cs) was dropped onto a substrate where various mineral particles were arranged. It was found that partially-vermiculitized biotite, which is termed “weathered biotite” (WB) in this study, from Fukushima sorbed 137Cs far more than the other clay minerals (fresh biotite, illite, smectite, kaolinite, halloysite, allophane, imogolite) on the same substrate. When WB was absent on the substrate, the amount of 137Cs sorbed to the other clay minerals was considerably increased, implying that selective sorption to WB caused depletion of radiocesium in the solution and less sorption to the coexisting minerals. Cs-sorption to WB continued for about one day, whereas that to ferruginous smectite was completed within one hour. The sorbed 137Cs in WB was hardly leached with hydrochloric acid at pH 1, particularly in samples with a longer sorption time. The presence/absence of WB sorbing radiocesium is a key factor affecting the dynamics and fate of radiocesium in Fukushima.

  17. Cesium adsorption/desorption behavior of clay minerals considering actual contamination conditions in Fukushima

    PubMed Central

    Mukai, Hiroki; Hirose, Atsushi; Motai, Satoko; Kikuchi, Ryosuke; Tanoi, Keitaro; Nakanishi, Tomoko M.; Yaita, Tsuyoshi; Kogure, Toshihiro

    2016-01-01

    Cesium adsorption/desorption experiments for various clay minerals, considering actual contamination conditions in Fukushima, were conducted using the 137Cs radioisotope and an autoradiography using imaging plates (IPs). A 50 μl solution containing 0.185 ~ 1.85 Bq of 137Cs (10−11 ~ 10−9 molL−1 of 137Cs) was dropped onto a substrate where various mineral particles were arranged. It was found that partially-vermiculitized biotite, which is termed “weathered biotite” (WB) in this study, from Fukushima sorbed 137Cs far more than the other clay minerals (fresh biotite, illite, smectite, kaolinite, halloysite, allophane, imogolite) on the same substrate. When WB was absent on the substrate, the amount of 137Cs sorbed to the other clay minerals was considerably increased, implying that selective sorption to WB caused depletion of radiocesium in the solution and less sorption to the coexisting minerals. Cs-sorption to WB continued for about one day, whereas that to ferruginous smectite was completed within one hour. The sorbed 137Cs in WB was hardly leached with hydrochloric acid at pH 1, particularly in samples with a longer sorption time. The presence/absence of WB sorbing radiocesium is a key factor affecting the dynamics and fate of radiocesium in Fukushima. PMID:26868138

  18. Neocrystallization, fabrics and age of clay minerals from an exposure of the Moab Fault, Utah

    USGS Publications Warehouse

    Solum, J.G.; van der Pluijm, B.A.; Peacor, D.R.

    2005-01-01

    Pronounced changes in clay mineral assemblages are preserved along the Moab Fault (Utah). Gouge is enriched up to ???40% in 1Md illite relative to protolith, whereas altered protolith in the damage zone is enriched ???40% in illite-smectite relative to gouge and up to ???50% relative to protolith. These mineralogical changes indicate that clay gouge is formed not solely through mechanical incorporation of protolith, but also through fault-related authigenesis. The timing of mineralization is determined using 40Ar/39Ar dating of size fractions of fault rocks with varying detrital and authigenic clay content. We applied Ar dating of illite-smectite samples, as well as a newer approach that uses illite polytypes. Our analysis yields overlapping, early Paleocene ages for neoformed (1Md) gouge illite (63??2 Ma) and illite-smectite in the damage zone (60??2 Ma), which are compatible with results elsewhere. These ages represent the latest period of major fault motion, and demonstrate that the fault fabrics are not the result of recent alteration. The clay fabrics in fault rocks are poorly developed, indicating that fluids were not confined to the fault zone by preferentially oriented clays; rather we propose that fluids in the illite-rich gouge were isolated by adjacent lower permeability, illite-smectite-bearing rocks in the damage zone. ?? 2005 Elsevier Ltd. All rights reserved.

  19. Leaching of clay minerals in a limestone environment

    USGS Publications Warehouse

    Carroll, D.; Starkey, H.C.

    1959-01-01

    Water saturated with CO2 at about 25??C was percolated through mixed beds of limestone or marble fragments and montmorillonite, "illite" and kaolinite in polyethylene tubes for six and fortyfive complete runs. The leachates were analysed for SiO2, A12O3 and Fe2O3, but only SiO2 was found. The minerals lost SiO2 in this order: montmorillonite > kaolinite > "illite". The differential removal of SiO2 during the short period of these experiments suggests a mechanism for the accumulation of bauxite deposits associated with limestones. ?? 1959.

  20. Genesis of clay mineral assemblages and micropaleoclimatic implications in the Tertiary Powder River Basin, Wyoming

    SciTech Connect

    Flores, R.M.; Weaver, J.N. ); Bossiroy, D.; Thorez, J. )

    1990-05-01

    An x-ray diffraction (XRD) study was undertaken on the clay mineralogy of the early Tertiary coal-bearing sequences of the Powder River basin. The vertical and lateral distribution of alternating fluvial conglomerates, sandstones, mudstones, shales, coals, and paleosols reveals a transition from alluvial fans along the basin margin to an alluvial plain and peat bogs basinward. Samples included unweathered shales and mudstones from a borehole and a variety of corresponding surface outcrop samples of Cambrian to Eocene age. Samples older than Tertiary were collected along the basin margin specifically to determine the potential source of parent material during Tertiary sedimentation. XRD analyses were performed on the <2-{mu}m fraction prepared as oriented aggregates. To investigate the materials in their natural state, no chemical pre-treatments the authors applied before the analysis. A series of specific post-treatments, consisting of catonic saturation (Li+, K+), a solution with polyalcohols, heating, acid attack and hydrazine saturation was selectively applied. These post-treatments permit a good discrimination between the mimetic clay minerals such as smectite and illite-smectite mixed layers that constitute the bulk of the clay fraction in the Tertiary rocks. When analyzed only using routine XRD, these swelling minerals are apparently uniformly distributed in the fluvial sedimentary rocks and are better interpreted as a single smectitic population. However, the post-treatments clearly differentiate both qualitatively and quantitatively this smectitic stock. Other clays include illite and kaolinite, which have different degrees of crystallinity, and minor interstratified clays (i.e., illite-chlorite, chlorite-smectite). The clay minerals in pre-Tertiary (and pedogenic) materials are different from those in the Tertiary rocks.

  1. Adsorption of herbicide paraquat by clay mineral regenerated from spent bleaching earth.

    PubMed

    Tsai, Wen-Tien; Lai, Chi-Wei

    2006-06-30

    The adsorption of herbicide paraquat (as model adsorbate) in aqueous solution onto regenerated clay mineral from bleaching earth waste has been studied in a batch reaction system. The adsorption rate has been investigated under the controlled process parameters including initial pH, salinity and temperature. Based on the high affinity between cationic paraquat and clay mineral, a pseudo-second order model has been developed using experimental data to predict the rate constant of adsorption, and equilibrium adsorption capacity. The results showed that the adsorption process could be satisfactorily described with the reaction model and were reasonably explained by assuming a competitive adsorption mechanism in the ion exchange process. Further, the fitted adsorption capacity at equilibrium decreased with increasing temperature. It implied that the strong interaction might play an important role in the paraquat-clay system. Overall, the results from this study demonstrated that the clay resource regenerated from bleaching earth waste could be used as a low-cost mineral adsorbent for the removal of environmental cationic organic pollutants from the aqueous solution. PMID:16343760

  2. Modified clay minerals efficiency against chemical and biological warfare agents for civil human protection.

    PubMed

    Plachá, Daniela; Rosenbergová, Kateřina; Slabotínský, Jiří; Kutláková, Kateřina Mamulová; Studentová, Soňa; Martynková, Gražyna Simha

    2014-04-30

    Sorption efficiencies of modified montmorillonite and vermiculite of their mono ionic Na and organic HDTMA and HDP forms were studied against chemical and biological warfare agents such as yperite and selected bacterial strains. Yperite interactions with modified clay minerals were observed through its capture in low-density polyethylene foil-modified clay composites by measuring yperite gas permeation with using chemical indication and gas chromatography methods. The antibacterial activities of synthetized organoclays were tested against selected Gram-positive and Gram-negative bacterial species in minimum inhibitory concentration tests. The obtained results showed a positive influence of modified clay minerals on the significant yperite breakthrough-time increase. The most effective material was the polyethylene-Na form montmorillonite, while the polyethylene-Na form vermiculite showed the lowest efficiency. With increasing organic cations loading in the interlayer space the montmorillonite efficiency decreased, and in the case of vermiculite an opposite effect was observed. Generally the modified montmorillonites were more effective than modified vermiculites. The HDP cations seem to be more effective compare to the HDTMA. The antibacterial activity tests confirmed efficiency of all organically modified clay minerals against Gram-positive bacteria. The confirmation of antibacterial activity against Y. pestis, plague bacteria, is the most interesting result of this part of the study. PMID:24603112

  3. Clay mineral distribution and provenance in the Heuksan mud belt, Yellow Sea

    NASA Astrophysics Data System (ADS)

    Cho, Hyen Goo; Kim, Soon-Oh; Kwak, Kyeong Yoon; Choi, Hunsoo; Khim, Boo-Keun

    2015-12-01

    The Heuksan mud belt (HMB), located in the southeastern Yellow Sea, runs parallel to the southwest coast of Korea. In this study, the distribution and relative contribution of four major clay minerals are investigated using 101 surface sediment samples collected in the course of KIOST (2001, 2010, 2011) and KIGAM (2012) cruises, as well as 33 river sediment samples (four from the Huanghe River, three from the Changjiang River, and 26 from Korean rivers) in order to clarify the provenance of fine-grained sediments in the HMB. Based on this currently largest and most robust dataset available for interpretation, the clay mineral assemblages of the fine-grained sediments in the HMB are found to be on average composed of 64.7% illite, 17.9% chlorite, 11.4% kaolinite, and 5.9% smectite. Overall, the clay mineral assemblages are similar in both the northern and the southern parts of the HMB, although smectite seems to be relatively enriched in the southern part, whereas kaolinite is slightly more dominant in the northern part. This clearly indicates that the clays are mostly derived from Korean rivers and, in the southern part of the HMB, partly also from the Huanghe River in China. The new data thus confirm and strengthen the tentative interpretation of some earlier work based on a more limited dataset.

  4. Bioremediating Oil Spills in Nutrient Poor Ocean Waters Using Fertilized Clay Mineral Flakes: Some Experimental Constraints

    PubMed Central

    Warr, Laurence N.; Friese, André; Schwarz, Florian; Schauer, Frieder; Portier, Ralph J.; Basirico, Laura M.; Olson, Gregory M.

    2013-01-01

    Much oil spill research has focused on fertilizing hydrocarbon oxidising bacteria, but a primary limitation is the rapid dilution of additives in open waters. A new technique is presented for bioremediation by adding nutrient amendments to the oil spill using thin filmed minerals comprised largely of Fullers Earth clay. Together with adsorbed N and P fertilizers, filming additives, and organoclay, clay flakes can be engineered to float on seawater, attach to the oil, and slowly release contained nutrients. Our laboratory experiments of microbial activity on weathered source oil from the Deepwater Horizon spill in the Gulf of Mexico show fertilized clay treatment significantly enhanced bacterial respiration and consumption of alkanes compared to untreated oil-in-water conditions and reacted faster than straight fertilization. Whereas a major portion (up to 98%) of the alkane content was removed during the 1 month period of experimentation by fertilized clay flake interaction; the reduced concentration of polyaromatic hydrocarbons was not significantly different from the non-clay bearing samples. Such clay flake treatment could offer a way to more effectively apply the fertilizer to the spill in open nutrient poor waters and thus significantly reduce the extent and duration of marine oil spills, but this method is not expected to impact hydrocarbon toxicity. PMID:23864952

  5. Bioremediating oil spills in nutrient poor ocean waters using fertilized clay mineral flakes: some experimental constraints.

    PubMed

    Warr, Laurence N; Friese, André; Schwarz, Florian; Schauer, Frieder; Portier, Ralph J; Basirico, Laura M; Olson, Gregory M

    2013-01-01

    Much oil spill research has focused on fertilizing hydrocarbon oxidising bacteria, but a primary limitation is the rapid dilution of additives in open waters. A new technique is presented for bioremediation by adding nutrient amendments to the oil spill using thin filmed minerals comprised largely of Fullers Earth clay. Together with adsorbed N and P fertilizers, filming additives, and organoclay, clay flakes can be engineered to float on seawater, attach to the oil, and slowly release contained nutrients. Our laboratory experiments of microbial activity on weathered source oil from the Deepwater Horizon spill in the Gulf of Mexico show fertilized clay treatment significantly enhanced bacterial respiration and consumption of alkanes compared to untreated oil-in-water conditions and reacted faster than straight fertilization. Whereas a major portion (up to 98%) of the alkane content was removed during the 1 month period of experimentation by fertilized clay flake interaction; the reduced concentration of polyaromatic hydrocarbons was not significantly different from the non-clay bearing samples. Such clay flake treatment could offer a way to more effectively apply the fertilizer to the spill in open nutrient poor waters and thus significantly reduce the extent and duration of marine oil spills, but this method is not expected to impact hydrocarbon toxicity. PMID:23864952

  6. Effect of clay minerals present in aquifer soils on the adsorption and desorption of hydrophobic organic compounds

    SciTech Connect

    Ghosh, D.R. ); Keinath, T.M. )

    1994-02-01

    Adsorption of hydrophobic organic compounds (HOCs) onto clay minerals and organic matter present in soils results in retarding their mobility. To study the impact of clay minerals on HOC sorption, kinetic and equilibrium studies were performed using naphthalene as a test surrogate contaminant. The results of these studies indicated that expandable clay minerals (clays that expand and expose large internal surface area on wetting), such as montmorillonite and vermiculite, had a significant impact on naphthalene partitioning. A mathematical model was developed from the equilibrium data which related clay mineral concentrations with the naphthalene partition coefficient. Equilibrium desorption studies were also performed by adding a micellar solution of a surfactant mixture (50:50) of Tween 20 and Aerosol AY-65 to mobilize the adsorbed naphthalene. The surfactant mixture was generally unable to mobilize the sorbed contaminant due to sorption irreversibility and adsorption hysteresis. 36 refs., 1 fig., 5 tabs.

  7. Iron-rich clay minerals on Mars - Potential sources or sinks for hydrogen and indicators of hydrogen loss over time

    NASA Technical Reports Server (NTRS)

    Burt, D. M.

    1989-01-01

    Although direct evidence is lacking, indirect evidence suggests that iron-rich clay minerals or poorly-ordered chemical equivalents are widespread on the Martian surface. Such clays can act as sources or sinks for hydrogen ('hydrogen sponges'). Ferrous clays can lose hydrogen and ferric clays gain it by the coupled substitution Fe(3+)O(Fe(2+)OH)-1, equivalent to minus atomic H. This 'oxy-clay' substitution involves only proton and electron migration through the crystal structure, and therefore occurs nondestructively and reversibly, at relatively low temperatures. The reversible, low-temperature nature of this reaction contrasts with the irreversible nature of destructive dehydroxylation (H2O loss) suffered by clays heated to high temperatures. In theory, metastable ferric oxy-clays formed by dehydrogenation of ferrous clays over geologic time could, if exposed to water vapor, extract the hydrogen from it, releasing oxygen.

  8. Reactive Clay Minerals in a land use sequence of disturbed soils of the Belgian Loam Belt

    NASA Astrophysics Data System (ADS)

    Barao, Lucia; Vandevenne, Floor; Ronchi, Benedicta; Meire, Patrick; Govers, Gerard; Struyf, Eric

    2014-05-01

    Clay minerals play a key role in soil biogeochemistry. They can stabilize organic matter, improve water storage, increase cation exchange capacity of the soil (CEC) and lower nutrient leaching. Phytoliths - the biogenic silica bodies (BSi) deposited in cell walls of plants - are important Si pools in soil horizons due to their higher solubility compared to minerals. They provide the source of Si for plant uptake in short time scales, as litter dissolves within soils. In a recent study, we analyzed the BSi pool differences across a set of different land uses (forests, pastures, croplands) in 6 long-term disturbed (multiple centuries) soil sites in the Belgium Loam Belt. Results from a simultaneous chemical extraction in 0.5M NaOH of Si and Al, showed that soils were depleted in the BSi pool while showing high levels of reactive secondary clay minerals, mainly in the deeper horizons and especially in the forests and the croplands. During the extraction, clays were similar in reactivity to the biogenic pool of phytoliths. In order to study the kinetics in a more natural environment, batch dissolution experiments were conducted. Samples from different soil depths for each land use site (0.5 g) were mixed with 0.5 L of demineralised water modified to pH 4, 7 and 10. Subsamples of 2 ml were taken during 3 months. In the end of the period, results for pH 7 showed that in the pastures, where reactive clays were almost absent, the ratio Si/RSi (defined as the Si concentration in the end of the batch experiment divided by the reactive silica extracted from the soil with the alkaline extraction) was lower than 0.005%. The same ratio was higher in the mineral horizons of forests (Si/RSi>0.01%) and croplands (0.005% < Si/RSi <0.01%) where clay minerals were the dominant fraction. These preliminary results highlight the clay minerals' strong potential for Si mobilization. More attention should be paid to this important fraction as it can contribute strongly to Si availability, in close competition with phytoliths and other soluble amorphous Si forms, strongly interfering with frequently applied methods to quantify biogenic Si in soils.

  9. Influence of clay minerals on sorption and bioreduction of arsenic under anoxic conditions.

    PubMed

    Ghorbanzadeh, Nasrin; Lakzian, Amir; Halajnia, Akram; Kabra, Akhil N; Kurade, Mayur B; Lee, Dae S; Jeon, Byong-Hun

    2015-12-01

    Adsorption of As(V) on various clay minerals including kaolinite (KGa-1), montmorillonite (SWy-1) and nontronites (NAU-1 and NAU-2), and subsequent bioreduction of sorbed As(V) to As(III) by bacterium Shewanella putrefaciens strain CN-32 were investigated. Nontronites showed relatively higher sorption capacity for As(V) primarily due to higher iron oxide content. Freundlich equation well described the sorption of As(V) on NAU-1, NAU-2 and SWy-1, while As(V) sorption isotherm with KGa-1 fitted well in the Langmuir model. The bacterium rapidly reduced 50% of dissolved As(V) to As(III) in 2 h, followed by its complete reduction (>ca. 98%) within 12 h. In contrast, sorption of As(V) to the mineral surfaces interferes with the activity of bacterium, resulting in low bioreduction of As(V) by 27% for 5 days of incubation. S. putrefaciens also promoted the reduction of Fe(III) present in the clay mineral to Fe(II). This study indicates that the sorption and subsequent bioreduction of As(V) on clay minerals can significantly influence the mobility of As(V) in subsurface environment. PMID:25971375

  10. Clay mineral continental amplifier for marine carbon sequestration in a greenhouse ocean

    PubMed Central

    Kennedy, Martin J.; Wagner, Thomas

    2011-01-01

    The majority of carbon sequestration at the Earth’s surface occurs in marine continental margin settings within fine-grained sediments whose mineral properties are a function of continental climatic conditions. We report very high mineral surface area (MSA) values of 300 and 570 m2 g in Late Cretaceous black shales from Ocean Drilling Program site 959 of the Deep Ivorian Basin that vary on subcentennial time scales corresponding with abrupt increases from approximately 3 to approximately 18% total organic carbon (TOC). The observed MSA changes with TOC across multiple scales of variability and on a sample-by-sample basis (centimeter scale), provides a rigorous test of a hypothesized influence on organic carbon burial by detrital clay mineral controlled MSA. Changes in TOC also correspond with geochemical and sedimentological evidence for water column anoxia. Bioturbated intervals show a lower organic carbon loading on mineral surface area of 0.1 mg-OC m-2 when compared to 0.4 mg-OC m-2 for laminated and sulfidic sediments. Although either anoxia or mineral surface protection may be capable of producing TOC of < 5%, when brought together they produced the very high TOC (10–18%) apparent in these sediments. This nonlinear response in carbon burial resulted from minor precession-driven changes of continental climate influencing clay mineral properties and runoff from the African continent. This study identifies a previously unrecognized land–sea connection among continental weathering, clay mineral production, and anoxia and a nonlinear effect on marine carbon sequestration during the Coniacian-Santonian Oceanic Anoxic Event 3 in the tropical eastern Atlantic. PMID:21576498

  11. Clay mineral continental amplifier for marine carbon sequestration in a greenhouse ocean.

    PubMed

    Kennedy, Martin J; Wagner, Thomas

    2011-06-14

    The majority of carbon sequestration at the Earth's surface occurs in marine continental margin settings within fine-grained sediments whose mineral properties are a function of continental climatic conditions. We report very high mineral surface area (MSA) values of 300 and 570 m(2) g in Late Cretaceous black shales from Ocean Drilling Program site 959 of the Deep Ivorian Basin that vary on subcentennial time scales corresponding with abrupt increases from approximately 3 to approximately 18% total organic carbon (TOC). The observed MSA changes with TOC across multiple scales of variability and on a sample-by-sample basis (centimeter scale), provides a rigorous test of a hypothesized influence on organic carbon burial by detrital clay mineral controlled MSA. Changes in TOC also correspond with geochemical and sedimentological evidence for water column anoxia. Bioturbated intervals show a lower organic carbon loading on mineral surface area of 0.1 mg-OC m(-2) when compared to 0.4 mg-OC m(-2) for laminated and sulfidic sediments. Although either anoxia or mineral surface protection may be capable of producing TOC of < 5%, when brought together they produced the very high TOC (10-18%) apparent in these sediments. This nonlinear response in carbon burial resulted from minor precession-driven changes of continental climate influencing clay mineral properties and runoff from the African continent. This study identifies a previously unrecognized land-sea connection among continental weathering, clay mineral production, and anoxia and a nonlinear effect on marine carbon sequestration during the Coniacian-Santonian Oceanic Anoxic Event 3 in the tropical eastern Atlantic. PMID:21576498

  12. Aqueous dissolution, solubilities and thermodynamic stabilities of common aluminosilicate clay minerals: Kaolinite and smectites

    USGS Publications Warehouse

    May, Howard M.; Klnniburgh, D.G.; Helmke, P.A.; Jackson, M.L.

    1986-01-01

    Determinations of the aqueous solubilities of kaolinite at pH 4, and of five smectite minerals in suspensions set between pH 5 and 8, were undertaken with mineral suspensions adjusted to approach equilibrium from over- and undersaturation. After 1,237 days, Dry Branch, Georgia kaolinite suspensions attained equilibrium solubility with respect to the kaolinite, for which Keq = (2.72 ?? 0.35) ?? 107. The experimentally determined Gibbs free energy of formation (??Gf,2980) for the kaolinite is -3,789.51 ?? 6.60 kj mol-1. Equilibrium solubilities could not be determined for the smectites because the composition of the solution phase in the smectite suspensions appeared to be controlled by the formation of gibbsite or amorphous aluminum hydroxide and not by the smectites, preventing attempts to determine valid ??Gf0 values for these complex aluminosilicate clay minerals. Reported solubility-based ??Gf0 determinations for smectites and other variable composition aluminosilicate clay minerals are shown to be invalid because of experimental deficiencies and of conceptual flaws arising from the nature of the minerals themselves. Because of the variable composition of smectites and similar minerals, it is concluded that reliable equilibrium solubilities and solubility-derived ??Gf0 values can neither be rigorously determined by conventional experimental procedures, nor applied in equilibriabased models of smectite-water interactions. ?? 1986.

  13. Subsurface water and clay mineral formation during the early history of Mars.

    PubMed

    Ehlmann, Bethany L; Mustard, John F; Murchie, Scott L; Bibring, Jean-Pierre; Meunier, Alain; Fraeman, Abigail A; Langevin, Yves

    2011-11-01

    Clay minerals, recently discovered to be widespread in Mars's Noachian terrains, indicate long-duration interaction between water and rock over 3.7 billion years ago. Analysis of how they formed should indicate what environmental conditions prevailed on early Mars. If clays formed near the surface by weathering, as is common on Earth, their presence would indicate past surface conditions warmer and wetter than at present. However, available data instead indicate substantial Martian clay formation by hydrothermal groundwater circulation and a Noachian rock record dominated by evidence of subsurface waters. Cold, arid conditions with only transient surface water may have characterized Mars's surface for over 4 billion years, since the early-Noachian period, and the longest-duration aqueous, potentially habitable environments may have been in the subsurface. PMID:22051674

  14. Role of clay minerals in oil-forming reactions.

    PubMed

    Geatches, Dawn L; Clark, Stewart J; Greenwell, Hugh C

    2010-03-18

    Mineral-catalyzed decarboxylation reactions are important in both crude oil formation and, increasingly, biofuel production. In this study we examined decarboxylation reactions of a model fatty acid, propionic acid, C(2)H(5)COOH, to an alkane, C(2)H(6), in a model of pyrophillite with an isomorphic substitution of aluminum in the tetrahedral layer. We model a postulated reaction mechanism (Almon, W. R.; Johns, W. D. 7th International Meeting on Organic Geochemistry 1975, Vol. 7) to ascertain the role of Al substitution and a counterion in decarboxylation reactions. We employ a periodic cell, planewave, ab initio DFT computation to examine the total energies and the frontier orbitals of different model sets, including the effects of charge on the reaction, the effect of Al substitution, and the role of Na counterions. The results show that an uncharged system with a sodium counterion is most feasible for catalyzing the decarboxylation reaction in an Al-substituted pyrophillite and, also, that analysis of the orbitals is a better indicator of a reaction than charge alone. PMID:20155955

  15. Clay-mineral assemblages from some levels of K-118 drill core of Maha Sarakham evaporites, northeastern Thailand

    NASA Astrophysics Data System (ADS)

    Suwanich, Parkorn

    Clay-mineral assemblages in Middle Clastic, Middle Salt, Lower Clastic, Potash Zone, and Lower Salt, totalling 13 samples from K-118 drill core, in the Maha Sarakham Formation, Khorat Basin, northeastern Thailand were studied. The clay-size particles were separated from the water-soluble salt by water leaching. Then the samples were leached again in the EDTA solution and separated into clay-size particles by using the timing sedimentation. The EDTA-clay residues were divided and analyzed by using the XRD and XRF method. The XRD peaks show that the major-clay minerals are chlorite, illite, and mixed-layer corrensite including traces of rectorite? and paragonite? The other clay-size particles are quartz and potassium feldspar. The XRF results indicate Mg-rich values and moderate MgAl atom ratio values in those clay minerals. The variable Fe, Na, and K contents in the clay-mineral assemblages can explain the environment of deposition compared to the positions of the samples from the core. Hypothetically, mineralogy and the chemistry of the residual assemblages strongly indicate that severe alteration and Mg-enrichment of normal clay detritus occurred in the evaporite environment through brine-sediment interaction. The various Mg-enrichment varies along the various members reflecting whether sedimentation is near or far from the hypersaline brine.

  16. Pedogenic formation of montmorillonite from a 2:1-2:2 intergrade clay mineral

    USGS Publications Warehouse

    Malcolm, R.L.; Nettleton, W.D.; McCracken, R.J.

    1969-01-01

    Montmorillonite was found to be the dominant clay mineral in surface horizons of certain soils of the North Carolina Coastal Plain whereas a 2:1-2:2 intergrade clay mineral was dominant in subjacent horizons. In all soils where this clay mineral sequence was found, the surface horizon was low in pH (below 4??5) and high in organic matter content. In contrast, data from studies of other soils of this region (Weed and Nelson, 1962) show that: (1) montmorillonite occurs infrequently; (2) maximum accumulation of the 2:1-2:2 intergrade normally occurs in the surface horizon and decreases with depth in the profile; (3) organic matter contents are low; and (4) pH values are only moderately acid (pH 5-6). It is theorized that the montmorillonite in the surface horizon of the soils studied originated by pedogenic weathering of the 2:1-2:2 intergrade clay mineral. The combined effects of low pH (below 4??5) and high organic matter content in surface horizons are believed to be the agents responsible for this mineral transformation. The protonation and solubilization (reverse of hydrolysis) of Al-polymers in the interlayer of expansible clay minerals will occur at or below pH 4??5 depending on the charge and steric effects of the interlayer. A low pH alone may cause this solubilization and thus mineral transformation, but in the soils studied the organic matter is believed to facilitate and accelerage the transformation. The intermediates of organic matter decomposition provide an acid environment, a source of protons, and a source of watersoluble mobile organic substances (principally fulvic acids) which have the ability to complex the solubilized aluminum and move it down the profile. This continuous removal of solubilized aluminum would provide for a favorable gradient for aluminum solubilization. The drainage class or position in a catena is believed to be less important than the chemical factors in formation of montmorillonite from 2:1-2:2 intergrade, because montmorillonite is present in all drainage classes if the surface horizon is low in pH and high in organic matter. ?? 1969.

  17. Application of short-wave infrared (SWIR) spectroscopy in quantitative estimation of clay mineral contents

    NASA Astrophysics Data System (ADS)

    You, Jinfeng; Xing, Lixin; Liang, Liheng; Pan, Jun; Meng, Tao

    2014-03-01

    Clay minerals are significant constituents of soil which are necessary for life. This paper studied three types of clay minerals, kaolinite, illite, and montmorillonite, for they are not only the most common soil forming materials, but also important indicators of soil expansion and shrinkage potential. These clay minerals showed diagnostic absorption bands resulting from vibrations of hydroxyl groups and structural water molecules in the SWIR wavelength region. The short-wave infrared reflectance spectra of the soil was obtained from a Portable Near Infrared Spectrometer (PNIS, spectrum range: 1300~2500 nm, interval: 2 nm). Due to the simplicity, quickness, and the non-destructiveness analysis, SWIR spectroscopy has been widely used in geological prospecting, chemical engineering and many other fields. The aim of this study was to use multiple linear regression (MLR) and partial least squares (PLS) regression to establish the optimizing quantitative estimation models of the kaolinite, illite and montmorillonite contents from soil reflectance spectra. Here, the soil reflectance spectra mainly refers to the spectral reflectivity of soil (SRS) corresponding to the absorption-band position (AP) of kaolinite, illite, and montmorillonite representative spectra from USGS spectral library, the SRS corresponding to the AP of soil spectral and soil overall spectrum reflectance values. The optimal estimation models of three kinds of clay mineral contents showed that the retrieval accuracy was satisfactory (Kaolinite content: a Root Mean Square Error of Calibration (RMSEC) of 1.671 with a coefficient of determination (R2) of 0.791; Illite content: a RMSEC of 1.126 with a R2 of 0.616; Montmorillonite content: a RMSEC of 1.814 with a R2 of 0.707). Thus, the reflectance spectra of soil obtained form PNIS could be used for quantitative estimation of kaolinite, illite and montmorillonite contents in soil.

  18. The First X-ray Diffraction Patterns of Clay Minerals from Gale Crater

    NASA Astrophysics Data System (ADS)

    Bristow, T.; Blake, D.; Bish, D. L.; Vaniman, D.; Ming, D. W.; Morris, R. V.; Chipera, S.; Rampe, E. B.; Farmer, J. D.; Treiman, A. H.; Downs, R.; Morrison, S.; Achilles, C.; Des Marais, D. J.; Crisp, J. A.; Sarrazin, P.; Morookian, J.; Grotzinger, J. P.; Team, M.

    2013-12-01

    The Mars Science Laboratory (MSL) Rover, Curiosity spent ~150 sols at Yellowknife Bay (YKB) studying a section of fluvio-lacustrine sedimentary rocks (with potential indications of volcanic influence), informally known as the Yellowknife Bay formation. YKB lies in a distal region of the Peace Vallis alluvial fan, which extends from the northern rim of Gale Crater toward the dune field at the base of Mt Sharp. Sedimentological and stratigraphic observations are consistent with the Yellowknife Bay formation being part of a distal fan deposit, which could be as young as middle Hesperian to even early Amazonian in age (~3.5 to 2.5 Ga). The Yellowknife Bay formation hosts a unit of mudstone called the Sheepbed member. Curiosity obtained powdered rock samples from two drill holes in the Sheepbed Member, named John Klein and Cumberland, and delivered them to instruments in Curiosity. Data from CheMin, a combined X-ray diffraction (XRD)/X-ray fluorescence instrument (XRF), has allowed detailed mineralogical analysis of mudstone powders revealing a clay mineral component of ~20 wt.% in each sample. The clay minerals are important indicators of paleoenvironmental conditions and sensitive recorders of post-depositional alteration processes. The XRD pattern of John Klein reveals a 02l band consistent with a trioctahedral phyllosilicate. A broad peak at ~10A with a slight inflexion at ~12A indicates the presence of 2:1 type clay minerals in the John Klein sample. The trioctahedral nature of the clay minerals, breadth of the basal reflection, and presence of a minor component with larger basal spacing suggests that John Klein contains a trioctahedral smectite (probably saponite), whose interlayer is largely collapsed because of the low-humidity conditions. The XRD patterns show no evidence of corrensite (mixed-layer chlorite/smectite) or chlorite, which are typical diagenetic products of trioctahedral smectites when subjected to burial and heating >60°C in the presence of water. Given estimated geothermal gradients on Mars temperatures <60 °C might still be consistent with (but do not require) moderate burial. However, our ability to identify interstratified minerals is greatly limited by the lack of access to traditional treatments methods used in the lab (e.g., ethylene glycol solvation). Our preferred explanation for the origin of trioctahedral smectites in Sheepbed mudstone is in situ production via reaction of olivine, water and Si-bearing amorphous material, an important mudstone component detected by XRD. Elevated levels of magnetite in the Sheepbed and the trioctahedral monomineralic nature of the clay minerals support this model. These observations, combined with previous studies of olivine stability, support the persistence of circum-neutral hydrous conditions for thousands of years at YKB.

  19. Authigenic clay minerals in the Rustler Formation, WIPP (Waste Isolation Pilot Plant) Site area, New Mexico

    SciTech Connect

    Brookins, D.G.; Ward, D.B. . Dept. of Geology); Lambert, S.J. )

    1990-05-01

    Transuranic waste is planned for disposal in the Late Permian evaporites of the Delaware Basin, southeastern New Mexico, at the WIPP Site. The disposal horizon is located in the bedded halite of the Salado Formation, which is overlain by the impure haliteanhydrite(gypsum)-siltstone-mudstone of the Rustler Formation. The Rustler Formation also contains two dolomite members, the Magenta and Culebra, which transmit water. The Culebra Member is suspected to have actively interacted with waters at time(s) from the Late Permian to the present, and it is important to assess the reactivity of these waters in conjunction with WIPP stability. We have investigated the Rb--Sr systematics of clay minerals from the Culebra Member and elsewhere in the Rustler Formation. The authigenic fraction is especially sensitive to chemical and isotopic exchange with waters, and an episodic exposure to a large amount of water will reset the clay minerals to such a time. Our data yield 259 {plus minus} 22 MaRb--Sr isochron, which is consistent with the Late Permian age of the Rustler Formation. This age demonstrates that age-determining cations in these clay minerals have preserved their isotopic and chemical integrity since the Late Permian. 16 refs.

  20. Can clay minerals account for the behavior of non-asperity on the subducting plate interface?

    NASA Astrophysics Data System (ADS)

    Katayama, Ikuo; Kubo, Tatsuro; Sakuma, Hiroshi; Kawai, Kenji

    2015-12-01

    Seismicity along the subducting plate interface shows regional variation, which has been explained by the seismic asperity model where large earthquakes occur at strongly coupled patches that are surrounded by weakly coupled regions. This suggests that the subduction plate interface is heterogeneous in terms of frictional properties; however, the mechanism producing the difference between strong and weak couplings remains poorly understood. Here, we propose that the heterogeneity of the fluid pathway and of the spatial distribution of clay minerals plays a key role in the formation of non-asperity at the subducting plate interface. We use laboratory measurements of frictional properties to show that clay minerals on a simulated fault interface are characterized by weak and slow recovery, whereas other materials such as quartz show relatively quick recovery and thereby strong coupling on the fault surface. Aqueous fluids change the mineralogy at the plate interface by producing clay minerals due to hydrate reactions, suggesting that the hydrated weakly coupled regions act as a non-asperity and form a barrier to rupture propagation along the plate boundary at the depths of seismogenic zone.

  1. Ancient and recent clay formation on Mars as revealed from a global survey of hydrous minerals in crater central peaks

    NASA Astrophysics Data System (ADS)

    Sun, Vivian Z.; Milliken, Ralph E.

    2015-12-01

    Clay minerals on Mars have commonly been interpreted as the remnants of pervasive water-rock interaction during the Noachian period (>3.7 Ga). This history has been partly inferred by observations of clays in central peaks of impact craters, which often are presumed uplifted from depth. However, combined mineralogical and morphological analyses of individual craters have shown that some central peak clays may represent post-impact, possibly authigenic processes. Here we present a global survey of 633 central peaks to assess their hydrous minerals and the prevalence of uplifted, detrital, and authigenic clays. Central peak regions are examined using high-resolution Compact Reconnaissance Imaging Spectrometer for Mars and High Resolution Imaging Science Experiment data to identify hydrous minerals and place their detections in a stratigraphic and geologic context. We find that many occurrences of Fe/Mg clays and hydrated silica are associated with potential impact melt deposits. Over 35% of central peak clays are not associated with uplifted rocks; thus, caution must be used when inferring deeper crustal compositions from surface mineralogy of central peaks. Uplifted clay-bearing rocks suggest the Martian crust hosts clays to depths of at least 7 km. We also observe evidence for increasing chloritization with depth, implying the presence of fluids in the upper portions of the crust. Our observations are consistent with widespread Noachian/Early Hesperian clay formation, but a number of central peak clays are also suggestive of clay formation during the Amazonian. These results broadly support current paradigms of Mars' aqueous history while adding insight to global crustal and diagenetic processes associated with clay mineral formation and stability.

  2. Investigating the Thermal Limit of Clay Minerals for Applications in Nuclear Waste Repository Design

    NASA Astrophysics Data System (ADS)

    Matteo, E. N.; Miller, A. W.; Kruichak, J.; Mills, M.; Tellez, H.; Wang, Y.

    2013-12-01

    Clay minerals are likely candidates to aid in nuclear waste isolation due to their low permeability, favorable swelling properties, and high cation sorption capacities. Establishing the thermal limit for clay minerals in a nuclear waste repository is a potentially important component of repository design, as flexibility of the heat load within the repository can have a major impact on the selection of repository design. For example, the thermal limit plays a critical role in the time that waste packages would need to cool before being transferred to the repository. Understanding the chemical and physical changes that occur in clay minerals at various temperatures above the current thermal limit (of 100 °C) can enable decision-makers with information critical to evaluating the potential trade-offs of increasing the thermal limit within the repository. Most critical is gaining understanding of how varying thermal conditions in the repository will impact radionuclide sorption and transport in clay materials either as engineered barriers or as disposal media. A variety of clays (illite, mixed layer illite/smectite, montmorillonite, and palygorskite) were heated for a range of temperatures between 100-500 °C. These samples were characterized by a variety of methods, including nitrogen adsorption, x-ray diffraction, thermogravimetric analysis, barium chloride exchange for cation exchange capacity (CEC), and iodide sorption. The nitrogen porosimetry shows that for all the clays, thermally-induced changes in BET surface area are dominated by collapse/creation of the microporosity, i.e. pore diameters < 17 angstroms. Changes in micro porosity (relative to no heat treatment) are most significant for heat treatments 300 °C and above. Alterations are also seen in the chemical properties (CEC, XRD, iodide sorption) of clays, and like pore size distribution changes, are most significant above 300 °C. Overall, the results imply that changes seen in pores size distribution correlate with cation exchange capacity and cation exchange processes. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's Nation Nuclear Security Administration under contract DE-AC04-94AL85000. SAND Number: 2013-6352A.

  3. Ammonia transformations and abundance of ammonia oxidizers in a clay soil underlying a manure pond.

    PubMed

    Sher, Yonatan; Baram, Shahar; Dahan, Ofer; Ronen, Zeev; Nejidat, Ali

    2012-07-01

    Unlined manure ponds are constructed on clay soil worldwide to manage farm waste. Seepage of ammonia-rich liquor into underlying soil layers contributes to groundwater contamination by nitrate. To identify the possible processes that lead to the production of nitrate from ammonia in this oxygen-limited environment, we studied the diversity and abundance of ammonia-transforming microorganisms under an unlined manure pond. The numbers of ammonia-oxidizing bacteria and anammox bacteria were most abundant in the top of the soil profile and decreased significantly with depth (0.5 m), correlating with soil pore-water ammonia concentrations and soil ammonia concentrations, respectively. On the other hand, the numbers of ammonia-oxidizing archaea were relatively constant throughout the soil profile (10(7) amoA copies per g(soil)). Nitrite-oxidizing bacteria were detected mainly in the top 0.2 m. The results suggest that nitrate accumulation in the vadose zone under the manure pond could be the result of complete aerobic nitrification (ammonia oxidation to nitrate) and could exist as a byproduct of anammox activity. While the majority of the nitrogen was removed within the 0.5-m soil section, possibly by combined anammox and heterotrophic denitrification, a fraction of the produced nitrate leached into the groundwater. PMID:22385337

  4. DE-FG02-06ER15364: Final Technical Report Nanoscale Reactivity of Clays, Clay Analogues (Micas), and Clay Minerals

    SciTech Connect

    Nagy, Kathryn L.

    2008-07-03

    The project objectives were to determine the nanoscale to molecular scale structure of the interface between muscovite mica and aqueous solutions containing various sorbates and to explore systematics that control the incorporation of inorganic and organic chemical components during aging of nanoparticles of iron-oxides and aluminosilicate clays. The basal surface of phyllosilicates is a primary sorbent of environmental contaminants, natural organic matter, and nutrients. Micas are also superb atomically-flat substrates used in materials science and surface physics applications. We applied X-ray scattering techniques using high brilliance synchrotron radiation to investigate molecular-scale details of mica’s interface structure in solutions containing common and toxic cations, anions, and natural organic molecules. Nanoparticles are ubiquitous in the environment and have a high capacity for sorbing contaminants through the combined effects of their high surface areas and pH-dependent surface charge. Aging of nanoparticles from metastable to stable phases can be inhibited by sorption of nonstructural components, but exact mechanisms are unknown. We synthesized Fe-oxides and aluminosilicate clay minerals from aqueous solutions in the presence of selected anions, and organic molecules, and quantified the uptake of these additives during aging and some implications for nanoparticle formation.

  5. Changes in Clay Mineral Preferred Orientations During Progressive Sediment Accretion in the Nankai Accretionary Prism

    NASA Astrophysics Data System (ADS)

    Sunderland, E. B.; Morgan, J. K.

    2002-12-01

    The development of clay mineral preferred orientations (CPOs) in sediments at the toe of an accretionary prism is controlled by a variety of parameters, including stress state, stress history, intergranular cementation, and proximity to discrete deformation structures. Typically, uncemented clay-rich sediments develop a horizontal preferred orientation during burial, which becomes more developed with depth due to increasing normal stress in consolidating sediments. Onset of accretion introduces a horizontal compressive stress that rotates mineral grains out of the horizontal plane. Intergranular cementation can inhibit grain rotation and CPO development, and may be correlated with increased brittle deformation. Using scanning electron microscopy, we examined CPOs of clay-rich sediments from drill cores collected during Ocean Drilling Project Leg 190 at the Nankai accretionary margin. Sediments were recovered from the tectonically deformed toe of the prism and from a seaward reference site. We compared CPOs from these cores to study changes in sediment microfabrics with depth and intensity of deformation, in particular, close to deformation structures such as faults, fractures, and deformation bands. Initial observations suggest that sediments far from discrete deformation structures have nearly uniform CPOs across a sample, whereas sediment microfabrics associated with brittle structures may vary dramatically over micro-scale distances. This implies that local stresses associated with the generation of brittle structures can overprint previously developed sediment microfabrics, obscuring the past deformation record. Clarifying the progressive changes in clay mineral preferred orientations during early sediment accretion is critical to better our understanding of the stress history and tectonic evolution of accretionary margins.

  6. Growth of iron(III)-reducing bacteria on clay minerals as the sole electron acceptor and comparison of growth yields on a variety of oxidized iron forms.

    PubMed

    Kostka, Joel E; Dalton, Dava D; Skelton, Hayley; Dollhopf, Sherry; Stucki, Joseph W

    2002-12-01

    Smectite clay minerals are abundant in soils and sediments worldwide and are typically rich in Fe. While recent investigations have shown that the structural Fe(III) bound in clay minerals is reduced by microorganisms, previous studies have not tested growth with clay minerals as the sole electron acceptor. Here we have demonstrated that a pure culture of Shewanella oneidensis strain MR-1 as well as enrichment cultures of Fe(III)-reducing bacteria from rice paddy soil and subsurface sediments are capable of conserving energy for growth with the structural Fe(III) bound in smectite clay as the sole electron acceptor. Pure cultures of S. oneidensis were used for more detailed growth rate and yield experiments on various solid- and soluble-phase electron acceptors [smectite, Fe(III) oxyhydroxide FeOOH, Fe(III) citrate, and oxygen] in the same minimal medium. Growth was assessed as direct cell counts or as an increase in cell carbon (measured as particulate organic carbon). Cell counts showed that similar growth of S. oneidensis (10(8) cells ml(-1)) occurred with smectitic Fe(III) and on other Fe forms [amorphous Fe(III) oxyhydroxide, and Fe citrate] or oxygen as the electron acceptor. In contrast, cell yields of S. oneidensis measured as the increase in cell carbon were similar on all Fe forms tested while yields on oxygen were five times higher, in agreement with thermodynamic predictions. Over a range of particle loadings (0.5 to 4 g liter(-1)), the increase in cell number was highly correlated to the amount of structural Fe in smectite reduced. From phylogenetic analysis of the complete 16S rRNA gene sequences, a predominance of clones retrieved from the clay mineral-reducing enrichment cultures were most closely related to the low-G+C gram-positive members of the Bacteria (Clostridium and Desulfitobacterium) and the delta-Proteobacteria (members of the Geobacteraceae). Results indicate that growth with smectitic Fe(III) is similar in magnitude to that with Fe(III) oxide minerals and is dependent upon the mineral surface area available. Iron(III) bound in clay minerals should be considered an important electron acceptor supporting the growth of bacteria in soils or sedimentary environments. PMID:12450850

  7. [Effect of treatments of hydrogen peroxide and sodium dithionite-citrate-bicarbonate on clay minerals of red earth sediments].

    PubMed

    Li, Rong-Biao; Hong, Han-Lie; Yin, Ke; Wang, Chao-Wen; Gao, Wen-Peng; Han, Wen; Wu, Qing-Feng

    2013-04-01

    As classical procedures for pretreatment of soil sediments, hydrogen peroxide (H2O2) and sodium dithionite-citrate-bicarbonate (DCB) treatment methods are very important in removing the organic matter and iron oxides acting as cementing agents in the soils. However, both of these methods have less been focused on the effect on the clay minerals when separating. Here, we report the comparable methods between H2O2 and DCB to reveal their effect on clay minerals in red earth sediments using X-ray diffraction (XRD). The XRD results suggested that mineral particles can be totally decentralized by either H2O2 or DCB method in the soils and high purity clay minerals can be obtained by separating quartz and other impurities from clay minerals effectively. However, the XRD data were distorted by the DCB treatment owning to the cation exchange between Na+ and interlayer cation. On the contrary, the authentic data can be obtained by H2O2 treatment. Therefore, the H2O2 treatment seems to be a more appropriate method to obtain authentic information of clay mineralogy when separating of clay minerals from red earth sediments. PMID:23841441

  8. Impact of clay mineral on air oxidation of PAH-contaminated soils.

    PubMed

    Biache, Coralie; Kouadio, Olivier; Lorgeoux, Catherine; Faure, Pierre

    2014-09-01

    This work investigated the impact of a clay mineral (bentonite) on the air oxidation of the solvent extractable organic matters (EOMs) and the PAHs from contaminated soils. EOMs were isolated from two coking plant soils and mixed with silica sand or bentonite. These samples, as well as raw soils and bentonite/soil mixtures, were oxidized in air at 60 and 100 °C for 160 days. Mineralization was followed by measuring the CO2 produced over the experiments. EOM, polycyclic aromatic compound (PAC), including PAH, contents were also determined. Oxidation led to a decrease in EOM contents and PAH concentrations, these diminutions were enhanced by the presence of bentonite. Transfer of carbon from EOM to insoluble organic matter pointed out a condensation phenomenon leading to a stabilization of the contamination. Higher mineralization rates, observed during the oxidation of the soil/bentonite mixtures, seem to indicate that this clay mineral had a positive influence on the transformation of PAC into CO2. PMID:24816462

  9. In situ measurements of tetraphenylboron degradation kinetics on clay mineral surfaces by IR

    SciTech Connect

    Hunter, D.B.; Bertsch, P.M. )

    1994-04-01

    An attenuated total reflectance Fourier transform infrared (ATR-IR) spectroscopic method has been developed to quantitatively measure, in situ, the surface-facilitated degradation of tetraphenylboron (TPB) in fully aquated clay pastes. Two pathways for degradation of TPB could be studied both independently and simultaneously. Surface-facilitated oxidation of TPB to diphenylboric acid (DPBA) at Lewis acid sites on clay mineral surfaces was investigated on three members of the smectite family of clays. No degradation of TPB occurred on hectorite, which contains no structural Fe. TPB degraded to DPBA on montmorillonite and nontronite. A color change in nontronite indicated the production of mixed valence Fe[sup 3+]-O-Fe[sup 2+] states and clearly demonstrates the reduction of structural iron during the course of the reaction. The degradation of TPB to triphenylboron (TriPB) at Bronsted acid sites could also be measured on aluminum-saturated clays either independently on hectorite or simultaneously to the Lewis acid reaction on montmorillonite by the ATR-IR method. First-order rate models are developed for both reactions and describe the data well. 28 refs., 4 figs., 1 tab.

  10. Synthesis of ZnO nanoparticles on a clay mineral surface in dimethyl sulfoxide medium.

    PubMed

    Németh, József; Rodríguez-Gattorno, Geonel; Díaz, David; Vázquez-Olmos, América R; Dékány, Imre

    2004-03-30

    Nanocrystalline ZnO particles have been prepared with different methods using zinc cyclohexanebutyrate as precursor in dimethyl sulfoxide (DMSO) medium via alkaline hydrolysis. A series of preparations were carried out in the presence of layered silicates (kaolinite and montmorillonite). It was revealed by different measurement techniques that the presence of the clay minerals has a stabilization influence on the size of the ZnO nanocrystals. UV-vis absorption spectra show a blue shift when the nanoparticles are prepared in the presence of the clay minerals. The average particle diameters calculated from the Brus equation ranged from 2.6 to 13.0 nm. The UV-vis spectra of the synthesized nanoparticles did not show any red shift after 2-3 days, demonstrating that stable ZnO nanocrystals are present in the dispersions. The presence of the ZnO nanoparticles was also proven by fluorescence measurements. A number of the nanoparticles are incorporated into the interlamellar space of the clays, and an intercalated structure is formed as proven by X-ray diffraction (XRD) measurements. The size of the nanoparticles in the interlamellar space is in the range of 1-2 nm according to the XRD patterns. Transmission electron microscopy and high-resolution transmission electron microscopy investigations were applied to determine directly the particle size and the size distribution of the nanoparticles. PMID:15835163

  11. Abundance retrieval of hydrous minerals around the Mars Science Laboratory landing site in Gale crater, Mars

    NASA Astrophysics Data System (ADS)

    Lin, Honglei; Zhang, Xia; Shuai, Tong; Zhang, Lifu; Sun, Yanli

    2016-02-01

    The detection of hydrous minerals on Mars is of great importance for revealing the early water environment as well as possible biotic activity. However, few studies focus on abundance retrieval of hydrous minerals for some difficulties. In this paper, we studied the area around the Mars Science Laboratory (MSL) landing site, to identify hydrous minerals and retrieve their abundance. Firstly, the distribution of hydrous minerals was extracted using their hydration features. Then, a sparse unmixing algorithm was applied along with the CRISM spectral library to retrieve the abundance of hydrous minerals in this area. As a result, seven hydrous minerals were retrieved, i.e. actinolite, montmorillonite, saponite, jarosite, halloysite, szomolnokite and magnesite and, the total concentration of all hydrous minerals was as high as 40 vol% near the lower reaches of Mount Sharp. Our results were consistent with results from related research and the in-situ analysis of the MSL rover Curiosity.

  12. Mineral contributions to atrazine and alachlor sorption in soil mixtures of variable organic carbon and clay content

    NASA Astrophysics Data System (ADS)

    Grundl, Tim; Small, Greg

    1993-09-01

    A sediment mixing approach was taken to systematically vary the organic carbon (oc) and clay content (cm) of a suite of organic-poor, clay-rich sediments. Organic carbon content ranged from 3.2% to 0.4% and clay content ranged from 24% to 51%. Atrazine and alachlor were shown to sorb to both natural organic carbon and clay minerals. Partition coefficients to natural organic carbon ( Koc) were found to be 217 and 412 L/kg organic carbon for atrazine and alachlor, respectively. Partition coefficients to the clay fraction were found to be 3.5 and 4.9 L/kg clay for atrazine and alachlor, respectively. When expressed in terms of surface area, the partition coefficients to clay for atrazine and alachlor were 1.80·10 -5 and 2.51·10 -5 L/m 2 clay, respectively. Critical cm/oc ratios at which mineral phase sorption accounts for 50% of the total are defined. Implications for the modelling of herbicide movement in the subsurface if mineral phase sorption is ignored is discussed.

  13. Hydrogen and oxygen isotope exchange reactions between clay minerals and water

    USGS Publications Warehouse

    O'Neil, J.R.; Kharaka, Y.K.

    1976-01-01

    The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100-350?? for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100??. Exchange rates were 3-5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure. Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O18 exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O18 exchange. At 350?? kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O18 exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor. ?? 1976.

  14. Removal of phosphate ions from aqueous solution using Tunisian clays minerals and synthetic zeolite.

    PubMed

    Hamdi, Noureddine; Srasra, Ezzeddine

    2012-01-01

    Phosphate ions are usually considered to be responsible for the algal bloom in receiving water bodies and aesthetic problems in water. From the environmental point of view, the management of such contaminant and valuable resource is very important. The present work deals with the removal of phosphate ions from aqueous solutions using kaolinitic and smectic clay minerals and synthetic zeolite as adsorbent. The pH effect and adsorption kinetic were studied. It was found that phosphate could be efficiently removed at acidic pH (between 4 and 6) and the second order model of kinetics is more adopted for all samples. The isotherms of adsorption of phosphate ions by the two clays and the zeolite samples show that the zeolite has the highest rate of uptake (52.9 mg P/g). Equilibrium data were well fitted with Langmuir and Freundlich isotherm. PMID:22894095

  15. Molecular simulation of carbon dioxide, brine, and clay mineral interactions and determination of contact angles.

    PubMed

    Tenney, Craig M; Cygan, Randall T

    2014-01-01

    Capture and subsequent geologic storage of CO2 in deep brine reservoirs plays a significant role in plans to reduce atmospheric carbon emission and resulting global climate change. The interaction of CO2 and brine species with mineral surfaces controls the ultimate fate of injected CO2 at the nanoscale via geochemistry, at the pore-scale via capillary trapping, and at the field-scale via relative permeability. We used large-scale molecular dynamics simulations to study the behavior of supercritical CO2 and aqueous fluids on both the hydrophilic and hydrophobic basal surfaces of kaolinite, a common clay mineral. In the presence of a bulk aqueous phase, supercritical CO2 forms a nonwetting droplet above the hydrophilic surface of kaolinite. This CO2 droplet is separated from the mineral surface by distinct layers of water, which prevent the CO2 droplet from interacting directly with the mineral surface. Conversely, both CO2 and H2O molecules interact directly with the hydrophobic surface of kaolinite. In the presence of bulk supercritical CO2, nonwetting aqueous droplets interact with the hydrophobic surface of kaolinite via a mixture of adsorbed CO2 and H2O molecules. Because nucleation and precipitation of minerals should depend strongly on the local distribution of CO2, H2O, and ion species, these nanoscale surface interactions are expected to influence long-term mineralization of injected carbon dioxide. PMID:24410258

  16. Syn- and post-sedimentary controls on clay mineral assemblages in a tectonically active basin, Andean Argentinean foreland

    NASA Astrophysics Data System (ADS)

    Do Campo, Margarita; Nieto, Fernando; del Papa, Cecilia; Hongn, Fernando

    2014-07-01

    In the northern part of the Calchaquí Valley (NW Argentina), Palaeogene Andean foreland sediments are represented by a 1400-metre-thick continental succession (QLC: Quebrada de Los Colorados Formation) consisting of claystones, siltstones, sandstones, and conglomerates representing sedimentation in fluvial-alluvial plains and alluvial fan settings. To understand the main syn- and postsedimentary variables controlling the clay mineral assemblages of this succession, we have studied the fine-grained clastic sediments by X-ray diffraction and electron microscopy, along with a detailed sedimentary facies analysis, for two representative sections. In the northern section, the whole succession was sampled and analysed by XRD, whereas in the second section, a control point 15 km to the south, only the basal levels were analysed. The XRD study revealed a strong contrast in clay mineral assemblages between these two sections as well as with sections in the central Calchaquí Valley studied previously. In the northernmost part of the study area, a complete evolution from smectite at the top to R3 illite/smectite mixed-layers plus authigenic kaolinite at the bottom, through R1-type mixed-layers in between, has been recognized, indicating the attainment of late diagenesis. In contrast, the clay mineral assemblages of equivalent foreland sediments cropping out only 15 km to the south contain abundant smectite and micas, subordinate kaolinite and chlorite, and no I/S mixed-layers to the bottom of the sequence. Early diagenetic conditions were also inferred in a previous study for equivalent sediments of the QLC Formation cropping out to the south, in the central Calchaquí Valley, as smectite occurs in basal strata. Burial depths of approximately 3000 m were estimated for the QLC Formation in the central and northern Calchaquí Valley; in addition, an intermediate to slightly low geothermal gradient can be considered likely for both areas as foreland basins are regarded as hypothermal basins. Consequently, the attainment of late diagenesis in the northernmost study area cannot be explained by significant differences in burial depth nor in geothermal gradient in relation to the section 15 km to the south nor with the central Calchaquí Valley. The formation of R3 mixed-layer I/S and authigenic kaolinite in the northern study area was most likely controlled by the circulation of hot, deep fluids along the reverse faults that bounded the Calchaquí valley. These faults were active during the Cenozoic, as evidenced by the syndepositional deformation features preserved in the studied sediments. Stress could also have been a driving force in burial diagenesis at the R3 mixed-layer I/S stage in these young continental sediments.

  17. Clays, specialty

    USGS Publications Warehouse

    Virta, R.L.

    1998-01-01

    Part of a special section on the state of industrial minerals in 1997. The state of the specialty clay industry worldwide for 1997 is discussed. The specialty clays mined in the U.S. are ball clay, fuller's earth, bentonite, fire clay, and kaolin. Sales of specialty clays in the U.S. were around 17 Mt in 1997. Approximately 53 kt of specialty clays were imported.

  18. Adsorption of iron cyanide complexes onto clay minerals, manganese oxide, and soil.

    PubMed

    Kang, Dong-Hee; Schwab, A Paul; Johnston, C T; Banks, M Katherine

    2010-09-01

    The adsorption characteristics of an iron cyanide complex, soluble Prussian blue KFe(III)[Fe(II)(CN)(6)], were evaluated for representative soil minerals and soil at pH 3.7, 6.4 and 9.7. Three specimen clay minerals (kaolinite, montmorillonite, and illite), two synthesized manganese oxides (birnessite and cryptomelane), and a Drummer soil from Indiana were used as the adsorbents. Surface protonation of variable charge sites increased with decreasing pH yielding positively charged sites on crystal edges and enhancing the attractive force between minerals and iron cyanide complexes. Anion adsorption on clays often is correlated to the metal content of the adsorbent, and a positive relationship was observed between iron or aluminum content and Prussian blue adsorption. Illite had high extractable iron and adsorbed more ferro-ferricyande anion, while kaolinite and montmorillonite had lower extractable iron and adsorbed less. However, less pH effect was observed on the adsorption of iron cyanide to manganese oxides. This may due to the manganese oxide mediated oxidation of ferrocyanide [Fe(II)(CN)(6)(4-)], to ferricyanide [Fe(III)(CN)(6)(3-)], which has a low affinity for manganese oxides. PMID:20665323

  19. [Research on characteristics of soil clay mineral evolution in paddy field and dry land by XRD spectrum].

    PubMed

    Zhang, Zhi-dan; Li, Qiao; Luo, Xiang-li; Jiang, Hai-chao; Zheng, Qing-fu; Zhao, Lan-po; Wang, Ji-hong

    2014-08-01

    The present paper took the typical saline-alkali soil in Jilin province as study object, and determinated the soil clay mineral composition characteristics of soil in paddy field and dry land. Then XRD spectrum was used to analyze the evolutionary mechanism of clay mineral in the two kinds of soil. The results showed that the physical and chemical properties of soil in paddy field were better than those in dry land, and paddy field would promote the weathering of mineral particles in saline-alkali soil and enhance the silt content. Paddy field soil showed a strong potassium-removal process, with a higher degree of clay mineral hydration and lower degree of illite crystallinity. Analysis of XRD spectrum showed that the clay mineral composition was similar in two kinds of soil, while the intensity and position of diffraction peak showed difference. The evolution process of clay mineral in dry land was S/I mixture-->vermiculite, while in paddy field it was S/I mixture-->vermiculite-->kaolinite. One kind of hydroxylated 'chlorite' mineral would appear in saline-alkali soil in long-term cultivated paddy field. Taking into account that the physical and chemical properties of soil in paddy field were better then those in dry land, we could know that paddy field could help much improve soil structure, cultivate high-fertility soil and improve saline-alkali soil. This paper used XRD spectrum to determine the characteristics of clay minerals comprehensively, and analyzed two'kinds of land use comparatively, and was a new perspective of soil minerals study. PMID:25508755

  20. [Research on characteristics of soil clay mineral evolution in paddy field and dry land by XRD spectrum].

    PubMed

    Zhang, Zhi-dan; Li, Qiao; Luo, Xiang-li; Jiang, Hai-chao; Zheng, Qing-fu; Zhao, Lan-po; Wang, Ji-hong

    2014-08-01

    The present paper took the typical saline-alkali soil in Jilin province as study object, and determinated the soil clay mineral composition characteristics of soil in paddy field and dry land. Then XRD spectrum was used to analyze the evolutionary mechanism of clay mineral in the two kinds of soil. The results showed that the physical and chemical properties of soil in paddy field were better than those in dry land, and paddy field would promote the weathering of mineral particles in saline-alkali soil and enhance the silt content. Paddy field soil showed a strong potassium-removal process, with a higher degree of clay mineral hydration and lower degree of illite crystallinity. Analysis of XRD spectrum showed that the clay mineral composition was similar in two kinds of soil, while the intensity and position of diffraction peak showed difference. The evolution process of clay mineral in dry land was S/I mixture-->vermiculite, while in paddy field it was S/I mixture-->vermiculite-->kaolinite. One kind of hydroxylated 'chlorite' mineral would appear in saline-alkali soil in long-term cultivated paddy field. Taking into account that the physical and chemical properties of soil in paddy field were better then those in dry land, we could know that paddy field could help much improve soil structure, cultivate high-fertility soil and improve saline-alkali soil. This paper used XRD spectrum to determine the characteristics of clay minerals comprehensively, and analyzed two'kinds of land use comparatively, and was a new perspective of soil minerals study. PMID:25474976

  1. Inelastic neutron scattering and molecular simulation of the dynamics of interlayer water in smectite clay minerals

    SciTech Connect

    Cygan, Randall T.; Daemen, Luke L.; Ilgen, Anastasia G.; Krumhansl, James L.; Nenoff, Tina M.

    2015-11-16

    The study of mineral–water interfaces is of great importance to a variety of applications including oil and gas extraction, gas subsurface storage, environmental contaminant treatment, and nuclear waste repositories. Understanding the fundamentals of that interface is key to the success of those applications. Confinement of water in the interlayer of smectite clay minerals provides a unique environment to examine the interactions among water molecules, interlayer cations, and clay mineral surfaces. Smectite minerals are characterized by a relatively low layer charge that allows the clay to swell with increasing water content. Montmorillonite and beidellite varieties of smectite were investigated to compare the impact of the location of layer charge on the interlayer structure and dynamics. Inelastic neutron scattering of hydrated and dehydrated cation-exchanged smectites was used to probe the dynamics of the interlayer water (200–900 cm–1 spectral region) and identify the shift in the librational edge as a function of the interlayer cation. Molecular dynamics simulations of equivalent phases and power spectra, derived from the resulting molecular trajectories, indicate a general shift in the librational behavior with interlayer cation that is generally consistent with the neutron scattering results for the monolayer hydrates. Both neutron scattering and power spectra exhibit librational structures affected by the location of layer charge and by the charge of the interlayer cation. Furthermore, divalent cations (Ba2+ and Mg2+) characterized by large hydration enthalpies typically exhibit multiple broad librational peaks compared to monovalent cations (Cs+ and Na+), which have relatively small hydration enthalpies.

  2. Inelastic neutron scattering and molecular simulation of the dynamics of interlayer water in smectite clay minerals

    DOE PAGESBeta

    Cygan, Randall T.; Daemen, Luke L.; Ilgen, Anastasia G.; Krumhansl, James L.; Nenoff, Tina M.

    2015-11-16

    The study of mineral–water interfaces is of great importance to a variety of applications including oil and gas extraction, gas subsurface storage, environmental contaminant treatment, and nuclear waste repositories. Understanding the fundamentals of that interface is key to the success of those applications. Confinement of water in the interlayer of smectite clay minerals provides a unique environment to examine the interactions among water molecules, interlayer cations, and clay mineral surfaces. Smectite minerals are characterized by a relatively low layer charge that allows the clay to swell with increasing water content. Montmorillonite and beidellite varieties of smectite were investigated to comparemore » the impact of the location of layer charge on the interlayer structure and dynamics. Inelastic neutron scattering of hydrated and dehydrated cation-exchanged smectites was used to probe the dynamics of the interlayer water (200–900 cm–1 spectral region) and identify the shift in the librational edge as a function of the interlayer cation. Molecular dynamics simulations of equivalent phases and power spectra, derived from the resulting molecular trajectories, indicate a general shift in the librational behavior with interlayer cation that is generally consistent with the neutron scattering results for the monolayer hydrates. Both neutron scattering and power spectra exhibit librational structures affected by the location of layer charge and by the charge of the interlayer cation. Furthermore, divalent cations (Ba2+ and Mg2+) characterized by large hydration enthalpies typically exhibit multiple broad librational peaks compared to monovalent cations (Cs+ and Na+), which have relatively small hydration enthalpies.« less

  3. Atomic-level studies of the depletion in reactive sites during clay mineral dissolution

    SciTech Connect

    Sanders, Rebecca L.; Washton, Nancy M.; Mueller, Karl T.

    2012-06-20

    Environmental weathering is typically viewed as a macroscopic phenomenon that is based on a number of competing atomic- or molecular-level processes. One important process is the release of metal or metalloid elements into solution at the water-rock interface. To both explain and predict environmental weathering, the atomic-level “reactive sites” on the surfaces of minerals must be characterized and quantified. Whether these sites are atomic in nature, represented by a chemical bond, or comprise a more complex assemblage of covalently or ionically linked atoms or molecules, the kinetic rate of atomic release (dissolution) depends on the available reactive surface. For one important class of materials, clay minerals, their reactive surface areas are a challenge to quantify as it is well recognized that there are two distinct types of surfaces: edge sites and basal planes1-3. Clay dissolution rates continuously decrease over time as reactive edge sites are preferentially depleted4. Changes in reactive surface area and the difficulties in quantifying this elusive variable have often been cited as one key reason for the complexity in developing accurate rate equations3,5,6. In this work, we demonstrate a solid-state nuclear magnetic resonance (SSNMR) method for counting the number of reactive surface sites on a defined quantity of a clay mineral. Using this SSNMR proxy7-9, changes in reactive surface area were monitored for a series of batch dissolution experiments of low-defect kaolinite KGa-1b at 21 ºC and pH 3 over the course of 80 days. While no changes (within error) were observed for specific surface area (as determined from BET gas isotherm data), the SSNMR proxy revealed decreases in the number of reactive surface sites per gram of kaolinite as a function of dissolution time. This observation can be tied to a concomitant decrease in the rates of release of Si and Al into solution. These results further highlight the need to account for changes in reactive surface area when developing and using dissolution rate models for clay minerals and other heterogeneous materials in the environment.

  4. Ball clay

    USGS Publications Warehouse

    Virta, R.L.

    2001-01-01

    Part of the 2000 annual review of the industrial minerals sector. A general overview of the ball clay industry is provided. In 2000, sales of ball clay reached record levels, with sanitary ware and tile applications accounting for the largest sales. Ball clay production, consumption, prices, foreign trade, and industry news are summarized. The outlook for the ball clay industry is also outlined.

  5. The First X-ray Diffraction Patterns of Clay Minerals from Gale Crater

    NASA Technical Reports Server (NTRS)

    Bristow, Thomas; Blake, David; Bish, David L.; Vaniman, David; Ming, Douglas W.; Morris, Richard V.; Chipera, Steve; Rampe, Elizabeth B.; Farmer, Jack, D.; Treiman, Allan H; Downs, Robert; Morrison, Shaunna; Achilles, Cherie; DesMarais, David J.; Crisp, Joy A.; Sarrazin, Philippe; Morookian, John Michael; Grotzinger. John P.

    2013-01-01

    The Mars Science Laboratory (MSL) Rover, Curiosity spent approx 150 sols at Yellowknife Bay (YKB) studying a section of fluvio-lacustrine sedimentary rocks (with potential indications of volcanic influence), informally known as the Yellowknife Bay formation. YKB lies in a distal region of the Peace Vallis alluvial fan, which extends from the northern rim of Gale Crater toward the dune field at the base of Mt Sharp. Sedimentological and stratigraphic observations are consistent with the Yellowknife Bay formation being part of a distal fan deposit, which could be as young as middle Hesperian to even early Amazonian in age (approx 3.5 to 2.5 Ga). The Yellowknife Bay formation hosts a unit of mudstone called the Sheepbed member. Curiosity obtained powdered rock samples from two drill holes in the Sheepbed Member, named John Klein and Cumberland, and delivered them to instruments in Curiosity. Data from CheMin, a combined X-ray diffraction (XRD)/X-ray fluorescence instrument (XRF), has allowed detailed mineralogical analysis of mudstone powders revealing a clay mineral component of approx 20 wt.% in each sample. The clay minerals are important indicators of paleoenvironmental conditions and sensitive recorders of post-depositional alteration processes. The XRD pattern of John Klein reveals a 021 band consistent with a trioctahedral phyllosilicate. A broad peak at approx 10A with a slight inflexion at approx 12A indicates the presence of 2:1 type clay minerals in the John Klein sample. The trioctahedral nature of the clay minerals, breadth of the basal reflection, and presence of a minor component with larger basal spacing suggests that John Klein contains a trioctahedral smectite (probably saponite), whose interlayer is largely collapsed because of the low-humidity conditions. The XRD patterns show no evidence of corrensite (mixed-layer chlorite/smectite) or chlorite, which are typical diagenetic products of trioctahedral smectites when subjected to burial and heating >60degC in the presence of water. Given estimated geothermal gradients on Mars temperatures <60 degC might still be consistent with (but do not require) moderate burial. However, our ability to identify interstratified minerals is greatly limited by the lack of access to traditional treatments methods used in the lab (e.g., ethylene glycol solvation). Our preferred explanation for the origin of trioctahedral smectites in Sheepbed mudstone is in situ production via reaction of olivine, water and Si-bearing amorphous material, an important mudstone component detected by XRD. Elevated levels of magnetite in the Sheepbed and the trioctahedral monomineralic nature of the clay minerals support this model. These observations, combined with previous studies of olivine stability, support the persistence of circum-neutral hydrous conditions for thousands of years at YKB.

  6. Paleoenvironmental Implications of Clay Minerals at Yellowknife Bay, Gale Crater, Mars

    NASA Technical Reports Server (NTRS)

    Bristow, Thomas F.; Blake, David F.

    2014-01-01

    The Mars Science Laboratory (MSL) Rover, Curiosity spent approx 150 sols at Yellowknife Bay (YKB) studying a section of fluvio-lacustrine sedimentary rocks (with potential indications of volcanic influence), informally known as the Yellowknife Bay formation. YKB lies in a distal region of the Peace Vallis alluvial fan, which extends from the northern rim of Gale Crater toward the dune field at the base of Mt Sharp. Sedimentological and stratigraphic observations are consistent with the Yellowknife Bay formation being part of a distal fan deposit, which could be as young as middle Hesperian to even early Amazonian in age (approx. 3.5 to 2.5 Ga). The Yellowknife Bay formation hosts a unit of mudstone called the Sheepbed member. Curiosity obtained powdered rock samples from two drill holes in the Sheepbed Member, named John Klein and Cumberland, and delivered them to instruments in Curiosity. Data from CheMin, a combined X-ray diffraction (XRD)/X-ray fluorescence instrument (XRF), has allowed detailed mineralogical analysis of mudstone powders revealing a clay mineral component of approx. 20 wt.% in each sample. The clay minerals are important indicators of paleoenvironmental conditions and sensitive recorders of post-depositional alteration processes. The XRD pattern of John Klein reveals a 02l band consistent with a trioctahedral phyllosilicate. A broad peak at approx. 10A with a slight inflexion at approx. 12A indicates the presence of 2:1 type clay minerals in the John Klein sample. The trioctahedral nature of the clay minerals, breadth of the basal reflection, and presence of a minor component with larger basal spacing suggests that John Klein contains a trioctahedral smectite (probably saponite), whose interlayer is largely collapsed because of the low-humidity conditions. The XRD patterns show no evidence of corrensite (mixed-layer chlorite/smectite) or chlorite, which are typical diagenetic products of trioctahedral smectites when subjected to burial and heating >60 C in the presence of water. Given estimated geothermal gradients on Mars temperatures <60 C might still be consistent with (but do not require) moderate burial. However, our ability to identify interstratified minerals is greatly limited by the lack of access to traditional treatments methods used in the lab (e.g., ethylene glycol solvation). Our preferred explanation for the origin of trioctahedral smectites in Sheepbed mudstone is in situ production via reaction of olivine, water and Si-bearing amorphous material, an important mudstone component detected by XRD. Elevated levels of magnetite in the Sheepbed and the trioctahedral monomineralic nature of the clay minerals support this model. These observations, combined with previous studies of olivine stability, support the persistence of circum-neutral hydrous conditions for thousands of years at YKB.

  7. Clay mineral weathering and contaminant dynamics in a casutic aqueous sytem II. Mineral transformation and microscale partitioning

    SciTech Connect

    Choi, Sunkyung; Crosson, Garry S.; Mueller, Karl T.; seraphin, supapan; Chorover, Jon

    2005-04-08

    Microscopic and spectroscopic studies were conducted to assess mineral transformation processes in aqueous suspensions of illite (Il), vermiculite (Vm) and montmorillonite (Mt) that were subjected to weathering in a simulated high-level radioactive tank waste leachate (0.05 m AlT, 2 m Na*, 1 m NO3 *, pH *14, Cs* and Sr2* present as co-contaminants). Time series (0 to 369 d) experiments were conducted at 298 K, with initial [Cs]0 and [Sr]0 concentrations from 10*5 to 10* mol kg*. Incongruent clay dissolution resulted in an accumulation of secondary aluminosilicate precipitates identified as nitrate-sodalite, nitrate-cancrinite and zeolite X, by molecular spectroscopy and electron microscopy (XRD, IR, NMR, SEM-EDS and TEM-EDS). Contaminant fate was dependent on competing uptake to parent clays and weathering products. TEM-EDS results indicated that high Il affinity for Cs was due to adsorption at frayed edge sites. The Il system also comprised Sr-rich aluminous precipitates after 369 d reaction time. In Mt systems, Cs and Sr were co-precipitated into increasingly recalcitrant spheroidal precipitates over the course of the experiment, whereas contaminant association with montmorillonite platelets was less prevalent. In contrast, Cs and Sr were found in association with weathered Vm particles despite the formation of spheroidal aluminosilicate precipitates that were comparable to those formed from Mt dissolution.

  8. Improved dewatering behavior of clay minerals dispersions via interfacial chemistry and particle interactions optimization.

    PubMed

    McFarlane, Angus; Bremmell, Kristen; Addai-Mensah, Jonas

    2006-01-01

    Orthokinetic flocculation of clay dispersions at pH 7.5 and 22 degrees C has been investigated to determine the influence of interfacial chemistry and shear on dewatering and particle interactions behavior. Modification of pulp chemistry and behavior was achieved by using kaolinite and Na-exchanged (swelling) smectite clay minerals, divalent metal ions (Ca(II), Mn(II)) as coagulants and anionic polyacrylamide copolymer (PAM A) and non-ionic polyacrylamide homopolymer (PAM N) as flocculants. The pivotal role of shear, provided by a two-blade paddle impeller, was probed as a function of agitation rate (100-500 rpm) and time (15/60 s). Particle zeta potential and adsorption isotherms were measured to quantify the interfacial chemistry, whilst rheology and cryogenic SEM were used to investigate particle interactions and floc structure and aggregate network, respectively. Osmotic swelling, accompanied by the formation of "honeycomb" particle network structure and high yield stress, was produced by the Na-exchanged smectite, but not kaolinite, dispersions. Dispersion of the clay particles in 0.05 M Ca(II) or Mn(II) solution led to a marked reduction in particle zeta potential, complete suppression of swelling, honeycomb network structure collapse and a concomitant reduction in shear yield stress of smectite pulps. Optimum conditions for improved, orthokinetic flocculation performance of negatively charged clay particles, reflecting faster settling flocs comprised (i) coagulation, (ii) moderate agitation rate, (iii) shorter agitation time, and (iv) anionic rather than non-ionic PAM. The optimum dewatering rates were significantly higher than those produced by standard, manual-mixing flocculation techniques (plunging and cylinder inversion) commonly used in industry for flocculant trials. The optimum flocculation conditions did not, however, have a significant impact on the final sediment solid content of 20-22 wt%. Further application of shear to pre-sedimented pulps improved consolidation by 5-7 wt% solid. Higher shear yield stresses and greater settling rates were displayed by PAM A based than PAM N based pulps and this is attributed to the former's more expanded interfacial conformation and greater clay particles bridging ability. It appears that the intrinsic clay particles' physico-chemical properties and interactions limit compact pulp consolidation. PMID:16038921

  9. Effect of clay minerals and nanoparticles on chromium fractionation in soil contaminated with leather factory waste.

    PubMed

    Taghipour, Marzieh; Jalali, Mohsen

    2015-10-30

    This study was conducted to investigate the effect of time, clay minerals and nanoparticles (NPs) on chromium (Cr) fractionation in a soil contaminated with leather factory waste (LFW). Soil was mixed with LFW, then, the contaminated soils were treated with clay minerals (bentonite and zeolite) and nanoparticles (MgO, TiO2 and ZnO) at 5% and 1%, respectively. The samples were incubated for 15-180 days at 25 °C and constant moisture. After incubation, Cr in control and treated soils was fractionated by the sequential extraction procedure. The distribution of various Cr fractions in control soil indicated that the greatest amounts of Cr were found in the residual fraction (RES) followed by the carbonate (CAR), organic matter (OM) and exchangeable (EXC) fractions. The addition of LFW in soils increased Cr concentration in all fractions. The higher proportion of EXC fraction in the soil treated with LFW indicates its higher potential of leaching and runoff transport. In all treated soils, the RES fraction was increased, while EXC and OM fractions were decreased during incubation. The results indicated that NPs are effective adsorbent for the removal of Cr ions from LFW treated soil, and they could be useful in reducing their environment risk. PMID:25956643

  10. Removal of polycyclic aromatic hydrocarbons (PAHs) from inorganic clay mineral: Bentonite.

    PubMed

    Karaca, Gizem; Baskaya, Hüseyin S; Tasdemir, Yücel

    2016-01-01

    There has been limited study of the removal of polycyclic aromatic hydrocarbons (PAHs) from inorganic clay minerals. Determining the amount of PAH removal is important in predicting their environmental fate. This study was carried out to the degradation and evaporation of PAHs from bentonite, which is an inorganic clay mineral. UV apparatus was designed specifically for the experiments. The impacts of temperature, UV, titanium dioxide (TiO2), and diethylamine (DEA) on PAH removal were determined. After 24 h, 75 and 44 % of ∑12 PAH in the bentonite were removed with and without UV rays, respectively. DEA was more effective as a photocatalyst than TiO2 during UV application. The ∑12 PAH removal ratio reached 88 % with the addition of DEA to the bentonite. It was concluded that PAHs were photodegraded at high ratios when the bentonite samples were exposed to UV radiation in the presence of a photocatalyst. At the end of all the PAH removal applications, higher evaporation ratios were obtained for 3-ring compounds than for heavier ones. More than 60 % of the amount of ∑12 PAH evaporated consisted of 3-ring compounds. PMID:26531715

  11. Preparation of clay mineral samples for high resolution x-ray imaging

    NASA Astrophysics Data System (ADS)

    Abbati, Gennaro; Seim, Christian; Legall, Herbert; Stiel, Holger; Thomas, Noel; Wilhein, Thomas

    2013-10-01

    In the development of optimum ceramic materials for plastic forming, it is of fundamental importance to gain insight into the compositions of the clay minerals. Whereas spectroscopic methods are adequate for determining the elemental composition of a given sample, a knowledge of the spatial composition, together with the shape and size of the particles leads to further, valuable insight. This requires an imaging technique such as high resolution X-ray microscopy. In addition, fluorescence spectroscopy provides a viable element mapping technique. Since the fine particle fraction of the materials has a major effect on physical properties like plasticity, the analysis is focused mainly on the smallest particles. To separate these from the bigger agglomerates, the raw material has to pass through several procedures like centrifugation and filtering. After that, one has to deposit a layer of appropriate thickness on to a suitable substrate. These preparative techniques are described here, starting from the clay mineral raw materials and proceeding through to samples that are ready to analyze. First results using high resolution x-ray imaging are shown.

  12. Zeolite-clay mineral zonation of volcaniclastic sediments within the McDermitt caldera complex of Nevada and Oregon

    USGS Publications Warehouse

    Glanzman, Richard K.; Rytuba, James J.

    1979-01-01

    Volcaniclastic sediments deposited in the moat of the collapsed McDermitt caldera complex have been altered chiefly to zeolites and potassium feldspar. The original rhyolitic and peralkaline ash-flow tuffs are included in conglomerates at the caldera rims and grade into a lacustrine series near the center of the collapse. The tuffs show a lateral zeolitic alteration from almost fresh glass to clinoptilolite, clinoptilolite-mordenite, and erionite; to analcime-potassium feldspar; and finally to potassium feldspar. Vertical zonation is in approximately the same order. Clay minerals in associated mudstones, on the other hand, show little lateral variation but a distinct vertical zonation, having a basal dioctahedral smectite, a medial trioctahedral smectite, and an upper dioctahedral smectite. The medial trioctahedral smectite is enriched in lithium (as much as 6,800 ppm Li). Hydrothermal alteration of the volcaniclastic sediments, forming both mercury and uranium deposits, caused a distinct zeolite and clay-mineral zonation within the general lateral zonation. The center of alteration is generally potassium feldspar, commonly associated with alunite. Potassium feldspar grades laterally and vertically to either clinoptilolite or clinoptilolite-mordenite, generally associated with gypsum. This zone then grades vertically and laterally into fresh glass. The clay minerals are a dioctahedral smectite, a mixed-layer clay mineral, and a 7-A clay mineral. The mixed-layer and 7-A clay minerals are associated with the potassium feldspar-alunite zone of alteration, and the dioctahedral smectite is associated with clinoptilolite. This mineralogical zonation may be an exploration guide for mercury and uranium mineralization in the caldera complex environment.

  13. Quantitative determination of mineral types and abundances from reflectance spectra using principal components analysis

    NASA Technical Reports Server (NTRS)

    Smith, M. O.; Adams, J. B.; Johnson, P. E.

    1985-01-01

    A procedure was developed for analyzing remote reflectance spectra, including multispectral images, that quantifies parameters such as types of mineral mixtures, the abundances of mixed minerals, and particle sizes. Principal components analysis reduced the spectral dimensionality and allowed testing the uniqueness and validity of spectral mixing models. By analyzing variations in the overall spectral reflectance curves, the type of spectral mixture was identified, mineral abundances quantified and the effects of particle size identified. The results demonstrate an advantage in classification accuracy over classical forms of analysis that ignore effects of particle-size or mineral-mixture systematics on spectra. The approach is applicable to remote sensing data of planetary surfaces for quantitative determinations of mineral abundances.

  14. Spectral stratigraphy and clay minerals analysis in parts of Hellas Planitia, Mars

    NASA Astrophysics Data System (ADS)

    Das, I. C.; Joseph, J.; Subramanian, S. K.; Dadhwal, V. K.

    2014-11-01

    Absorption features that occur in reflectance spectra are a sensitive indicator of mineralogy and chemical composition for a wide variety of materials. The investigation of the mineralogy and chemical composition of surfaces give information about the origin and evolution of planetary bodies. On Mars, the processes of formation of different types of clay minerals result from different types of wet conditions viz. hydrothermalism, subsurface/groundwater weathering, surface alteration etc. The image analyzed in the present study was frt000947f- 164-trr3 (-27.87N-65.06E). Through the spectral stratigraphic characterization along a crater wall, eight (8) different layers were identified considering the spectral variability and their position. In Hellas Planitia, the alteration minerals identified by CRISM based on distinctive absorptions from 0.4 to3.9 μm include Al-rich smectite, montmorillonite, phyllosilicate mineral at 2.2 μm and 2.35 μm, including strong absorption feature noticed at 1.9 μm. We conclude that the layers exposed in the crater wall help characterize the compositional stratigraphy for confirming the presence of hydrated minerals in this region as an outcome of geohydrological weathering process.

  15. Ball clay

    USGS Publications Warehouse

    Virta, R.L.

    2007-01-01

    The article offers information on ball clay. Among the companies that mine ball clay in the U.S. are H.C. Spinks Clay, Kentucky-Tennessee Clay and Old Hickory Clay. In 2006, an estimated 1.2 million tons of the mineral was sold or used domestically and exported. Forty-percent of the total sales is accounted for ceramic floor and wall tile followed by sanitaryware and miscellaneous ceramics. Its average value was $ 45 per ton in 2006.

  16. First-principles study of cesium adsorption to weathered micaceous clay minerals

    NASA Astrophysics Data System (ADS)

    Okumura, Masahiko; Nakamura, Hiroki; Machida, Masahiko

    2014-05-01

    A large amount of radioactive nuclides was produced into environment due to the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident. Residents near FDNPP were suffering from radioactive cesium and then evacuated, because which has long half-life and is retained by surface soil for long time. The Japanese government has been decontaminating the cesium by removing the surface soil in order to return them to their home. This decontamination method is very effective, but which produces huge amount of waste soil. This becomes another big problem in Fukushima, because it is not easy to find large storage sites. Then effective and economical methods to reduce the volume of the waste soil are needed. However, it has not been invented yet. One of the reasons is lack of knowledge about microscopic process of adsorption/desorption of cesium to/from soil. It is known that weathered micaceous clay minerals play crucial role on adsorption and retention of cesium. They are expected to have special sorption sites, called frayed edge sites (FESs), which adsorb cesium selectively and irreversibly. Properties of FES have been intensely investigated by experiments. But microscopic details of the adsorption process on FES are still unclear. Because direct observation of the process with current experimental techniques is quite difficult. We investigated the adsorption of cesium to FES in muscovite, which is a typical micaceous clay mineral, via first-principles calculations (density functional theory). We made a minimal model of FES and evaluate the energy difference before and after cesium adsorption to FES. This is the first numerical modeling of FES. It was shown that FES does adsorb cesium if the weathering of muscovite has been weathered. In addition, we revealed the mechanism of cesium adsorption to FES, which is competition between ion radius of cesium and the degree of weathering. I plan to discuss volume reduction of the waste soil based on our result. Reference M. Okumura, H. Nakamura, and M. Machida, Mechanism of Strong Affinity of Clay Minerals to Radioactive Cesium : First-Principles Calculation Study for Adsorption of Cesium at Frayed Edge Sites in Muscovite, Journal of the Physical Society of Japan 82, 033802 (2013).

  17. Terrestrial Analogs for Clay Minerals at Yellowknife Bay, Gale Crater, Mars

    NASA Technical Reports Server (NTRS)

    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 the last three varieties may be contemporaneous. One sample shows agate (alpha- quartz) that was precipitated between the episodes of deposition of the fine-grained and coarse-grained 'griffithite.' 'Griffithite' is not unique as a possible terrestrial analog - some clay minerals from the Doushantou formation, China, have similar 02L diffraction bands, and many basalts contain smectites in vesicles and as replacements after olivine. Similar trioctahedral smectites occur also in the nakhlite martian meteorites - as veinlets and replacements of olivine. By understanding the formation of these terrestrial clays, we hope to constrain the nature and mechanism of formation of the Sheepbed clay mineral.

  18. Understanding the role of clay minerals in the chromium(VI) bioremoval by Pseudomonas aeruginosa CCTCC AB93066 under growth condition: microscopic, spectroscopic and kinetic analysis.

    PubMed

    Kang, Chunxi; Wu, Pingxiao; Li, Yuewu; Ruan, Bo; Li, Liping; Tran, Lytuong; Zhu, Nengwu; Dang, Zhi

    2015-11-01

    Laboratory batch experiments were conducted to investigate the role of clay minerals, e.g., kaolinite and vermiculite, in microbial Cr(VI) reduction by Pseudomonas aeruginosa under growth condition in glucose-amended mediums as a method for treating Cr(VI)-contaminated subsurface environment such as soil. Our results indicated that glucose could acted as an essential electron donor, and clay minerals significantly enhanced microbial Cr(VI) reduction rates by improving the consumption rate of glucose and stimulating the growth and propagation of P. aeruginosa. Cr(VI) bioreduction by both free cells and clay minerals-amended cells followed the pseudo-first-order kinetic model, with the latter one fitting better. The mass balance analyses and X-ray photoelectron spectroscopy analysis found that Cr(VI) was reduced to Cr(III) and the adsorption of total chromium on clay minerals-bacteria complex was small, implying that Cr(VI) bioremoval was not mainly due to the adsorption of Cr(VI) onto cells or clay minerals or clay minerals-cells complex but mainly due to the Cr(VI) reduction capacity of P. aeruginosa under the experimental conditions studied (e.g., pH 7). Atomic force microscopy revealed that the addition of clay minerals (e.g. vermiculite) decreased the surface roughness of Cr(VI)-laden cells and changed the cell morphology and dimension. Fourier transform infrared spectroscopy revealed that organic matters such as aliphatic species and/or proteins played an important role in the combination of cells and clay minerals. Scanning electron microscopy confirmed the attachment of cells on the surface of clay minerals, indicating that clay minerals could provide a microenvironment to protect cells from Cr(VI) toxicity and serve as growth-supporting materials. These findings manifested the underlying influence of clay minerals on microbial reduction of Cr(VI) and gave an understanding of the interaction between pollutants, the environment and the biota. PMID:26296415

  19. The composition of clay minerals transported to Israel as indicators of Saharan dust emission

    NASA Astrophysics Data System (ADS)

    Ganor, Eliezer

    Ambient particles, following dust storms originating in the Saharan region as identified by meteorological analysis of synoptic maps, satellite pictures and back-trajectory calculations, transported over Israel, were collected and analysed. In studies of 28 heavy dust storms originating in the Saharan region, during a 22 year period (1967-1988), clay mineral analysis provided information about the characteristics of dust particles transported over Israel. Relatively high concentrations of montmorillonite and mixed-layer minerals were found in the particles when the storms originated on the western deserts of the Tibesti mountains. Following storms that originated in Saudi Arabia, Jordan and the Dead Sea deserts, the dust particles contained a high percentage of palygorskite. Following storms that originated in the Chad, Lybian plateau deserts and the Great Sand Sea of Ahaggar Massif, predominantly high concentrations of illite was found in the ambient particles in Israel. These data indicate that ambient particles in Israel following dust storms originating in the Saharan region may be characterized by their mineral content.

  20. Influence of crop residues on trifluralin mineralization in a silty clay loam soil.

    PubMed

    Farenhorst, Annemieke

    2007-01-01

    Trifluralin is typically applied onto crop residues (trash, stubble) at the soil surface, or onto the bare soil surface after the incorporation of crop residues into the soil. The objective of this study was to quantify the effect of the type and amount of crop residues in soil on trifluralin mineralization in a Wellwood silty clay loam soil. Leaves and stubble of Potato (Solanum tuberosum) (P); Canola (Brassica napus) (C), Wheat (Triticum aestivum) (W), Oats (Avena sativa), (O), and Alfalfa (Medicago sativa) (A) were added to soil microcosms at rates of 2%, 4%, 8% and 16% of the total soil weight (25 g). The type and amount of crop residues in soil had little influence on the trifluralin first-order mineralization rate constant, which ranged from 3.57E-03 day(-1) in soil with 16% A to 2.89E-02 day(-1) in soil with 8% W. The cumulative trifluralin mineralization at 113 days ranged from 1.15% in soil with 16% P to 3.21% in soil with 4% C, again demonstrating that the observed differences across the treatments are not of agronomic or environmental importance. PMID:17454379

  1. Interactions Between Chlorinated Waste Solvents and Clay Minerals in Low Permeability Subsurface Layers

    NASA Astrophysics Data System (ADS)

    Ayral, D.; Otero-Diaz, M.; Demond, A. H.

    2014-12-01

    Waste organic contaminants stored in low permeability subsurface layers serve as long-term sources for dissolved phase contaminant plumes. These layers may have a different mineralogical make up than the surrounding geologic media; specifically, they may be characterized by a high clay content. Although these layers are often considered inert, interactions may occur between the clay minerals and the waste liquids that may influence transport. Measurements of the basal spacing of Na-montmorillonite in contact with pure chlorinated organic liquids such as trichloroethylene (TCE) showed that it is similar to that with water; however, its basal spacing in contact with waste chlorinated liquids was reduced, leading to cracking. In fact, the basal spacing in contact with the waste chlorinated liquids was closer to that in contact with air than in contact with water. The observation that contact with pure organic liquids did not cause cracking, but contact with chlorinated wastes obtained from the field did, suggests that other components of the waste are critical to the basal spacing reduction process. Screening experiments indicated that the presence of a binary mixture of surfactants, a nonionic and an anionic surfactant, in the chlorinated solvent were necessary to cause the cracking at the same rate and magnitude as the chlorinated wastes obtained from the field. Fourier transform infrared (FT-IR) spectroscopy measurements suggest that the mixture alters the adsorbed water OH-bending band, implying a displacement of adsorbed water. Coupling these results with sorption and x-ray diffraction (XRD) measurements, a hypothesis of component conformation in the clay interlayer space that leads to cracking can be constructed.

  2. Comparison of three different statistical methods for retrieving the lunar mineral abundance

    NASA Astrophysics Data System (ADS)

    Li, L.; Li, S.

    2010-12-01

    Our current work aims to develop the most reliable model for estimating lunar mineral abundances. In our previous studies, partial least squares (PLS) and genetic algorithm - partial least squares (GA-PLS) models have been used. PLS has two limitations: 1) redundant spectral bands cannot be removed effectively; and 2) non-linearity between lunar soil reflectance spectra and lunar mineral abundances cannot be accommodated. GA is an effective tool for selecting a set of spectral bands that are most sensitive to lunar minerals, and to some extent overcomes the first limitation. One objective of this study is to compare the PLS and GA-PLS performances in estimating lunar mineral abundances. Given the fact that GA-PLS is still subjected to the effect of nonlinearity, a hybrid PLS-BPNN model is developed and tested to determine how effective back propagation neural network (BPNN) is for overcoming the two limitations. BPNN accommodates nonlinearity with the sigmoid functions connecting BPNN layers of nodes, and the weights of redundant spectral bands are significantly decreased through the learning process. The lunar soil characterization consortium (LSCC) dataset is the only complete 'ground truth' data of the Moon consisting both soil reflectance spectra and mineral abundances. The LSCC dataset is composed of totally 19 Apollo samples and each sample has four particle size groups (< 10 µm, 10 - 20 µm, 20 - 45 µm, < 45 µm). Although the mineral abundances of the group < 45 µm are not measured, the mineral abundances of this group (validation set) are assumed to be the average of the mineral abundances of samples in other three groups (calibration set). PLS, GA-PLS and PLS-BPNN are assessed based on R-squares and relative root mean square error for the validation. The results indicates that GA-PLS performs better than PLS for retrieving the mineral abundance of agglutinate, plagioclase, pyroxene, and volcanic glasses (Figure 1), but PLS is preferred over GA-PLS for modeling the abundance of olivine and ilmenite (Figure 1). Comparison among the three models indicates that PLS-BPNN performs significantly better than both PLS and GA-PLS for estimating agglutinate, pyroxene, olivine, ilmenite, and volcanic glasses (Figure 1). For estimation of plagioclase, both PLS-BPNN and GA-PLS perform equally well. Overall PLS-BPNN is preferred over both PLS and GA-PLS for quantifying all lunar surface dominant minerals. Figure 1. Comparison of R- squares and relative root mean square errors resulting from the PLS, GA-PLS and PLS-BPNN validation.

  3. Mineralogic and isotopic constraints on impact related clay mineral alteration, in the Woodleigh impact structure, Western Australia

    NASA Astrophysics Data System (ADS)

    Uysal, I. T.; Golding, S. D.; Mory, A. J.; Glikson, A. Y.

    2003-04-01

    Clay mineral fractions from one of the largest Phanerozoic impact structures, the Woodleigh impact structure were investigated by XRD, electron microscopy and K-Ar and stable isotopic studies. Samples were collected from the central uplifted Precambrian basement granitoid, conglomeratic rocks derived from reworked impact rocks, and from the Ordovician-Devonian sandstones located 30 km west of the central uplift. There are remarkable lateral and vertical variations in authigenic clay mineral compositions and illite crystallinity (IC) values (Kbler index). Clay minerals from shocked granitoid basement rocks are mainly smectite-rich (>75%) mixed-layer illite-smectite with some discrete illite formed as an alteration-product (replacement) of biotite. Clay minerals in the conglomeratic rocks consist of mainly illite and Fe-rich chlorite, and in the lower part of the section, chlorite-rich (>50%) mixed-layer chlorite-smectite. Smectite in the oxidised upper part of the conglomeratic section is probably a weathering- product. Clay minerals from the Ordovician-Devonian sandstones further away from the central part of the impact structure include illite, less chlorite, and in the Devonian strata smectite. IC values of the <2 mm grain-size fraction in the conglomeratic rocks range from 0.51 to 0.56 ^o? 2? in the upper part and from 0.75 to 0.82 ^o? 2? in the lower part of the section. Illites from the Ordovician-Devonian sandstones show significantly higher IC values ranging from 0.75 to 1.45 ^o? 2?. Results of the clay mineralogy suggest that variations of clay mineral compositions and IC values are related to the changes in rock lithology and the variable effects of impact-induced hydrothermal processes. K-Ar dating of the authigenic illites of the coarser size-fractions (2-1 ?m and 0.5-0.2 ?m) containing no smectite yield concordant ages around 365 Ma. These K-Ar age data are consistent with previous results (Uysal et al., 2001;EPSL, 192:281--289) and, together with stratigraphic age constraints, confirm that the impact event was coeval with the Late Devonian mass extinction. Woodleigh impact-related clay minerals have significantly high ?18O values from 13.4 to 18.9 ppm. The calculated fluid ?18O values ranges from 6.5 to 11.7 ppm that are highly enriched in 18O relative to seawater, meteoric water and most basinal brines and may indicate the hydrothermal fluids interacted with 18O-rich condensed meteoritic components injected into the crater floor.

  4. Sedimentary processes on the Mekong subaqueous delta: Clay mineral and geochemical analysis

    NASA Astrophysics Data System (ADS)

    Xue, Zuo; Paul Liu, J.; DeMaster, Dave; Leithold, Elana L.; Wan, Shiming; Ge, Qian; Nguyen, Van Lap; Ta, Thi Kim Oanh

    2014-01-01

    Sedimentary processes on the inner Mekong Shelf were investigated by examining the characteristics of sediments sampled in gravity cores at 15 locations, including grain size, clay mineralogy, sediment accumulation rates, and the elemental and stable carbon isotopic composition of organic matter (atomic C/N ratios and δ13C). Deltaic deposits exhibit contrasting characteristics along different sides of the delta plain (South China Sea, SCS hereafter, to the east and Gulf of Thailand, GOT hereafter, to the west) as well as on and off the subaqueous deltaic system. On one hand, cores recovered from the subaqueous delta in the SCS/GOT are consisted of poorly/well sorted sediments with similar/different clay mineral assemblage with/from Mekong sediments. Excess 210Pb profiles, supported by 14C chronologies, indicate either "non-steady" (SCS side) or "rapid accumulation" (GOT side) processes on the subaqueous delta. The δ13C and C/N ratio indicate a mixture of terrestrial and marine-sourced organic matter in the deltaic sediment. On the other hand, cores recovered from areas with no deltaic deposits or seaward of the subaqueous delta show excess 210Pb profiles indicating "steady-state" accumulation with a greater proportion of marine-sourced organic matter. Core analysis's relevance with local depositional environment and previous acoustic profiling are discussed.

  5. Wind-blown sandstones cemented by sulfate and clay minerals in Gale Crater, Mars

    NASA Astrophysics Data System (ADS)

    Milliken, R. E.; Ewing, R. C.; Fischer, W. W.; Hurowitz, J.

    2014-02-01

    Gale Crater contains Mount Sharp, a ~5 km thick stratigraphic record of Mars' early environmental history. The strata comprising Mount Sharp are believed to be sedimentary in origin, but the specific depositional environments recorded by the rocks remain speculative. We present orbital evidence for the occurrence of eolian sandstones within Gale Crater and the lower reaches of Mount Sharp, including preservation of wind-blown sand dune topography in sedimentary strata—a phenomenon that is rare on Earth and typically associated with stabilization, rapid sedimentation, transgression, and submergence of the land surface. The preserved bedforms in Gale are associated with clay minerals and elsewhere accompanied by typical dune cross stratification marked by bounding surfaces whose lateral equivalents contain sulfate salts. These observations extend the range of possible habitable environments that may be recorded within Gale Crater and provide hypotheses that can be tested in situ by the Curiosity rover payload.

  6. Clay fractions from a soil chronosequence after glacier retreat reveal the initial evolution of organo-mineral associations

    NASA Astrophysics Data System (ADS)

    Dümig, Alexander; Häusler, Werner; Steffens, Markus; Kögel-Knabner, Ingrid

    2012-05-01

    Interactions between organic and mineral constituents prolong the residence time of organic matter in soils. However, the structural organization and mechanisms of organic coverage on mineral surfaces as well as their development with time are still unclear. We used clay fractions from a soil chronosequence (15, 75 and 120 years) in the foreland of the retreating Damma glacier (Switzerland) and from mature soils outside the proglacial area (>700 and <3000 years) to elucidate the evolution of organo-mineral associations during initial soil formation. The chemical composition of the clay-bound organic matter (OM) was assessed by solid-state 13C NMR spectroscopy while the quantities of amino acids and neutral sugar monomers were determined after acid hydrolysis. The mineral phase was characterized by X-ray diffraction, oxalate extraction, specific surface area by N2 adsorption (BET approach), and cation exchange capacity at pH 7 (CECpH7). The last two methods were applied before and after H2O2 treatment. We found pronounced shifts in quantity and quality of OM during aging of the clay fractions, especially within the first one hundred years of soil formation. The strongly increasing organic carbon (OC) loading of clay-sized particles resulted in decreasing specific surface areas (SSA) of the mineral phases and increasing CECpH7. Thus, OC accumulation was faster than the supply of mineral surfaces and cation exchange capacity was mainly determined by the OC content. Clay-bound OC of the 15-year-old soils showed high proportions of carboxyl C and aromatic C. This may point to remnants of ancient OC which were inherited from the recently exposed glacial till. With increasing age (75 and 120 years), the relative proportions of carboxyl and aromatic C decreased. This was associated with increasing O-alkyl C proportions, whereas accumulation of alkyl C was mainly detected in clay fractions from the mature soils. These findings from solid-state 13C NMR spectroscopy are in line with the increasing amounts of microbial-derived carbohydrates with soil age. The large accumulation of proteins, which was comparable to those of carbohydrates, and the very low C/N ratios of H2O2-resistant OM indicated strong and preferential associations between proteinaceous compounds and mineral surfaces. In the acid soils, poorly crystalline Fe oxides were the main providers of mineral surface area and important for the stabilization of OM during aging of the clay fractions. This was indicated by (I) the strong correlations between oxalate soluble Fe and both, SSA of H2O2-treated clay fractions and OC content, and (II) the low formation of expandable clays due to small extents of mineral weathering. Our chronosequence approach provided new insights into the evolution of organo-mineral interactions in acid soils. The formation of organo-mineral associations started with the sorption of proteinaceous compounds and microbial-derived carbohydrates on mineral surfaces which were mainly provided by ferrihydrite. The sequential accumulation of different organic compounds and the large OC loadings point to multiple accretion of OM in distinct zones or layers during the initial evolution of clay fractions.

  7. Clay minerals and its influence on soil respiration in southern Brazil

    NASA Astrophysics Data System (ADS)

    Marques, José, Jr.; Tadeu Pereira, Gener; La Scala, Newton, Jr.

    2010-05-01

    Carbon dioxide is the greenhouse gas with the highest concentration increases in the last century caused by human activities. Despite all the efforts, new investigations should be conducted in order to understand how agricultural management and its variations would impact on soil respiration and consequently in soils potential for carbon sequestration. Soil iron content is an important aspect of tropical soils, especially in sugarcane fields, that are located in regions where iron content in soil is among the highest concentrations in world. In this work we show that as iron content increases and changes its constitution FCO2 decreases monotonically. A transect was established on an acid oxisol in a direction where soil color changed from a yellow (10 YR), passing to a red (5 YR) and finishing with a dark red latosol (2.5 YR), in just 420 meters. Soil respiration was taken each 10 meters (42 points) while soil samples were extracted (0-20 cm) in each point for further soil property analysis. X-ray analysis shows that the goethite per hematite ratio and kaolinite per gibbsite ratio are directly related to soil respiration rates, and this is confirmed by spectroreflectance analysis performed in the same samples. Also, soils with iron clay minerals having lower degree of cristalinity were the ones having the higher soil respirations. Our study suggests a more complex relationship between clay minerals and biological activity, including soil iron level as an important factor in order to infer the ecological impact of tropical soil management in the biosphere. Due to the distinguishable characteristics of the Brazilian soils in terms of iron level, new experiments are needed to elucidate the relationship of iron content and CO2 loss in different classes of soils.

  8. Removal of organic pollutants in model water and thermal wastewater using clay minerals.

    PubMed

    Szabó, Emese; Vajda, Krisztina; Veréb, Gábor; Dombi, András; Mogyorósi, Károly; Ábrahám, Imre; Májer, Marcell

    2011-01-01

    Water treatment method was developed for the removal of different anionic dyes such as methyl orange and indigo carmine, and also for thymol applying sodium bentonite and cationic surfactant - hexadecyltrimethylammonium bromide (HTAB) - or polyelectrolytes (polydiallyldimethylammonium chloride, poly-DADMAC and poly-amines). The removal efficiency of these model substrates was examined in model water using UV-Vis spectrophotometry, HPLC and TOC analysis. The clay mineral and HTAB were added in one step to the polluted model water in Jar-test experiments. The influence of the cation exchange capacity (CEC) of the applied clay mineral and the presence of polyaluminium chloride coagulant (BOPAC) were also tested for the water treatment process. The structures of the in situ produced and pre-prepared organoclay composites were compared by XRD analysis. The rapid formation of organoclay adsorbents provided very efficient removal of the dyes (65-90 % in 3-10 mg/L TOC(0) range) with 200 mg/L sodium bentonite dose, however thymol was less efficiently separated. Adsorption efficiencies of the composites were compared at different levels of ion exchange such as at 40, 60 and 100 %. In the case of thymol, the elimination of inorganic carbon from the model water before the TOC analysis resulted in some loss of the analysed volatile compound therefore the HPLC analysis was found to be the most suitable tool for the evaluation of the process. This one-step adsorption method using in situ formed organoclay was better performing than the conventional process in which the montmorillonite-surfactant composite is pre-preapared and subsequently added to the polluted water. The purification performance of this method was also evaluated on raw and artificially polluted thermal wastewater samples containing added thymol. PMID:21929471

  9. Structural charge site influence on the interlayer hydration of expandable three-sheet clay minerals

    USGS Publications Warehouse

    Kerns, R.L., Jr.; Mankin, C.J.

    1968-01-01

    Previous investigations have demonstrated the influences of interlayer cation composition, relative humidity, temperature, and magnitude of interlayer surface charge on the interlayer hydration of montmorillonites and vermiculites. It has been suggested that the sites of layer charge deficiencies may also have an influence upon the amount of hydration that can take place in the interlayers of expandable clay minerals. If the interlayer cation-to-layer bonds are considered as ideally electrostatic, the magnitude of the forces resisting expansion may be expressed as a form of Coulomb's law. If this effect is significant, expandable structures in which the charge-deficiency sites are predominantly in the tetrahedral sheet should have less pronounced swelling properties than should structures possessing charge deficiencies located primarily in the octahedral sheet. Three samples that differed in location of layer charge sites were selected for study. An important selection criterion was a non-correlation between tetrahedral charge sites and high surface-charge density, and between octahedral charge sites and low surface-charge density. The effects of differences in interlayer cation composition were eliminated by saturating portions of each sample with the same cations. Equilibrium (001) d values at controlled constant humidities were used as a measure of the relative degree of interlayer hydration. Although no correlation could be made between the degree of interlayer hydration and total surface-charge density, the investigation does not eliminate total surface-charge density as being significant to the swelling properties of three-sheet clay-mineral structures. The results do indicate a correlation between more intense expandability and predominance of charge deficiencies in the octahedral sheet. Conversely, less intense swelling behavior is associated with predominantly tetrahedral charge deficiencies. ?? 1968.

  10. Abundance and distribution of mineral components associated with Moses Rock (kimberlite) diatreme

    NASA Technical Reports Server (NTRS)

    Mustard, J. F.; Pieters, C. M.

    1986-01-01

    The surface mineralogy in and around Moses Rock diatreme, a kimberlite-bearing dike in SW Utah, was examined using internally calibrated Airborne Imaging Spectrometer (AIS) data. Distinct near-infrared absorption characteristics of clays, gypsum, and serpentine (a key marker for kinberlite concentration) allowed the surface units containing these components to be identified spatially and the relative abundance of each component measured. Within the dike itself, channels and dispersed components of kimberlite and blocks of country rocks were accurately determined.

  11. The origin of the pozzolanic activity of calcined clay minerals: A comparison between kaolinite, illite and montmorillonite

    SciTech Connect

    Fernandez, Rodrigo; Martirena, Fernando; Scrivener, Karen L.

    2011-01-15

    This paper investigates the decomposition of three clayey structures (kaolinite, illite and montmorillonite) when thermally treated at 600 {sup o}C and 800 {sup o}C and the effect of this treatment on their pozzolanic activity in cementitious materials. Raw and calcined clay minerals were characterized by the XRF, XRD, {sup 27}Al NMR, DTG and BET techniques. Cement pastes and mortars were produced with a 30% substitution by calcined clay minerals. The pozzolanic activity and the degree of hydration of the clinker component were monitored on pastes using DTG and BSE-IA, respectively. Compressive strength and sorptivity properties were assessed on standard mortars. It was shown that kaolinite, due to the amount and location of OH groups in its structure, has a different decomposition process than illite or montmorillonite, which results in an important loss of crystallinity. This explains its enhanced pozzolanic activity compared to other calcined clay-cement blends.

  12. Interplay between cataclasis, clay mineral diagenesis and porosity reduction in deformation bands in unconsolidated arkosic sands

    NASA Astrophysics Data System (ADS)

    Lommatzsch, Marco; Exner, Ulrike; Gier, Susanne

    2013-04-01

    As a response to tectonic and gravitational stresses, unconsolidated sediments can develop zones of localized deformation, commonly described as deformation bands. These are tabular fault zones in high porosity rocks and sediments characterized by small offsets causing reduction of porosity through grain rotation, translation and fracturing. Classified by deformation mechanism and depth of formation, there are two main types of deformation bands: disaggregation bands, where compaction is achieved only by grain rotation and translation, and cataclastic bands, which show intense grain size reduction by grain fracturing. In various examples the porosity and permeability reduction in these fault zones inhibits the flow of fluids. The timing of deformation band formation relative to diagenesis and fluid migration is relevant in relation to the quality and connectivity of hydrocarbon or groundwater reservoirs. The investigated outcrop in a sandpit near Eisenstadt (Eisenstadt-Sopron Basin, Austria) exposes numerous conjugate deformation bands, which are formed in lower Miocene uncemented, arkosic sands and gravels. These deformation bands formed at shallow burial depth (< 1km) and are kinematically related to the nearby Eisenstadt Fault. This outcrop offers the unique possibility to investigate deformation bands with identical kinematic boundary conditions in highly variable sediments, i.e. with a wide range of different grain sizes from fine sand to coarse gravel, variable porosity and mineral content, different stages of diagenesis and carbonate-free or carbonatic sediments. The fact that cataclasis is one of the dominant mechanisms at these shallow depths (< 1km) is unusual and an exception to most cataclastic bands described in literature. This is probably related to the composition, coarse grain size and the high porosity of the sediments. The coarse host sediment mainly consists of detrital quartz, albite, biotite, sericite, muscovite and metamorphic lithoclasts. The dominant deformation mechanisms and the magnitude of porosity reduction in the carbonate-free lithologies are controlled by the initial mica content, mean grain size, level of alteration and albite content in the host rock. The studied deformation bands show a preferred fracturing of sericitized albite grains and the smearing of micas into the pore space. These processes increase the amount of phyllosilicates in the pore space and facilitate the growth of various authigenic clay minerals like smectite, vermiculite, kaolinite and illite. Because of the changed petrophysical properties the deformation bands show a different diagenetic evolution in comparison with the host rock. We identified 4 steps in the development from a high-porosity host rock to a low porosity deformation band. The measured reduction in porosity by up to 18% is associated with a permeability reduction, reflected in the retention of fluids along the deformation bands with the highest content of authigenic clay minerals.

  13. Is the clogging process in Maqarin natural analogue controlled by accessory clay minerals? A reactive transport study with new data.

    NASA Astrophysics Data System (ADS)

    Shao, H.; Kosakowski, G.; Berner, U.; Kulik, D.; Mäder, U.; Kolditz, O.

    2012-04-01

    The safety of nuclear waste repositories is based on the functionality of multiple natural and engineered barriers for very long time. The barrier system typically combines geochemically different materials that might interact with each other. One example is the long term alteration of sedimentary host rocks by the interaction with high pH pore water from cement materials used for tunnel support, seals and as backfill material. Within this context the Maqarin site in Jordan was investigated since more than 20 years as a natural analogue for rock alterations and pore clogging due to ingress of high pH solutions. In this work we examine the geochemical evolution of Maqarin marl rock in contact with a fracture through which a hyper-alkaline groundwater is circulating. The new reactive transport calculations were performed with the code OpenGeoSys-GEMS and utilize a state-of-the-art geochemical model for cement-clay interactions. The simulations reveal that the precipitation of ettringite, and to a smaller extent the precipitation of calcium-silicate-hydrate (CSH), is responsible for pore clogging in the rock matrix. Clogging of the pore space effectively seals the rock matrix on a centimeter scale after some hundreds of years and suppresses mass transfer of solutes from the fracture into the adjacent rock. In our Maqarin marl rock model typical clay minerals like kaolinite and illite are present in accessory mineral quantities only. A sensitivity analysis reveals that in this setup clay minerals are the main source for Al, necessary for the formation of ettringite-type solid solutions. It is thus the clay mineral content and the dissolution reactions that to a large degree control the spatial and temporal precipitation of ettringites and the associated pore clogging. Recently collected mineralogy and porosity data will be used to re-calibrate the model and to verify our improved findings that overall Maqarin system is controlled by accessory clay minerals.

  14. Effect of organic matter properties, clay mineral type and thermal maturity on gas adsorption in organic-rich shale systems

    USGS Publications Warehouse

    Zhang, Tongwei; Ellis, Geoffrey S.; Ruppel, Stephen C.; Milliken, Kitty; Lewan, Mike; Sun, Xun

    2013-01-01

    A series of CH4 adsorption experiments on natural organic-rich shales, isolated kerogen, clay-rich rocks, and artificially matured Woodford Shale samples were conducted under dry conditions. Our results indicate that physisorption is a dominant process for CH4 sorption, both on organic-rich shales and clay minerals. The Brunauer–Emmett–Teller (BET) surface area of the investigated samples is linearly correlated with the CH4 sorption capacity in both organic-rich shales and clay-rich rocks. The presence of organic matter is a primary control on gas adsorption in shale-gas systems, and the gas-sorption capacity is determined by total organic carbon (TOC) content, organic-matter type, and thermal maturity. A large number of nanopores, in the 2–50 nm size range, were created during organic-matter thermal decomposition, and they significantly contributed to the surface area. Consequently, methane-sorption capacity increases with increasing thermal maturity due to the presence of nanopores produced during organic-matter decomposition. Furthermore, CH4 sorption on clay minerals is mainly controlled by the type of clay mineral present. In terms of relative CH4 sorption capacity: montmorillonite ≫ illite – smectite mixed layer > kaolinite > chlorite > illite. The effect of rock properties (organic matter content, type, maturity, and clay minerals) on CH4 adsorption can be quantified with the heat of adsorption and the standard entropy, which are determined from adsorption isotherms at different temperatures. For clay-mineral rich rocks, the heat of adsorption (q) ranges from 9.4 to 16.6 kJ/mol. These values are considerably smaller than those for CH4 adsorption on kerogen (21.9–28 kJ/mol) and organic-rich shales (15.1–18.4 kJ/mol). The standard entropy (Δs°) ranges from -64.8 to -79.5 J/mol/K for clay minerals, -68.1 to -111.3 J/mol/K for kerogen, and -76.0 to -84.6 J/mol/K for organic-rich shales. The affinity of CH4 molecules for sorption on organic matter is stronger than for most common clay minerals. Thus, it is expected that CH4 molecules may preferentially occupy surface sites on organic matter. However, active sites on clay mineral surfaces are easily blocked by water. As a consequence, organic-rich shales possess a larger CH4-sorption capacity than clay-rich rocks lacking organic matter. The thermodynamic parameters obtained in this study can be incorporated into model predictions of the maximum Langmuir pressure and CH4- sorption capacity of shales under reservoir temperature and pressure conditions.

  15. The study of the soil clay minerals within the framework of the integrated research headed by N.I. Bazilevich

    NASA Astrophysics Data System (ADS)

    Chizhikova, N. P.

    2010-11-01

    The main areas of the integrated biogeochemical studies performed under the supervision of N.I. Bazilevich dealing with the investigation of soil minerals were considered. The development of the clay profiles in soils under the effect of chernozem formation, solodization, salinization, solonetzization, and gleyzation, the spatial differentiation of which favored the development of the pronounced complexity of the soil cover in the forest-steppe zone of the Baraba Lowland, was described. It was shown that irrigation with sodic water induces the evolution of chernozems to solodized soils due to the dispersion and destruction of the clay minerals. The behavior of the minerals in the sodic solonetz-solonchaks of Armenia during their reclamation with sulfuric acid and iron (II) sulfate was explained. The effect of the root exudates from black saxaul ( Haloxylon aphyllum) on the transformation of the layered silicates in the rooting zone of sandy desert soils was noted.

  16. Simple algorithms for remote determination of mineral abundances and particle sizes from reflectance spectra

    NASA Technical Reports Server (NTRS)

    Johnson, Paul E.; Smith, Milton O.; Adams, John B.

    1992-01-01

    Algorithms were developed, based on Hapke's (1981) equations, for remote determinations of mineral abundances and particle sizes from reflectance spectra. In this method, spectra are modeled as a function of end-member abundances and illumination/viewing geometry. The method was tested on a laboratory data set. It is emphasized that, although there exist more sophisticated models, the present algorithms are particularly suited for remotely sensed data, where little opportunity exists to independently measure reflectance versus article size and phase function.

  17. Organic and clay mineral diagenesis in Neogene sediments of western Taiwan

    SciTech Connect

    Hsueh, C.M.

    1985-01-01

    Three deep wells (two in the northern region and one in the southern region) with completion depths of over 5000m have been selected and the rock samples thoroughly examined. The TOC data of most samples studied are less than 1%, which is the TOC of an average shale. The low TOC is unfavorable for the Neogene sediments in western Taiwan as good source rocks. The data of C,H elemental analysis and Rock-Eval pyrolysis imply that the quality of kerogen in the northern region inclines to type II wet-gas prone, and in the southern region inclines to type III dry-gas prone. The maturity parameters of bitumen ratio, vitrinite reflectance, Tmax of Rock-Eval pyrolysis, and TTI of Lopatin's method show that the threshold of the oil-generative zone (about 0.6% Ro) in the northern region is in middle Miocene (about 3000m) and in the southern region is in lower Pliocene (about 4500m). The result of clay mineral analysis reveals that the transformation of smectitic clays to ordered mixed-layered smectite-illite can be identified and correlated with 0.6% Ro vitrinite reflectance. The illite crystallinity values are in the range of incipient to weak metamorphism and decrease with burial depth implying that the source area of low-grade metamorphic rocks has been uplifted rapidly so that the erosion from the exposed source area where the metamorphic grade became higher and higher was sufficiently fast to prevent weathering of illite. The Neogene sediments studied would not be expected to generate substantial amounts of oil. However, it can be expected that the pre-Miocene sediments in the northern region and the pre-Pliocene sediments in the southern region should have generated substantial amounts of gas at deeper depths.

  18. Controls on clay minerals assemblages in an early paleogene nonmarine succession: Implications for the volcanic and paleoclimatic record of extra-andean patagonia, Argentina

    NASA Astrophysics Data System (ADS)

    Raigemborn, María Sol; Gómez-Peral, Lucía E.; Krause, Javier Marcelo; Matheos, Sergio Daniel

    2014-07-01

    The distribution of the clay minerals of the Banco Negro Inferior-Río Chico Group succession (BNI-RC), a middle Danian-middle Eocene mainly continental epiclastic-pyroclastic succession exposed in the Golfo San Jorge Basin, extra-Andean Patagonia (∼46° LS), is assessed in order to determine the possible origin of clay and specific non-clay minerals using X-ray diffraction and scanning electron microscopy analyses. The control over the clay mineralogy of the sedimentary settings, contemporary volcanism, paleoclimate and weathering conditions is considered. A paleoclimatic reconstruction is provided and correlated with the main global warming events that occurred during the early Paleogene. Mineralogical analyses of BNI-RC demonstrate that smectite and kaolin minerals (kaolinite, halloysite and kaolinite/smectite mixed layers) are the main clay minerals, whereas silica polymorphs (volcanic glass and opal) are common non-clay minerals. Throughout the succession, smectite and kaolin minerals are arranged in different proportions in the three clay-mineral assemblages. These show a general vertical trend in which the smectite-dominated assemblage (S1) is replaced by the smectite-dominated assemblage associated with other clays (S2) and the kaolinite-dominated assemblage (K), and finally by S2 up-section. The detailed micromorphological analysis of the clay and non-clay minerals allows us to establish that the origins of these are by volcanic ash weathering, authigenic and pedogenic, and that different stages in the evolution of mineral transformations have occurred. The supply of labile pyroclastic material from an active volcanic area located to the northwest of the study area could have acted as precursor of the authigenic and volcanogenic minerals of the analyzed succession. Diverse fine-grained lithological facies (muddy and tuffaceous facies) and sedimentary settings (coastal swamp and transitional environments, and different fluvial systems) together with variable climate and weathering conditions controlled the mineralogical transformations and the arrangement of clay-mineral assemblages. The paleoclimatic reconstruction suggests a general warm and humid climate. However, the temporal trend of the clay-mineral assemblages, the ratios between smectite and kaolinite and the micromorphological analysis of clay minerals contrasted with evidence from sedimentological analyses suggest a warm and seasonal climate for the basal part of the unit, a warm and humid climate with a relatively more perennial rainfall regime in the middle part of the unit, and a warm and less humid, probably subhumid, climate up-section. Such a reconstruction makes it possible to establish a correlation with some of the hyperthermal events of the Early Paleogene Global Warming (EPGW) and, consequently, constitute one of the most complete time records of the EPGW in South America.

  19. Environmental Weathering of Aluminosilicate Clay Minerals: Solid-State NMR Studies of Transformations Leading to Radionuclide Sequestration

    SciTech Connect

    Mueller, Karl T.; Crosson, Garry; Chorover, Jon; Choi, Sunkyung

    2004-03-28

    Mobilities of radionuclides (such as 137Cs and 90Sr) are governed by their interactions with natural soil particles in the saturated and unsaturated zones at Department of Energy sites. High surface area aluminosilicate clay minerals are a component of the natural soils beneath the leaking waste tanks at these sites and serve as possible radionuclide sorbents. However, due to the characteristics of the contaminant medium (high pH, high Al and high ionic strength), clay minerals are susceptible to transformations during exposure to tank waste leachates. We are currently studying the transformation of clays under specific chemical conditions that mimic the composition of known contaminant solutions. In these studies, specimen clay samples are reacted for varying time periods (up to one year) with simulated tank waste leachate solutions. Mineral dissolution and transformation are followed with solution analysis, x-ray diffraction and a number of other analytical methods. We report here results from 27Al MAS NMR at variable magnetic field strengths (up to 18.8 T), 29Si MAS NMR and 1H/29Si CPMAS NMR and evaluate these results along with those of other parallel analytic studies.

  20. CLAY MINERALOGY OF INSOLUBLE RESIDUES IN MARINE EVAPORITES.

    USGS Publications Warehouse

    Bodine, Marc W., Jr.

    1985-01-01

    Insoluble residues from three sequences of Paleozoic marine evaporites (Retsof salt bed in western New York, Salado Formation in south-eastern New Mexico, and Paradox Member of the Hermosa Formation in southeastern Utah) are rich in trioctahedral clays. Chlorite (clinochlore), corrensite (mixed-layer chlorite-trioctahedral smectite), talc, and illite (the only dioctahedral clay) are the dominant clay minerals; serpentine, discrete trioctahedral smectite (saponite), and interstratified talc-trioctahedral smectite are sporadically abundant. These clay-mineral assemblages differ chemically and mineralogically from those observed in most continental and normal marine rocks, which commonly contain kaolinite, dioctahedral smectite (beidellite-montmorillonite), illite, mixed-layer illite-dioctahedral smectite, and, in most cases, no more than minor quantities of trioctahedral clay minerals. The distinctive clay mineralogy in these evaporite sequences suggests a largely authigenic origin. These clay minerals are thought to have formed during deposition and early diagenesis through interaction between argillaceous detritus and Mg-rich marine evaporite brines.

  1. Orientation and optical properties of methylene blue crystal for better understanding of interactions with clay mineral surface

    NASA Astrophysics Data System (ADS)

    Milošević, Maja; Logar, Mihovil

    2013-04-01

    The properties of cationic dye Methylene blue (MB) adsorbed on diferent surfaces have been investigated intensively over the years and various models for the orientation of its cations have been proposed (Hang and Brindley, 1970; Bujdak et al., 2003; Li and Zare, 2004; Marr III et al., 1973; Bujdak, 2006).The main objective of this work is to investigate and determine orientation and optical properties of metylene blue crystal upon its crystallization on a glass slate and to use those findings in better understanding of interactions with clay minerals. Cationic dyes have very high affinity for clay surfaces and those interactions are easily detected, therefore these dyes are used to determine several properties of clay surfaces (morphology, layer charge, CEC). For this study, we have selected a group of MB crystal and carried out XRD analysis, polarized absorption spectra measurement (400 - 900 nm) and determination of optical properties (pleochroism, determination of twining and extinction angle) using polarizing microscope. Methylene blue crystals are exhibiting mostly needle like habitus with huge difference in width - length ratio. According to X-ray diffraction it is quite obvious that the y (b) axis is perpendicular to the crystal surface. The x (a) and z (c) axis lie in the crystal plane (010). Crystals exhibit prominent dichroism: from blue (E || elong.) to colorless. In accordance with current interpretation of MB spectra peaks at 647 and 570 nm can be assigned as dimer aggregation and peaks at 475 and 406 nm as higher level of aggregation. All of them exhibit pronounced polarization dependence. The group of peaks at lower energy (700 to 900 nm) do not show significant polarization dependence and they correspond to the J - aggregates. Peak at around 800 nm have been noticed as fluorescence active. In dependence with thickness of the crystals and vibration direction we have observed presence of polysynthetic twinning which can be compared with polysynthetic twinning of feldspar minerals. Final result of molecular polymerization is represented as crystal framework of methylene blue. Model of the MB molecular aggregation in the crystal structure could be used as a way for the interpretation of the thin layer structure and the molecular aggregation on the clay surface. References - Hang P.T. & Brindley G.W., (1970), Clays and Clay Minerals, 18, 203-212. - Bujdak J., Iyi N., Kaneko Y. and Sasai R., (2003), Clay Minerals (2003), 38, 561-572. - Li F. and Zare R.N., (2005), J. Phys. Chem. B 2005, 109, 3330-3333. - Marr III, H.E., Stewart, J.M. and Chiu, M.F., (1973), Acta Cryst. (1973), B29, 847. - Bujdak J., (2006), Applied Clay Science 34 (2006) 58 - 73

  2. Distribution of clay minerals in surface sediments of the western Gulf of Thailand: Sources and transport patterns

    NASA Astrophysics Data System (ADS)

    Shi, Xuefa; Liu, Shengfa; Fang, Xisheng; Qiao, Shuqing; Khokiattiwong, Somkiat; Kornkanitnan, Narumol

    2015-06-01

    A high density sampling program during two joint China-Thailand scientific cruises in 2011-2012 included collection of 152 gravity box cores in the Gulf of Thailand (GoT). Samples from the top 5 cm of each core were analyzed by X-ray diffraction for clay mineral content. Several systemic analytical approaches were applied to examine the distribution pattern and the constraint factors of clay minerals in the surface sediments of the western GoT. The clay minerals mainly comprise illite, kaolinite, chlorite and smectite, having the average weight percent distributions of 50%, 34%, 14% and 2%, respectively. Based on the spatial distribution characteristics and statistical results, the study area can be classified into three provinces. Province I contains high concentrations of smectite, and covers the northern GoT, sediments in this province are mainly from rivers discharging into the upper GoT, especially the Chao Phraya and Mae Klong Rivers. Sediments in Province II are characterized by higher values of illite, located in the central GoT, where fine sediments are contributed by the Mekong River and from the South China Sea. Province Ш, in the coastal regions of southwestern GoT close to Malaysia, exhibits a clay mineral assemblage with complex distribution patterns, and may contain terrestrial materials from the Mae Klong River as well as re-suspended sediments. Results of integrative analysis also demonstrate that the hydrodynamic environment in the study area, especially the seasonal various circumfluence and eddies, play an important role in the spatial distribution and dispersal of clay fraction in sediments.

  3. Clays, common

    USGS Publications Warehouse

    Virta, R.L.

    1998-01-01

    Part of a special section on the state of industrial minerals in 1997. The state of the common clay industry worldwide for 1997 is discussed. Sales of common clay in the U.S. increased from 26.2 Mt in 1996 to an estimated 26.5 Mt in 1997. The amount of common clay and shale used to produce structural clay products in 1997 was estimated at 13.8 Mt.

  4. Minerals

    NASA Astrophysics Data System (ADS)

    1983-06-01

    The Minerals Program of the Australian Bureau of Mineral Resources aims to develop the understanding of the origin, abundance, age, and distribution of Australia's mineral resources in the context of the structure and geological history of the continent as a basis for exploration and assessment. Research from the following subprograms of the Minerals Program was reviewed: (1) the origin and distribution of minerals in space and time, (2) the metallogenic provinces of Australia, (3) remote sensing techniques applied to Australia's weathered zone and its related minerals, (4) airborne geophysical mapping, (5) crustal geophysics, and (6) the origin and distribution of offshore mineral deposits.

  5. Numerical Simulation of Injectivity Effects of Mineral Scaling and Clay Swelling in a Fractured Geothermal Reservoir

    SciTech Connect

    Xu, Tianfu; Pruess, Karsten

    2004-05-10

    A major concern in the development of hot dry rock (HDR) and hot fractured rock (HFR) reservoirs is achieving and maintaining adequate injectivity, while avoiding the development of preferential short-circuiting flow paths such as those caused by thermally-induced stress cracking. Past analyses of HDR and HFR reservoirs have tended to focus primarily on the coupling between hydrology (flow), heat transfer, and rock mechanics. Recent studies suggest that rock-fluid interactions and associated mineral dissolution and precipitation effects could have a major impact on the long-term performance of HFR reservoirs. The present paper uses recent European studies as a starting point to explore chemically-induced effects of fluid circulation in HFR systems. We examine ways in which the chemical composition of reinjected waters can be modified to improve reservoir performance by maintaining or even enhancing injectivity. Chemical manipulations considered here include pH modification and dilution with fresh water. We performed coupled thermo-hydrologic-chemical simulations in which the fractured medium was represented by a one-dimensional MINC model (multiple interacting continua), using the non-isothermal multi-phase reactive geochemical transport code TOUGHREACT. Results indicate that modifying the injection water chemistry can enhance mineral dissolution and reduce clay swelling. Chemical interactions between rocks and fluids will change a HFR reservoir over time, with some changes favorable and others not. A detailed, quantitative understanding of processes and mechanisms can suggest chemical methods for reservoir management, which may be employed to improve the performance of the geothermal system.

  6. Chemical and Structural Changes in Aluminosilicate Clay Minerals Caused by Exposure to Acid and Implications for Ice Nucleation

    NASA Astrophysics Data System (ADS)

    Sihvonen, S.; Lyktey, N. A.; Freedman, M. A.

    2013-12-01

    Several recent studies have shown that sulfuric acid lowers the activity of clay minerals toward ice nucleation. In order to understand the origins of the reported decrease in ice nucleation activity, we have investigated the chemical and structural changes that occur to swelling and non-swelling clay minerals upon processing with sulfuric and nitric acid. Using X-ray diffraction (XRD), we have observed that kaolinite and montmorillonite reactions with sulfuric acid result in the formation of hydrated aluminum sulfate. In addition, the montmorillonite lattice changes during the reaction. Nitric acid has no effect on either type of mineral. Structural changes to the minerals were additionally visualized using transmission electron microscopy (TEM). These images suggest that sulfuric acid attacks the edges of kaolinite. We have also performed inductively coupled plasma - atomic emission spectroscopy (ICP-AES) to investigate the leaching of cations from these minerals. We will discuss the implications of our results for heterogeneous ice nucleation, and will show results from ice nucleation experiments with our processed minerals.

  7. Use of clay-mineral alteration patterns to define syntectonic permeability of joints (cleat) in Pennsylvania anthracite coal

    NASA Astrophysics Data System (ADS)

    Daniels, E. J.; Marshak, S.; Altaner, S. P.

    1996-10-01

    Joints (cleat) in Pennsylvania anthracite contain two distinct clay-mineral assemblages, both of which formed by alteration of preexisting kaolinite at peak metamorphic conditions during the Alleghanian orogeny. The first assemblage, NH 4-illite or pyrophyllite ± quartz, formed by reaction of kaolinite with methane-rich fluids derived from within the coal. The second assemblage, sudoite ± tosudite ± rectorite ± berthierine, formed by the reaction of kaolinite with ferromagnesian-bearing hydrothermal fluids which must have come from outside the coal. In an earlier paper, we suggested that the first assemblage indicated clay diagenesis in low-permeability environments, and that the second assemblage indicated clay diagenesis in high-permeability environments. If this premise is correct, then the distribution of clay-mineral alteration assemblages serves to define syntectonic permeability variations in coal cleat. The first assemblage dominates in the coal matrix itself, in isolated cleat, in cleat that parallel the regional trend of Alleghanian folds, and in the mirror portions of cleat oriented perpendicular to the fold trends, suggesting that these regions are low-permeability environments. The second assemblage dominates in the hackle fringe of interconnected cleat that trend perpendicular to the strike of the Appalachian orogen, suggesting that these regions are high-permeability environments. Our results emphasize that syntectonic cleat permeability is a function of cleat orientation, macroscopic cleat interconnectivity and orientation, as well as microscopic cleat-surface morphology.

  8. Mineral-produced high-pressure striae and clay polish: Key evidence for nonballistic transport of ejecta from Ries crater

    USGS Publications Warehouse

    Chao, E.C.T.

    1976-01-01

    Recently discovered mineral-produced, deeply incised striae and mirror-like polish on broken surfaces of limestone fragments from the sedimentary ejecta of the Ries impact crater of southern Germany are described. The striae and polish were produced under high confining pressures during high-velocity nonballistic transport of the ejecta mass within the time span of the cratering event (measured in terms of seconds). The striae on these fragments were produced by scouring by small mineral grains embedded in the surrounding clay matrix, and the polish was formed under the same condition, by movements of relatively fragment-free clay against the fragment surfaces. The occurrence of these striae and polish is key evidence for estimating the distribution and determining the relative importance of nonballistic and ballistic transport of ejecta from the shallow Ries stony meteorite impact crater.

  9. Clay mineral reactions caused by frictional heating during an earthquake: An example from the Taiwan Chelungpu fault

    NASA Astrophysics Data System (ADS)

    Hirono, Tetsuro; Fujimoto, Koichiro; Yokoyama, Tadashi; Hamada, Yohei; Tanikawa, Wataru; Tadai, Osamu; Mishima, Toshiaki; Tanimizu, Masaharu; Lin, Weiren; Soh, Wonn; Song, Sheng-Rong

    2008-08-01

    To understand the chemical reactions of clay minerals in a fault zone during an earthquake, we analyzed the clay minerals in the Chelungpu fault, which slipped during the 1999 Chi-Chi earthquake. X-ray diffraction spectroscopy showed that kaolinite and smectite contents were lower in the black gouge zone than in the surrounding gray gouge, breccia, or fracture-damaged zones. We applied a chemical kinetics approach to examine whether dehydroxylation of kaolinite and dehydration of interlayer water, dehydroxylation, and illitization of smectite occurred during coseismic frictional heating, and found that the first two reactions could complete under the temperature-time profile of the Chi-Chi earthquake, reconstructed by a previous study. Because dehydration of smectite interlayer water and dehydroxylation of kaolinite would have completed 3.6 and 8.2 s after the beginning of slip, the resulting release of water might have affected the frictional mechanism during the earthquake.

  10. New information on the glacial history of the NW Barents Sea from clay minerals and radiocarbon dates

    NASA Astrophysics Data System (ADS)

    Hogan, Kelly; Dowdeswell, Julian; Hillenbrand, Claus-Dieter; Ehrmann, Werner

    2014-05-01

    Here we present results from new analyses on marine sediment cores that recovered subglacial and postglacial units deposited in the NW Barents Sea during the LGM and the Holocene. We have performed a pilot study on clay-mineral assemblages in three cores collected in palaeo-ice stream troughs surrounding Nordaustlandet (Hinlopen, Erik Eriksen and Kvitøya troughs) to investigate the provenance and pathways of subglacial sediment transported by the Barents Sea Ice Sheet (BSIS) during the LGM and of Holocene marine sediments. In all of the cores there is a clear change in clay mineral composition between the subglacial diamicts and the postglacial muds, and the clay-mineral assemblage in the diamicts is distinctive in each core. This suggests that the clay mineral composition records different pathways of subglacially transported detritus around eastern Svalbard. We interpret these data in relation to local source rocks on the Svalbard archipelago and in the central Barents Sea in order to provide new information regarding the BSIS dynamics during the last glacial period, about which there is still considerable debate for the central-northern Barents Sea sector (cf. Landvik and Ingolfsson, 2013). In addition, new radiocarbon ages from sediment cores around Nordaustlandet suggest that grounded ice had retreated from the shelf break north of Nordaustlandet and in Kvitøya Trough east of Svalbard by 13.3-13.6 14C kyrs BP. This is in line with deglacial dates of 13-13.3 14C kyrs BP from the other major troughs on the northern Barents Sea margin (Saint Anna and Franz Victoria troughs). In Hinlopen Trough our deglacial date confirms that the Polar Front was in the vicinity of the core site on the continental shelf some 20 km landward of the shelf break by 11.0 14C kyrs BP.

  11. Role of Clay Minerals in Long-Distance Transport of Landslides in Valles Marineris, Mars

    NASA Astrophysics Data System (ADS)

    Watkins, J.; Ehlmann, B. L.; Yin, A.

    2014-12-01

    Long-runout (> 50 km) subaerial landslides are rare on Earth, but are common features episodically shaping Mars' Valles Marineris (VM) trough system over the past 3.5 billion years. They display two end-member morphologies: a thick-skinned inner zone, characterized by fault-bounded, rotated blocks near their source region, and a thin-skinned, exceptionally long-runout outer zone, characterized by thin sheets spreading over 10s of km across the trough floor. Four decades of studies on the latter have resulted in two main competing hypotheses to explain their long-distance transport: (1) movement of landslides over layers of trapped air or soft materials containing ice or snow, enabling basal lubrication, and (2) fluidization of landslide materials with or without the presence of water and volatiles. To address this issue, we examine the mineralogic composition of landslides across VM using Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) near-infrared spectral data analysis coupled with detailed geologic mapping and morphometric analysis of satellite images. Our survey reveals a general correlation between transport distance, significant lateral spreading, and the presence of hydrated silicates among VM landslides. Given that smectite clay absorbs water into its layered crystal structure and can reduce the friction coefficient by a factor of three v. that of dry rocks, these results suggest that hydrated silicates played a decisive role in facilitating long-runout landslide transport in VM. We propose that, concurrent with downslope failure and sliding of broken trough-wall rock, frontal landslide masses overrode and entrained hydrated-silicate-bearing trough-floor deposits, lubricating the basal sliding zones and permitting the landslide outer zones to spread laterally while moving forward over the low-friction surface. The key participation of hydrated silicates in episodic, sustained landslide activity throughout the canyon implies that clay minerals, generated by water-rock interactions in the Noachian and Hesperian (4.1- 3.3 Ga), exert a long-lasting influence on geomorphic processes that shape the surface of the planet.

  12. Geochemical studies of clay minerals III. The determination of free silica and free alumina in montmorillonites

    USGS Publications Warehouse

    Foster, M.D.

    1953-01-01

    Determination of free silica by the method proposed made possible the derivation of logical formulas for several specimens of montmorillonites for which the formulas could not be derived from the analyses alone. Other montmorillonites, for which logical formulas could be derived from their analyses, were found to contain small amounts of free silica or free alumina. Others were found to contain neither free silica nor free alumina. The method consists of the following steps: (1) digestion of 1 g of the specimen with 0.5 N NaOH solution in a covered platinum crucible or dish on a steam bath for 4 hrs, stirring the mixture at 30-min intervals, (2) filtration of the undissolved material, followed by washing several times with 1% NaOH solution, (3) neutralization of the filtrate with HCl, addition of 5 ml HCl in excess and determination of SiO and Al2O3 in the usual way and (4) calculation of the amount of free SiO2 or free Al2O3 if any and the amount of attack of the clay structure by the treatment from the ratio of SiO2 to Al2O3 dissolved and the ratio of SiO2 to Al2O3 obtained on analysis. Tests with 5% Na2CO3 solution, the reagent formerly used for the solution of free SiO2 in rocks and minerals, showed that solution of opal by this reagent is always fractional, never complete, no matter how small the amount present or how long the period of treatment. Re-treatment of the sample results in 90-95% solution if 10 mg or less of opal is present, but for larger amounts of opal the percentage dissolved decreases as the amount present increases. On the other hand, 75 ml of 0.5 N NaOH completely dissolves as much as 400 mg of opal in 4 hrs digestion in a covered platinum crucible or dish, on a steam bath. However, a weaker solution or a shorter period of digestion does not effect complete solution. The same amount (75 ml) of 0.5 N NaOH also dissolves 90 mg of cristobalite and 57 mg of quartz having a grain size of less than 2 microns. Use of NaOH also permits determination of the amount of alumina dissolved, and estimation of the extent to which the clay structure was attacked by the treatment. ?? 1953.

  13. Geoscientific Applications of Particle Detection and Imaging Techniques withSpecial Focus on the Monitoring Clay Mineral Reactions

    NASA Astrophysics Data System (ADS)

    Warr, Laurence N.; Grathoff, Georg H.

    The combined use of focused X-ray, electron, and ion beams offers a diverse range of analytical capabilities for characterizing nanoscale mineral reactions that occur in hydrous environments. Improved image and microanalytical techniques (e.g., electron diffraction and energy-dispersive X-ray spectroscopy), in combination with controlled sample environments, are currently leading to new advances in the understanding of fluid-mineral reactions in the Earth Sciences. One group of minerals playing a key role in the containment of radioactive waste and the underground storage of CO2 is the clay minerals: these small, expandable, and highly adsorbent hydrous phyllosilicates form important low-permeable geological barriers by which waste can be safely deposited. In this article we summarize some of the state-of-the-art particle and imaging techniques employed to predict the behavior of both engineered and natural clay mineral seals in proposed storage sites. Particular attention is given to two types of low-permeability geomaterials: engineered bentonite backfill and natural shale in the subsurface. These materials have contrasting swelling properties and degrees of chemical stability that require detailed analytical study for developing suitable disposal or storage solutions.

  14. Oxygen isotope evidence of climate change from pedogenic clay minerals in the Himalayan molasse

    SciTech Connect

    Stern, L.A.; Chamberlain, C.P.; Reynolds, R.C.; Johnson, G.D.

    1997-02-01

    In this study, we examine the oxygen isotope ratios of smectite and kaolinite in a stratigraphic sequence of paleosols in the Siwalik Himalayan molasse on the Potwar Plateau, northern Pakistan. There is a 3-4{per_thousand} increase in the smectite {delta}{sup 18}O values synchronous with a {approximately}3.5{per_thousand} increase in {delta}{sup 18}O values of pedogenic calcite at 8.5-6.5 Ma. The covariation of the {delta}{sup 18}O values of smectite with calcite {delta}{sup 18}O values through time strongly suggests a pedogenic origin of smectite and that its {delta}{sup 18}O values reflect the oxygen isotope ratio of the soil water present during pedogenesis. These data show that the {delta}{sup 18}O values of clay minerals in paleosols in aggrading sedimentary sequences are viable paleoclimate indicators. Kaolinite {delta}{sup 18}O values are similar to smectite {delta}{sup 18}O values, as would be expected for pedogenic kaolinite, but there is greater variation in these data which we attribute to incomplete mineral separation. The measured permil oxygen isotope fractionation between calcite and smectite within individual paleosols is, on average, {approximately}3{per_thousand} higher than the equilibrium fractionation. This isotopic disequilibrium can be explained by the calcite forming predominantly during the dry winter season and the smectite forming predominantly during the wet summer season. The synchronous 3.5{per_thousand} increase in oxygen isotope ratios of smectite and calcite at 8.5-6.5 Ma indicates that this {sup 18}O/{sup 16}O increase is not due to diagenesis, but rather results from a climate change. The most likely causes of the {sup 18}O/ {sup 16}O increase in smectite and calcite are either increased aridity resulting in increased soil water evaporation (thus {sup 18}O enrichment) and/or a change from more continental to more marine-sourced precipitation. 83 refs., 8 figs., 2 tabs.

  15. Non-selective oxidation of humic acid in heterogeneous aqueous systems: a comparative investigation on the effect of clay minerals.

    PubMed

    Kavurmaci, Sibel Sen; Bekbolet, Miray

    2014-01-01

    Application of photocatalysis for degradation of natural organic matter (NOM) has received wide interest during the last decades. Besides NOM, model compounds more specifically humic acids (HAs) were also studied. As a continuation of the previous research, TiO2 photocatalytic degradation of HA was investigated in the presence of clay minerals, i.e., montmorillonite (Mt) and kaolinite (Kt). Degradation of HA was expressed by the pseudo-first-order kinetic modelling of dissolved organic carbon (DOC) and UV-VIS parameters (Colour436 and UV254). A slight rate enhancement was attained for Colour436 and UV254 in the presence of either Mt or Kt. The presence of clay particles did not significantly change the DOC degradation rate of HA. The effect of ionic strength (Ca2+ loading from 5 x 10(-4) M to 5 x 1(-3) M) was also assessed for the photocatalytic degradation of sole HA and HA in the presence of either Mt or Kt. Following photocatalytic treatment, molecular size distribution profiles of HA were presented. Besides the effective removal of higher molecular size fractions (100 and 30 kDa fractions), transformation to lower molecular size fractions (<3 kDa) was more pronounced for sole HA rather than HA in the presence of clay minerals. Scanning electron microscopic images with the energy dispersive X-ray analysis confirmed the diversities in surface morphologies of the binary and ternary systems composed of HA, TiO2 and Mt or Kt both prior to and following photocatalysis. This study demonstrated that photocatalysis could be applicable for DOC degradation in the presence of clay minerals in natural waters. PMID:25145193

  16. Carbonation of Clay Minerals Exposed to scCO2/Water at 200 degrees and 250 degrees C

    SciTech Connect

    Sugama, T.; Ecker, L.; Gill, S.; Butcher, T.; Bour, D.

    2010-11-01

    To clarify the mechanisms of carbonation of clay minerals, such as bentonite, kaolinite, and soft clay, we exposed them to supercritical carbon dioxide (scCO2)/water at temperatures of 200 and 250 C and pressures of 1500 and 2000 psi for 72- and 107-hours. Bentonite, comprising three crystalline phases, montmorillonite (MMT), anorthoclase-type albite, and quartz was susceptible to reactions with ionic carbonic acid yielded by the interactions between scCO2 and water, particularly MMT and anorthoclase-type albite phases. For MMT, the cation-exchangeable ions, such as Na+ and Ca2+, present in its basal interplanar space, were replaced by proton, H+, from ionic carbonic acid; thereafter, the cations leaching from MMT directly reacted with CO32- as a counter ion of H+ to form carbonate compounds. Such in-situ carbonation process in basal space caused the shrinkage and breakage of the spacing structure within MMT. In contrast, the wet carbonation of anorthoclase-type albite, categorized as rock minerals, entailed the formation of three amorphous by-products, such as carbonates, kaolinite-like compounds, and silicon dioxide. Together, these two different carbonations caused the disintegration and corruption of bentonite. Kaolinite clay containing the amorphous carbonates and silicon dioxide was inert to wet carbonation. We noted only a gain in weight due to its water uptake, suggesting that kaolinite-like by-products generated by the wet carbonation of rock minerals might remain unchanged even during extended exposure. Soft clay consisting of two crystalline phases, dolomite and silicon dioxide, also was unaltered by wet carbonation, despite the uptake of water.

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

    NASA Technical Reports Server (NTRS)

    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.

  18. Mineralogy. Discovery of bridgmanite, the most abundant mineral in Earth, in a shocked meteorite.

    PubMed

    Tschauner, Oliver; Ma, Chi; Beckett, John R; Prescher, Clemens; Prakapenka, Vitali B; Rossman, George R

    2014-11-28

    Meteorites exposed to high pressures and temperatures during impact-induced shock often contain minerals whose occurrence and stability normally confine them to the deeper portions of Earth's mantle. One exception has been MgSiO3 in the perovskite structure, which is the most abundant solid phase in Earth. Here we report the discovery of this important phase as a mineral in the Tenham L6 chondrite and approved by the International Mineralogical Association (specimen IMA 2014-017). MgSiO3-perovskite is now called bridgmanite. The associated phase assemblage constrains peak shock conditions to ~ 24 gigapascals and 2300 kelvin. The discovery concludes a half century of efforts to find, identify, and characterize a natural specimen of this important mineral. PMID:25430766

  19. A recommended procedure for the preparation of oriented clay-mineral specimens for X-ray diffraction analysis; modifications to Drever's filter-membrane peel technique

    USGS Publications Warehouse

    Pollastro, R.M.

    1982-01-01

    Extremely well-oriented clay mineral mounts for X-ray diffraction analysis can be prepared quickly and without introducing segregation using the filter-membrane peel technique. Mounting problems encountered with smectite-rich samples can be resolved by using minimal sample and partial air-drying of the clay film before transfer to a glass slide. Samples containing small quantities of clay can produce useful oriented specimens if Teflon masks having more restrictive areas are inserted above the membrane filter during clay deposition. War]page and thermal shock of glass slides can be controlled by using a flat, porous, ceramic plate as a holding surface during heat treatments.

  20. [Mineralogy and genesis of mixed-layer clay minerals in the Jiujiang net-like red soil].

    PubMed

    Yin, Ke; Hong, Han-Lie; Li, Rong-Biao; Han, Wen; Wu, Yu; Gao, Wen-Peng; Jia, Jin-Sheng

    2012-10-01

    Mineralogy and genesis were investigated using X-ray diffraction (XRD), Fourier infrared absorption spectroscopy (FTIR) and high resolution transmission electron microscopy (HRTEM) to understand the mineralogy and its genesis significance of mixed-layer clay minerals in Jiujiang red soil section. XRD and FTIR results show that the net-like red soil sediments are composed of illite, kaolinite, minor smectite and mixed-layer illite-smectite and minor mixed-layer kaolinite-smectite. HRTEM observation indicates that some smectite layers have transformed into kaolinite layers in net-like red soil. Mixed-layer illite-smectite is a transition phase of illite transforming into smectite, and mixed-layer kaolinite-smectite is a transitional product relative to kaolinite and smectite. The occurrence of two mixed-layer clay species suggests that the weathering sequence of clay minerals in net-like red soil traversed from illite to mixed-layer illite-smectite to smectite to mixed-layer kaolinite-smectite to kaolinite, which indicates that net-like red soil formed under a warm and humid climate with strengthening of weathering. PMID:23285883

  1. Provenance and distribution of clay minerals in the sediments of the western continental shelf and slope of India

    NASA Astrophysics Data System (ADS)

    Purnachandra Rao, V.; Ramalingeswara Rao, B.

    1995-12-01

    The distribution of clay minerals from 156 surficial sediments of the western continental margin of India, ranging from 17 to 2000 m water depth, indicate that there are three principal sources of sediments. The illite and chlorite-rich assemblage derived from the Indus (Indus Province) is predominant in the continental margin sediments to the north of the Gulf of Kachchh. An assemblage of smectite with minor kaolinite, illite and chlorite, mostly derived from the Deccan Trap basalts (Deccan Trap Province), occurs all along the inner shelf from Saurashtra to Goa. Illite, however, dominates smectite in the outer shelf of Saurashtra and on the continental slope from Saurashtra to Goa. Some samples on the outer shelf of the Gulf of Cambay-Goa show trace contents of all clay minerals, while others from the same region show the dominance of smectite over illite. A smectite and kaolinite-rich assemblage with minor illite, chlorite and gibbsite derived from the Gneissic Province occurs both on the shelf and slope between Goa and Cochin. It appears that the Indus derived sediments are transported onto the continental slope and, to a lesser extent, the outer shelf of western India by a southerly surface current and admix with clays transported from the hinterland. The influence of the Indus borne sediments on the continental slope decreases from north to south and cross shelf transport processes dominate in the southwestern continental margin between Goa and Cochin.

  2. Swelling properties of montmorillonite and beidellite clay minerals from molecular simulation: Comparison of temperature interlayer cation, and charge location effects

    DOE PAGESBeta

    Teich-McGoldrick, Stephanie L.; Greathouse, Jeffery A.; Jove-Colon, Carlos F.; Cygan, Randall Timothy

    2015-08-27

    In this study, the swelling properties of smectite clay minerals are relevant to many engineering applications including environmental remediation, repository design for nuclear waste disposal, borehole stability in drilling operations, and additives for numerous industrial processes and commercial products. We used molecular dynamics and grand canonical Monte Carlo simulations to study the effects of layer charge location, interlayer cation, and temperature on intracrystalline swelling of montmorillonite and beidellite clay minerals. For a beidellite model with layer charge exclusively in the tetrahedral sheet, strong ion–surface interactions shift the onset of the two-layer hydrate to higher water contents. In contrast, for amore » montmorillonite model with layer charge exclusively in the octahedral sheet, weaker ion–surface interactions result in the formation of fully hydrated ions (two-layer hydrate) at much lower water contents. Clay hydration enthalpies and interlayer atomic density profiles are consistent with the swelling results. Water adsorption isotherms from grand canonical Monte Carlo simulations are used to relate interlayer hydration states to relative humidity, in good agreement with experimental findings.« less

  3. Swelling properties of montmorillonite and beidellite clay minerals from molecular simulation: Comparison of temperature interlayer cation, and charge location effects

    SciTech Connect

    Teich-McGoldrick, Stephanie L.; Greathouse, Jeffery A.; Jove-Colon, Carlos F.; Cygan, Randall Timothy

    2015-08-27

    In this study, the swelling properties of smectite clay minerals are relevant to many engineering applications including environmental remediation, repository design for nuclear waste disposal, borehole stability in drilling operations, and additives for numerous industrial processes and commercial products. We used molecular dynamics and grand canonical Monte Carlo simulations to study the effects of layer charge location, interlayer cation, and temperature on intracrystalline swelling of montmorillonite and beidellite clay minerals. For a beidellite model with layer charge exclusively in the tetrahedral sheet, strong ion–surface interactions shift the onset of the two-layer hydrate to higher water contents. In contrast, for a montmorillonite model with layer charge exclusively in the octahedral sheet, weaker ion–surface interactions result in the formation of fully hydrated ions (two-layer hydrate) at much lower water contents. Clay hydration enthalpies and interlayer atomic density profiles are consistent with the swelling results. Water adsorption isotherms from grand canonical Monte Carlo simulations are used to relate interlayer hydration states to relative humidity, in good agreement with experimental findings.

  4. Detection of Soluble and Fixed NH4+ in Clay Minerals by DTA and IR Reflectance Spectroscopy : A Potential Tool for Planetary Surface Exploration

    NASA Technical Reports Server (NTRS)

    Janice, Bishop; Banin, A.; Mancinelli, R. L.; Klovstad, M. R.; DeVincenzi, Donald L. (Technical Monitor)

    2001-01-01

    Nitrogen is an essential element for life. It is the only element among the six major biogenic elements, C, O, S, O, P, H, whose presence in the Martian soil has not been positively and directly established. We describe here a study assessing the ability to detect NH4 in soils by two methods: differential thermal analysis (DTA) and infrared (IR) reflectance spectroscopy. Four standard clay minerals (kaolinite, montmorillonite, illite and attapulgite) and an altered tephra sample from Mauna Kea were treated with NH4 in this study. Samples of the NH4-treated and leached clays were analyzed by DTA and infrared (IR) reflectance spectroscopy to quantify the delectability of soluble and sorbed/fixed NH4. An exotherm at 270-280 C was clearly detected in the DTA curves of NH4-treated (non-leached) samples. This feature is assigned to the thermal decomposition reaction of NH4. Spectral bands observed at 1.56, 2.05, 2.12, 3.06, 3.3, 3.5, 5.7 and 7.0 microns in the reflectance spectra of NH4-treated and leached samples are assigned to the sorbed/fixed ammonium in the clays. The montmorillonite has shown the most intense absorbance due to fixed ammonium among the leached samples in this study, as a result of its high cation sorption capacity. It is concluded that the presence of sorbed or fixed NH4 in clays may be detected by infrared (IR) reflectance or emission spectroscopy. Distinction between soluble and sorbed NH4 may be achieved through the presence or absence of several spectral features assigned to the sorbed NH4 moietyi and, specifically, by use of the 4.2 micrometer feature assigned to solution NH4. Thermal analyses furnish supporting evidence of ammonia in our study through detection of N released at temperatures of 270-330 C. Based on these results it is estimated that IR spectra measured from a rover should be able to detect ammonia if present above 20 mg NH4/g sample in the surface layers. Orbital IR spectra and thermal analyses measured on a rover may be able to detect ammonia in soils as well but at higher abundances. The spectral features at 3.06 and 7.0 microns due to bound NH4 in clays and altered Hawaiian tephra appear to be the most promising for detection by orbital spectrometers. If N species are present on Mars the sedimentary deposits may be the best regions to look for them.

  5. Alteration of glass as a possible source of clay minerals on Mars

    NASA Technical Reports Server (NTRS)

    Gooding, J. L.; Keil, K.

    1978-01-01

    Thermodynamic calculations show that, under present Martian surface conditions, favorable gas-solid weathering products of feldspar glasses should include beidellites (clays of the montmorillonite series) + carbonates + quartz. The gas-solid weathering of mafic silicate glass ( of volcanic or impact origin) may similarly favor the production of metastable Fe-rich montmorillonite clays. Simple mass-balance calculations suggest that gas-solid weathering of Martian proto-regolith containing 10% glass could conceivably produce a global blanket of clays at a rate of at least 0.4 cm/b.y. The production rate should be expected to increase significantly with the glass content and rate of reworking of the proto-regolith and with the availability of water. Complete extraction of altered glass from a lunar-like proto-regolith might yield a global Martian clay blanket about 10-100 cm in thickness.

  6. Ismenius Cavus: Ancient Lake Deposits and Clay Minerals Surrounded by Amazonian Glaciers

    NASA Astrophysics Data System (ADS)

    Mangold, N.; Dehouck, E.; Poulet, F.; Ansan, V.; Le Moulic, S.

    2015-10-01

    Landing site at the bottom of a 600 m deep paleolake nearby thick clay-rich sediments at lake bottom and deltaic deposits. Strong exobiological interest including ice-rich glacial landforms as water resource in same location.

  7. Protection of Nitrosomonas europaea colonizing clay minerals from inhibition by nitrapyrin.

    PubMed

    Powell, S J; Prosser, J I

    1991-08-01

    Nitrate production by Nitrosomonas europaea in inorganic liquid medium containing ammonium was limited by reduction in pH. In the presence of montmorillonite and vermiculite, expanding clays with high cation-exchange-capacity (CEC), nitrite yield was increased, ammonia oxidation continued at pH values below those which inhibited growth in the absence of clays and growth was biphasic. The first phase was similar to that in the absence of clays, while the second was characterized by a lower rate of nitrite production. Illite, a non-expanding clay with low CEC, had no significant effect on ammonia oxidation, while oxidation of ammonia-treated vermiculite (ATV) occurred with no significant change in the pH of the medium. ATV, montmorillonite and vermiculite, but not illite, protected cells from inhibition by nitrapyrin at concentrations inhibitory to cells growing in suspended culture. This protection was maintained in ATV homo-ionic to Al3+, but montmorillonite made homo-ionic to Al3+ did not provide protection from inhibition. Attachment of cells to clays with high CEC is therefore advantageous in providing exchange at the clay surface of NH+4 and H+ produced by ammonia oxidation, in reducing pH toxicity, and in protecting cells from inhibition. PMID:1955871

  8. Calcium-ammonium exchange experiments on clay minerals using a (45)Ca tracer technique in marine pore water.

    PubMed

    Ockert, Charlotte; Wehrmann, Laura M; Kaufhold, Stephan; Ferdelman, Tim G; Teichert, Barbara M A; Gussone, Nikolaus

    2014-01-01

    Understanding cation exchange processes is important for evaluating early diagenetic and synsedimentary processes taking place in marine sediments. To quantify calcium (Ca) exchange and Ca-ammonium exchange in a seawater environment, we performed experiments with a radioactive (45)Ca tracer on clay mineral standards (Fithian illite, montmorillonite and kaolinite) and marine sediments from the North Atlantic Integrated Ocean Drilling Program Site U1306A in artificial seawater (ASW). The results show that equilibrium during the initial attachment of Ca as well as the exchange of Ca by [Formula: see text] is attained in less than 2 min. On average 8-20% of the exchangeable sites of the clay minerals were occupied by Ca in a seawater medium. The conditional selectivity coefficient, describing the [Formula: see text] exchange in ASW is mineral specific and it was determined to be 0.07 for montmorillonite, 0.05 for a natural marine sediment and 0.013 for Fithian illite. PMID:24437731

  9. [X-ray powder diffraction of clay minerals of SZK01 core of Zabuye Lake, Tibetan Plateau].

    PubMed

    Zhang, Xue-Fei; Zheng, Mian-Ping

    2014-11-01

    The present article chooses the core from the borehole SZK01 in Zabuye Lake as the main research object. According to the results of X-ray powder diffraction of clay minerals, the major components are illite, illite and smectite mixed layer mineral (I/S), kaolinite and chlorite. According to the different species and contents of clay, integration of the characteristics of mineral and the results of Δ18O, we reestablished the evolution process of paleoclimate in Zabuye Lake. In compaison with SZK02 core in Zabuye, Greenland GISP2 and GRIP and Guliya ice core, it contains 5 stages since 115 ka in Zabuye: the last interglacial (15-75.5 ka), the earlier last glacial (75.5-60 ka), the interstage of the last glacial (60-30.1 ka), the last glacial maximum (30.1-16.7 ka) and deglacial-holocene (since 16.7 ka). We also recognized 6 Heinrich events (H1-H6) and warm event in 71 ka. In particular, the content of kaolinite is low, with the negative-skewed value of Δ18O in 52-53 ka, while the value of Δ18O in SZK02 and Guliya ice core is negative-skewed too, indicating the cold event in Tibet plateau, named H5-1. All the above demonstrated that the climate in Tibet plateau is global since the earlier last glacial, and it also has regional characteristics. PMID:25752070

  10. Ball clay

    USGS Publications Warehouse

    Virta, R.L.

    2000-01-01

    Part of the 1999 Industrial Minerals Review. The state of the ball clay industry in 1999 is presented. Record highs in the sales and use of ball clay were attained in 1999 due to the continued strength of the U.S. economy. U.S. production was estimated at 1.25 million st for the year, with more than half of that amount mined in Tennessee. Details of the consumption, price, imports, and exports of ball clay in 1999 and the outlook for ball clay over the next few years are provided.

  11. Vesta and the HED meteorites: Mid-infrared modeling of minerals and their abundances

    NASA Astrophysics Data System (ADS)

    Donaldson Hanna, K.; Sprague, A. L.

    2009-12-01

    We demonstrate that the use of an established spectral deconvolution algorithm with midinfrared spectral libraries of mineral separates of varying grain sizes is capable of identifying the known mineral compositions and abundances of a selection of howardite, eucrite, and diogenite (HED) meteorite samples. In addition, we apply the same technique to mid-infrared spectral emissivity measurements of Vesta that have been obtained from Cornell’s Mid-Infrared Asteroid Spectroscopy (MIDAS) Survey and the Infrared Space Observatory (ISO). Each Vesta measurement was made over a different range of longitudes. Our spectral deconvolution results to the Vesta spectra corroborate that Vesta’s surface is howardite or eucrite-like in composition and heterogeneous across its surface. The spectral fits produced by the linear deconvolution algorithm yields good results for the HED samples of known composition, thus giving us a high degree of confidence that our results for Vesta are valid.

  12. The titration of clay minerals I. Discontinuous backtitration technique combined with CEC measurements.

    PubMed

    Tournassat, Christophe; Greneche, Jean-Marc; Tisserand, Delphine; Charlet, Laurent

    2004-05-01

    Previous experimental studies on clay potentiometric titration have been unable to distinguish inorganic cation exchange in the interlayer and on basal plane surfaces from specific pH-dependent sorption of cations and anions on the edges. In this study, we refined a titration technique, combining discontinuous backtitration and cation exchange capacity (CEC) measurements, and applied it to the potentiometric titration of Na- and Ca-conditioned montmorillonites. This technique can be used to accurately measure cation exchange, edge surface proton charge, dissolution of clay, and precipitation of new phases. Thus, a precise measurement of the variations of net proton surface charge is possible. This has important implications for clay surface modeling (see part II of this article) and for processes that depend on the clay surface charge, e.g., alteration, rheological processes, and contamination retention applications. In addition, this study confirms the adsorption of ionic pairs such as CaCl+ in exchange site positions and shows that CaOH+ could behave like CaCl+. This result, together with the evidence of precipitation of a Ca?Si phase over a short time-scale (1 week) at high pH and low temperature, can be used to model clay-concrete interactions more accurately. We confirmed and quantified the H+/Na+ exchange reaction at low pH. Finally, we demonstrate that both the edge surface charge and the permanent structural charge are compensated for by the nonspecific sorption of cations from solution across the entire pH range from 4 to 11. Under these conditions, the surface potential is fully screened and does not need to be invoked in modeling sorption processes on clay particles in dilute suspensions. PMID:15051456

  13. An improved radiative transfer model for estimating mineral abundance of immature and mature lunar soils

    NASA Astrophysics Data System (ADS)

    Liu, Dawei; Li, Lin; Sun, Ying

    2015-06-01

    An improved Hapke's radiative transfer model (RTM) is presented to estimate mineral abundance for both immature and mature lunar soils from the Lunar Soil Characterization Consortium (LSCC) dataset. Fundamental to this improved Hapke's model is the application of an alternative equation to describe the effects of larger size submicroscopic metallic iron (SMFe) (>50 nm) in the interior of agglutinitic glass that mainly darken the host material, contrasting to the darkening and reddening effects of smaller size SMFe (<50 nm) residing in the rims of mineral grains. Results from applying a nonlinear inversion procedure to the improved Hapke's RTM show that the average mass fraction of smaller and larger size SMFe in lunar soils was estimated to be 0.30% and 0.31% respectively, and the particle size distribution of soil samples is all within their measured range. Based on the derived mass fraction of SMFe and particle size of the soil samples, abundances of end-member components composing lunar soil samples were derived via minimizing the difference between measured and calculated spectra. The root mean square error (RMSE) between the fitted and measured spectra is lower than 0.01 for highland samples and 0.005 for mare samples. This improved Hapke's model accurately estimates abundances of agglutinitic glass (R-squared = 0.88), pyroxene (R-squared = 0.69) and plagioclase (R-squared = 0.95) for all 57 samples used in this study including both immature and mature lunar soils. However, the improved Hapke's RTM shows poor performance for quantifying abundances of olivine, ilmenite and volcanic glass. Improving the model performance for estimation of these three end-member components is the central focus for our future work.

  14. Anomalous small angle x-ray scattering studies of heavy metal ion solvation behavior in clay minerals

    SciTech Connect

    Carrado, K.A.; Thiyagarajan, P.; Winans, R.E.; Song, Kang

    1997-09-01

    The authors have exploited anomalous small angle x-ray scattering (ASAXS) to monitor the solvation behavior of Cu(II), Er(III) and Yb(III) ions within the interlayers of the natural aluminosilicate clay mineral montmorillonite. The ASAXS technique can reveal the distribution of specific metallic species within a heterogeneous and disordered matrix. The variations of signal intensity as a function of absorption energy were monitored for all of the metal-clays as a function of hydration. Two different hydration levels were probed: as prepared at ambient conditions, or so-called {open_quotes}dry{close_quotes} powders, and {open_quotes}wet{close_quotes} pastes. ASAXS intensities should increase with absorption energy if the metal ion is associated with the interlayer solvent (water in this case), and decrease if the metal ion is associated with the solid matrix. The results show that: (1) Cu(II) is solvated within the interlayers of the wet sample, as expected, and (2) Er(III) and Yb(III) decrease in ASAXS intensity with increased hydration. This latter result was not expected and there is speculation that these ions have associated as hydrolyzed products with the clay surface. The basic principles underlying SAXS and ASAXS will also be presented in this paper.

  15. Cation diffusion in the interlayer space of swelling clay minerals - A combined macroscopic and microscopic study

    NASA Astrophysics Data System (ADS)

    Tertre, Emmanuel; Delville, Alfred; Prêt, Dimitri; Hubert, Fabien; Ferrage, Eric

    2015-01-01

    This study investigates the diffusion process of calcium cations confined in the interlayer space of 5 mm disks of vermiculite swelling clay minerals during the Na-for-Ca exchange process. Diffusion experiments were performed at four NaCl salinities (3 × 10-3, 5 × 10-2, 0.1 and 1 M) of the exchanger solution. A macroscopic analysis of the diffusion process based on the aqueous calcium concentrations released in the solution and on Ca-profiles obtained in the solid was performed using a pore diffusion model that has been classically used in the literature. The results obtained at the macroscopic scale showed that the apparent diffusion coefficients describing both aqueous and profiles data for Ca depend on the diffusion time and salinity of the aqueous reservoir. Such variations suggested that interlayer diffusion was driven by (1) the gradient of the sorbed species in the interlayer, which depends on the diffusion time due to the ion exchange equilibrium; and (2) the discontinuity, due to Donnan equilibrium, existing at the limit between the "internal disk border" and the "external disk border" in contact with the aqueous reservoir. Then, a set of molecular and Brownian dynamics simulations was used to (1) assess such interpretations and (2) quantitatively predict aqueous and profile data obtained at the macroscopic scale. For an aqueous reservoir with high salinity (1 M NaCl), a good agreement was obtained between the macroscopic data and the predictions obtained from Brownian dynamics simulations, confirming the role played by the gradient of the interlayer species that is suggested at the macroscopic scale and which is at the basis of the "surface diffusion models" published in literature. In addition, for aqueous reservoirs with lower salinity (5 × 10-2 M), the results obtained by Brownian dynamics simulations and normalized to the exchange rate measured at infinite time showed that the diffusion properties of the species in the aqueous reservoir cannot be neglected to correctly interpret macroscopic data. This behavior confirms the role played by the ionic flux that exists at the "disk border", which can limit the global diffusion process in a low salinity reservoir, even if it is well stirred. Moreover, by assuming a tortuosity equal to 1 for monocrystals, the self-diffusion coefficient issued from molecular dynamics simulations is in good agreement with the apparent diffusion coefficient describing macroscopic data when the gradient of sorbed concentrations within the solid is null; this latter condition is obtained in our case at infinite time (20 days) when the initial Ca-saturated disks are fully exchanged with Na cations. Finally, the use of monocrystals allows us to have only interlayer porosity and then to obtain a self-diffusion coefficient for Ca from Molecular Dynamic simulations, which is in good agreement with Ca-surface mobility, which was defined by some authors to predict the "surface diffusion process" at the macroscopic scale.

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

    NASA Astrophysics Data System (ADS)

    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.

  17. Structural Investigation of Alkali Activated Clay Minerals for Application in Water Treatment Systems

    NASA Astrophysics Data System (ADS)

    Bumanis, G.; Bajare, D.; Dembovska, L.

    2015-11-01

    Alkali activation technology can be applied for a wide range of alumo-silicates to produce innovative materials with various areas of application. Most researches focuse on the application of alumo-silicate materials in building industry as cement binder replacement to produce mortar and concrete [1]. However, alkali activation technology offers high potential also in biotechnologies [2]. In the processes where certain pH level, especially alkaline environment, must be ensured, alkali activated materials can be applied. One of such fields is water treatment systems where high level pH (up to pH 10.5) ensures efficient removal of water pollutants such as manganese [3]. Previous investigations had shown that alkali activation technology can be applied to calcined clay powder and aluminium scrap recycling waste as a foam forming agent to create porous alkali activated materials. This investigation focuses on the structural investigation of calcined kaolin and illite clay alkali activation processes. Chemical and mineralogical composition of both clays were determined and structural investigation of alkali activated materials was made by using XRD, DTA, FTIR analysis; the microstructure of hardened specimens was observed by SEM. Physical properties of the obtained material were determined. Investigation indicates the essential role of chemical composition of the clay used in the alkali activation process, and potential use of the obtained material in water treatment systems.

  18. CARBON SEQUESTRATION IN CLAY MINERAL FRACTIONS FROM 14C-LABELED PLANT RESIDUES

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An understanding of organic C dynamics in soils is necessary to develop management options to enhance soil organic C sequestration. The objective of this research was to study the distribution of newly formed humic materials into mineralogically distinct clay-size fractions of a silt loam soil. Oats...

  19. ADSORPTION, DESORPTION AND OXIDATION OF ARSENIC AFFECTED BY CLAY MINERALS AND AGING PROCESS

    EPA Science Inventory

    Adsorption/desorption and oxidation/reduction of arsenic at clay surfaces are very important to the natural attenuation of arsenic in the subsurface environment. Although numerous studies have concluded that iron oxides have high affinities for the adsorption of As(V), very litt...

  20. Suitability of the methylene blue test for determination of cation exchange capacity of clay minerals related to ammonium acetate method

    NASA Astrophysics Data System (ADS)

    Milošević, Maja; Logar, Mihovil; Dojčinović, Biljana; Erić, Suzana

    2015-04-01

    Cation exchange capacity (CEC) represents one of the most important parameters of clay minerals which reflects their ability to exchange cations with liquid phases in near contact. Measurement of CEC is used for characterizing sample plasticity, adsorbing and swelling properties which later define their usage in industrial purposes. Several methods have been developed over the years for determination of layer charge, charge density, charge distribution, etc. and have been published in numerous papers (Czimerova et al., 2006; Yukselen and Kaya, 2008). The main goal of present study is comparison of suitability of more recent method - methylene blue test in regard to older method - ammonium acetate for determination of CEC. For this study, we selected one montmorillonite clay (Bogovina, Serbia) and two mainly kaolinite clays (Miličinica, Serbia). Chemicals used for CEC determinations were solution of methylene blue (MB)(14*10-6M/ml) and ammonium acetate (AA) solution (1M). The obtained results are showing generally lower values in case of MB method. The main difference is due to molecular aggregation of MB on the clay surface. AA method is highly sensitive to the presence of CaO. Release of Ca ion from the sample into the solution can limit the saturation of exchange sites by the ammonium ion. This is clearly visible in case of montmorillonite clay. Fe2+ and Mg ions are difficult to move by the ammonium ion because of their ion radius, but in case of MB molecule there is no such restriction in removing them from the exchange sites. MB solution, even in a low concentration (2*10-6M/ml), is showing preferable results in moving the ions from their positions which is already visible after adding a small quantity of solution (25cm3). Both MB-titration and MB-spot test yield similar results and are much simpler methods than AA and they also give other information such as specific surface area (external and internal) whereas AA method only provides information about cations in exchangeable positions. Both methods, methylene blue test and ammonium acetate method, have advantages and disadvantages and differ in their requirements for the sample preparations but in general method selection is depending on the specific application of the given sample. References: - Yukselen, Y. and Kaya, A., Engineering Geology 102 (2008) 38-45 - Czimerova, A., Bujdak, J. and Dohrmann, R., Applied Clay Science 34 (2006) 2-13

  1. Clay minerals in chernozem-like soils of mesodepressions in the northern forest-steppe of European Russia

    NASA Astrophysics Data System (ADS)

    Sokolova, T. A.; Zaidel'Man, F. R.; Ginzburg, T. M.

    2010-01-01

    In the northern forest-steppe of European Russia, under the conditions of surface waterlogging (freshwater) and a stagnant-percolative regime, gleyic podzolic chernozem-like soils with thick light-colored eluvial horizons are formed. These horizons are close or similar to the podzolic horizons of bog-podzolic soils in many properties of their solid phase. They are bleached in color and characterized by the removal of Ca, Mg, Fe, Al, and Mn and the relative accumulation of quartz SiO2. These soils differ from leached chernozems in their acid reaction and very low CEC, the presence of Fe-Mn concretions and coatings, and the significant decrease in the clay content in the A2 horizon as compared to the parent rock. The soils studied differ significantly from loamy podzolic and bog-podzolic soils by the composition of the clay minerals in the A2 horizons: (1) no essential loss of smectite minerals from this horizon was found as compared to the rest of the solum, (2) pedogenic chlorites (HIV and HIS) are absent, and (3) the distinct accumulation of illites is observed as compared to the subsoil and parent material, probably, due to the process of illitization.

  2. Remediation of hexavalent chromium from aqueous solution using clay mineral Fe(II)-montmorillonite: Encompassing anion exclusion impact

    NASA Astrophysics Data System (ADS)

    Vinuth, Mirle; Bhojya Naik, Halehatty Seethya; Manjanna, Jayappa

    2015-12-01

    We have explored the highly efficient and environmentally benign clay mineral, Fe(II)-montmorillonite, for the reduction of Cr(VI) in aqueous solution. Fe(II)-Mt was treated with K2Cr2O7 solution at different pH, temperature and solid-to-liquid ratio. The [Cr2O7]2- was estimated by UV-vis spectra with a correction for anion exclusion impact. In general, the Cr(VI) reduction was rapid at acidic pH and increased with temperature up to 50 °C. A complete reduction occurred in about 5 min at pH 3-5. The time taken for complete reduction at 0 °C, RT (30 °C) and 40 °C are 12 min, 8 min and 5 min, respectively. The reduction followed by immobilization of Cr(III) on the spent clay mineral was well characterized by EDX and chemical extraction analysis. This remediation process could be easily scaled-up for real system applications.

  3. Vapor-phase sorption of hexachlorobenzene on typical municipal solid waste (MSW) incineration fly ashes, clay minerals and activated carbon.

    PubMed

    Gao, Yuan; Zhang, Haijun; Chen, Jiping

    2010-11-01

    Column sorption experiments were conducted at 330°C and 250°C to study the vapor-phase sorption of hexachlorobenzene (HCB) on two kinds of municipal solid waste (MSW) incinerator fly ashes, kaolinite, montmorillonite and activated carbon (AC). Both Freundlich equation and linear equation well fitted the sorption isotherms of HCB vapor on fly ashes and clay minerals at 330°C (r(2)>0.87), while the sorption isotherm of HCB vapor on AC at 330°C was in the shape of Brunauer type-II adsorption. Catalytic dechlorination of HCB was found to occur on the surface of fly ashes, and pentachlorobenzene was the only dechlorination product detected in the effluent gas. Increasing temperature decreased the sorption of HCB vapor on fly ashes, and promoted the catalytic dechlorination of HCB. On the assumption that the organic carbon and clay minerals in fly ash were derived from AC, kaolinite and montmorillonite, the relative contributions of these components to the apparent sorption capacity of fly ashes at 330°C were estimated. It was found that very small percentage of AC contributed the most to the apparent sorption of HCB vapor on fly ash. The sorption coefficient of HCB on montmorillonite at 250°C was 37 times higher than that at 330°C, suggesting montmorillonite could be a kind of low-cost sorbent to effectively reduce the emission of vapor-phase organochlorine compounds from MSW incinerators. PMID:20875668

  4. Adsorption mechanisms of emerging micro-pollutants with a clay mineral: Case of tramadol and doxepine pharmaceutical products.

    PubMed

    Thiebault, Thomas; Guégan, Régis; Boussafir, Mohammed

    2015-09-01

    A sodium exchanged smectite clay mineral (Mt) was used as geo-sorbent for the adsorption of tramadol and doxepin: two pharmaceutical products (PPs) defined as emerging pollutants due to their presence at significant concentration in numerous water compartments. The adsorption isotherms for both the temperatures of 20 and 40°C and the derived data determined through the fitting procedure by using Langmuir, Freundlich and Dubinin-Radushkevich equation models explicitly pointed out that the sorption of both tramadol and doxepin is mainly driven by electrostatic interaction. The studied PPs are intercalated in a monolayer arrangement within the interlayer space through a cation exchange in stoichiometric proportion with the Na(+) cations leading to adsorbed PPs amounts that match the cation exchange capacity (CEC) of Mt. Due to their hydrophobic character, additional doxepin molecules could be adsorbed by weak molecular interaction driving to an increase of the adsorbed amount beyond the CEC at low temperature (20°C). The confinement of PPs within the interlayer space of Mt confirms the use of clay minerals as potential material for the wastewater treatment as well as it drives to an amorphous or glassy state, which can find echo in biopharmaceutical applications for a controlled release of PPs. PMID:25950945

  5. Equilibrium, kinetic and thermodynamic studies on the adsorption of the toxins of Bacillus thuringiensis subsp. kurstaki by clay minerals

    NASA Astrophysics Data System (ADS)

    Fu, Qingling; Deng, Yali; Li, Huishu; Liu, Jie; Hu, Hongqing; Chen, Shouwen; Sa, Tongmin

    2009-02-01

    The persistence of Bacillus thuringiensis ( Bt) toxins in soil is further enhanced through association with soil particles. Such persistence may improve the effectiveness of controlling target pests, but impose a hazard to non-target organisms in soil ecosystems. In this study, the equilibrium adsorption of the Bt toxin by four clay minerals (montmorillonite, kaolinite, goethite, and silicon dioxide) was investigated, and the kinetic and thermodynamic parameters were calculated. The results showed that Bt toxin could be adsorbed easily by minerals, and the adsorption was much easier at low temperature than at high temperature at the initial concentration varying from 0 to 1000 mg L -1. The adsorption fitted well to both Langmuir and Freundlich isotherm models, but the Freundlich equation was more suitable. The pseudo-second-order (PSO) was the best application model to describe the adsorption kinetic. The adsorption process appeared to be controlled by chemical process, and the intra-particle diffusion was not the only rate-controlling step. The negative standard free energy ( ΔGmθr) values of the adsorption indicated that the adsorption of the Bt toxin by the minerals was spontaneous, and the changes of the standard enthalpy ( ΔHmθr) showed that the adsorption of the Bt toxin by montmorillonite was endothermic while the adsorption by the other three minerals was exothermic.

  6. Impact of clay mineral, wood sawdust or root organic matter on the bacterial and fungal community structures in two aged PAH-contaminated soils.

    PubMed

    Cébron, Aurélie; Beguiristain, Thierry; Bongoua-Devisme, Jeanne; Denonfoux, Jérémie; Faure, Pierre; Lorgeoux, Catherine; Ouvrard, Stéphanie; Parisot, Nicolas; Peyret, Pierre; Leyval, Corinne

    2015-09-01

    The high organic pollutant concentration of aged polycyclic aromatic hydrocarbon (PAH)-contaminated wasteland soils is highly recalcitrant to biodegradation due to its very low bioavailability. In such soils, the microbial community is well adapted to the pollution, but the microbial activity is limited by nutrient availability. Management strategies could be applied to modify the soil microbial functioning as well as the PAH contamination through various amendment types. The impact of amendment with clay minerals (montmorillonite), wood sawdust and organic matter plant roots on microbial community structure was investigated on two aged PAH-contaminated soils both in laboratory and 1-year on-site pot experiments. Total PAH content (sum of 16 PAHs of the US-EPA list) and polar polycyclic aromatic compounds (pPAC) were monitored as well as the available PAH fraction using the Tenax method. The bacterial and fungal community structures were monitored using fingerprinting thermal gradient gel electrophoresis (TTGE) method. The abundance of bacteria (16S rRNA genes), fungi (18S rRNA genes) and PAH degraders (PAH-ring hydroxylating dioxygenase and catechol dioxygenase genes) was followed through qPCR assays. Although the treatments did not modify the total and available PAH content, the microbial community density, structure and the PAH degradation potential changed when fresh organic matter was provided as sawdust and under rhizosphere influence, while the clay mineral only increased the percentage of catechol-1,2-dioxygenase genes. The abundance of bacteria and fungi and the percentage of fungi relative to bacteria were enhanced in soil samples supplemented with wood sawdust and in the plant rhizospheric soils. Two distinct fungal populations developed in the two soils supplemented with sawdust, i.e. fungi related to Chaetomium and Neurospora genera and Brachyconidiellopsis and Pseudallescheria genera, in H and NM soils respectively. Wood sawdust amendment favoured the development of PAH-degrading bacteria holding Gram-negative PAH-ring hydroxylating dioxygenase, catechol-1,2-dioxygenase and catechol-2,3-dioxygenase genes. Regarding the total community structure, bacteria closely related to Thiobacillus (β-Proteobacteria) and Steroidobacter (γ-Proteobacteria) genera were favoured by wood sawdust amendment. In both soils, plant rhizospheres induced the development of fungi belonging to Ascomycota and related to Alternaria and Fusarium genera. Bacteria closely related to Luteolibacter (Verrucomicrobia) and Microbacterium (Actinobacteria) were favoured in alfalfa and ryegrass rhizosphere. PMID:25616383

  7. Post-fire spatial patterns of soil nitrogen mineralization and microbial abundance.

    PubMed

    Smithwick, Erica A H; Naithani, Kusum J; Balser, Teri C; Romme, William H; Turner, Monica G

    2012-01-01

    Stand-replacing fires influence soil nitrogen availability and microbial community composition, which may in turn mediate post-fire successional dynamics and nutrient cycling. However, fires create patchiness at both local and landscape scales and do not result in consistent patterns of ecological dynamics. The objectives of this study were to (1) quantify the spatial structure of microbial communities in forest stands recently affected by stand-replacing fire and (2) determine whether microbial variables aid predictions of in situ net nitrogen mineralization rates in recently burned stands. The study was conducted in lodgepole pine (Pinus contorta var. latifolia) and Engelmann spruce/subalpine fir (Picea engelmannii/Abies lasiocarpa) forest stands that burned during summer 2000 in Greater Yellowstone (Wyoming, USA). Using a fully probabilistic spatial process model and Bayesian kriging, the spatial structure of microbial lipid abundance and fungi-to-bacteria ratios were found to be spatially structured within plots two years following fire (for most plots, autocorrelation range varied from 1.5 to 10.5 m). Congruence of spatial patterns among microbial variables, in situ net N mineralization, and cover variables was evident. Stepwise regression resulted in significant models of in situ net N mineralization and included variables describing fungal and bacterial abundance, although explained variance was low (R²<0.29). Unraveling complex spatial patterns of nutrient cycling and the biotic factors that regulate it remains challenging but is critical for explaining post-fire ecosystem function, especially in Greater Yellowstone, which is projected to experience increased fire frequencies by mid 21(st) Century. PMID:23226324

  8. Post-Fire Spatial Patterns of Soil Nitrogen Mineralization and Microbial Abundance

    PubMed Central

    Smithwick, Erica A. H.; Naithani, Kusum J.; Balser, Teri C.; Romme, William H.; Turner, Monica G.

    2012-01-01

    Stand-replacing fires influence soil nitrogen availability and microbial community composition, which may in turn mediate post-fire successional dynamics and nutrient cycling. However, fires create patchiness at both local and landscape scales and do not result in consistent patterns of ecological dynamics. The objectives of this study were to (1) quantify the spatial structure of microbial communities in forest stands recently affected by stand-replacing fire and (2) determine whether microbial variables aid predictions of in situ net nitrogen mineralization rates in recently burned stands. The study was conducted in lodgepole pine (Pinus contorta var. latifolia) and Engelmann spruce/subalpine fir (Picea engelmannii/Abies lasiocarpa) forest stands that burned during summer 2000 in Greater Yellowstone (Wyoming, USA). Using a fully probabilistic spatial process model and Bayesian kriging, the spatial structure of microbial lipid abundance and fungi-to-bacteria ratios were found to be spatially structured within plots two years following fire (for most plots, autocorrelation range varied from 1.5 to 10.5 m). Congruence of spatial patterns among microbial variables, in situ net N mineralization, and cover variables was evident. Stepwise regression resulted in significant models of in situ net N mineralization and included variables describing fungal and bacterial abundance, although explained variance was low (R2<0.29). Unraveling complex spatial patterns of nutrient cycling and the biotic factors that regulate it remains challenging but is critical for explaining post-fire ecosystem function, especially in Greater Yellowstone, which is projected to experience increased fire frequencies by mid 21st Century. PMID:23226324

  9. The 1.7- to 4.2-micron spectrum of asteroid 1 Ceres - Evidence for structural water in clay minerals

    NASA Technical Reports Server (NTRS)

    Lebofsky, L. A.; Feierberg, M. A.; Larson, H. P.; Johnson, J. R.; Tokunaga, A. T.

    1981-01-01

    A high-resolution Fourier spectrum (1.7-3.5 microns) and medium-resolution spectrophotometry (2.7-4.2 microns) were obtained for Asteroid 1 Ceres. The presence of the 3-micron absorption feature due to water of hydration was confirmed. The 3-micron feature is compared with the 3-micron bands due to water of hydration in clays and salts. It is concluded that the spectrum of Ceres shows a strong absorption at 2.7-2.8 microns due to structural OH groups in clay minerals. The dominant minerals on the surface of Ceres are therefore hydrated clay minerals structurally similar to terrestrial montmorillonites. There is also a narrow absorption feature at 3.1 microns which is attributable to a very small amount of water ice on Ceres. This is the first evidence for ice on the surface of an asteroid.

  10. Mineral abundances at the final four curiosity study sites and implications for their formation

    NASA Astrophysics Data System (ADS)

    Poulet, F.; Carter, J.; Bishop, J. L.; Loizeau, D.; Murchie, S. M.

    2014-03-01

    A component of the landing site selection process for the Mars Science Laboratory (MSL) involved the presence of phyllosilicates as the main astrobiological targets. Gale crater was selected as the MSL landing site from among 4 down selected study sites (Gale, Eberswalde and Holden craters, Mawrth Vallis) that addressed the primary scientific goal of assessing the past habitability of Mars. A key constraint on the formation process of these phyllosilicate-bearing deposits is in the precise mineralogical composition. We present a reassessment of the mineralogy of the sites combined with a determination of the modal mineralogy of the major phyllosilicate-bearing deposits of the four final study sites from the modeling of near-infrared spectra using a radiative transfer model. The largest abundance of phyllosilicates (30-70%) is found in Mawrth Vallis, the lowest one in Eberswalde (<25%). Except for Mawrth Vallis, the anhydrous phases (plagioclase, pyroxenes and martian dust) are the dominant phases, suggesting formation conditions with a lower alteration grade and/or a post-formation mixing with anhydrous phases. The composition of Holden layered deposits (mixture of saponite and micas with a total abundance in the range of 25-45%) suggests transport and deposition of altered basalts of the Noachian crust without major chemical transformation. For Eberswalde, the modal mineralogy is also consistent with detrital clays, but the presence of opaline silica indicates that an authigenic formation occurred during the deposition. The overall composition including approximately 20-30% smectite detected by MSL in the rocks of Yellow-knife Bay area interpreted to be material deposited on the floor of Gale crater by channels (http://www.nasa.gov/mission_pages/msl/news/msl20130312.html) is consistent with the compositions modeled for the Eberswalde and Holden deltaic rocks. At Gale, the paucity, the small diversity and the low abundance of nontronite do not favor a complex and long drainage system. Localized aqueous processes in space and time environments could have produced both nontronites and sulfates. However, most materials in Gale are unfortunately dust covered, so that orbital data are limited by spatial resolution and surficial fines that could dilute and obscure the spectral influence of phyllosilicates in the rocks. Potential formation processes of diverse and abundant Mawrth Vallis deposits include low temperature hydrothermal alteration in marine environments and/or pedogenesis.

  11. Gram-negative Biomass in Clay Minerals Analogs: Testing Habitability Potential for the 2011 Mars Science Laboratory Mission

    NASA Astrophysics Data System (ADS)

    Bonaccorsi, R.; McKay, C. P.

    2009-12-01

    Landing sites of next missions to Mars i.e., the US 2011 Mars Science Laboratory (MSL11) and the ESA2016 Pasteur ExoMars, will include phyllosilicate outcrops as targets for investigating the geological and biological history of that planet. In this context, we present a study assessing the living biomass and habitability potential in mineralogical Mars analogs such as phyllosilicates and hematite-rich deposits encompassing a broad arid-hyper-arid climate range (annual rainfall <0.2 to ~700mm/y). Samples from the Atacama Desert (Chile), the Death Valley (CA), and the California Coast (USA) were analyzed for microbial lipopolysaccharide (LPS) as proxy for Gram-negatives biomass with the Limulus-Amebocite-Lysate (LAL) assay. Mineral phases were identified using X-Ray-Diffraction (XRD). These samples resulted to contain phyllosilicate phases similar to those identified, or inferred [1], on the surface of Mars by the OMEGA-Mars/Express [e.g., 2], the Mars Reconnaissance Orbiter (MRO) instruments (HiRISE and CRISM) [3]. Basic observations were: 1) there is no systematic pattern in biomass content of clays vs. non-clays (oxidized) materials from the study sites; 2) Atacama desiccation polygons (muscovite and kaolinite) and contiguous hematite-rich hyper-arid deposits contain the lowest biomass, i.e., ~104to-105 cells/g, respectively; 3) the hyper-arid clays contain three-order magnitude lower Gram-negative biomass than those (montmorillonite, illite, and chlorite) from the arid Death Valley site (~107cells/g); and 4) finally, the Gram-negative (~107cells/g) of clay minerals-rich materials from the arid site is about the same than that (~1.5 to ~3.0 x 107cells/g) of water-saturated massive deposits (kaolinite, illite, and vermiculite) from the wetter California coast. Results from this investigation will help testing for the habitability potential of phyllosilicate deposits sampled by the MSL11 Mission. REFERENCES:[1] Bibring et al., 2006, Science 312:400-404; [2] Wang et al., 2006 JGR E02S16 Vol.111; [3] Bishop et al., 2008. Science, 321,830-833.

  12. Near-infrared reflectance spectra of mixtures of kaolin-group minerals: use in clay mineral studies

    USGS Publications Warehouse

    Crowley, J.K.; Vergo, N.

    1988-01-01

    Near-infrared (NIR) reflectance spectra for mixtures of ordered kaolinite and ordered dickite have been found to simulate the spectral response of disordered kaolinite. The amount of octahedral vacancy disorder in nine disordered kaolinite samples was estimated by comparing the same spectra to the spectra of reference mixtures. The resulting estimates are consistent with previously published estimates of vacancy disorder for similar kaolin minerals that were modeled from calculated X-ray diffraction patterns. -from Authors

  13. Effect of chlorine in clay-mineral specimens prepared on silver metal-membrane mounts for X-ray powder diffraction analysis

    USGS Publications Warehouse

    Poppe, L.J.; Commeau, J.A.; Pense, G.M.

    1989-01-01

    Silver metal-membrane filters are commonly used as substrates in the preparation of oriented clay-mineral specimens for X-ray powder diffraction (XRD). The silver metal-membrane filters, however, present some problems after heat treatment if either the filters or the samples contain significant amounts of chlorine. At elevated temperature, the chloride ions react with the silver substrate to form crystalline compounds. These compounds change the mass-absorption coefficient of the sample, reducing peak intensities and areas and, therefore, complicating the semiquantitative estimation of clay minerals. A simple procedure that eliminates most of the chloride from a sample and the silver metal-membrane substrate is presented here.

  14. Stability of guanine adsorbed in a clay mineral under gamma irradiation at temperatures (77 and 298 K): Implications for chemical evolution studies

    NASA Astrophysics Data System (ADS)

    Meléndez-López, A. L.; Ramos-Bernal, S.; Ramírez-Vázquez, M. L.

    2014-07-01

    Chemical evolution is a physical and chemical preamble prior the appearance of life. In these processes, clay minerals might have played an important role on the early Earth. The relevance of these solids in the emergence of life is due to their ancient origin, wide distribution, and especially, their physico-chemical properties. Clays, therefore, are considered the most likely inorganic materials to promote organic reactions in the primitive Earth. John D. Bernal suggested clays as concentrators of biological precursor molecules, as catalysis and clays might protect these molecules from high-energy radiation. On the other hand, nucleic acid bases and their derivatives are important compounds in biological systems. Their synthesis and stability in environmental conditions are of paramount importance in chemical evolution. The aim of this work is to extend the knowledge of the role of clays in the prebiotic epoch in relation to the behavior of guanine, a nucleic acid base, adsorbed in a clay mineral. To this end, we studied its adsorption in clays, its site of binding, and its survival under a high radiation field and at different temperatures and pH. The results showed guanine adsorption onto clays increased with the decreasing of the pH. This result could be explained by electrostatic forces between guanine positively charged at an acid pH and the negatively charged interlamellar channel of the clay. X-ray diffractograms showed that guanine is adsorbed onto the clay at the interlayer channel. To study the survival of guanine in a high radiation field, the system guanine-clay was irradiated under different irradiation doses, temperatures, and pH. The results showed that more than 90% of the guanine survives, and when the radiolysis is made without clay, the decomposition of this molecule occurs at low irradiation doses. The radiolysis performed at 77 K showed very low decomposition, which is important in cometary chemistry. These results show the protection role of the clay toward ionizing radiation of an organic compound adsorbed into it.

  15. Microtomographic quantification of hydraulic clay mineral displacement effects during a CO2 sequestration experiment with saline aquifer sandstone.

    PubMed

    Sell, Kathleen; Enzmann, Frieder; Kersten, Michael; Spangenberg, Erik

    2013-01-01

    We combined a noninvasive tomographic imaging technique with an invasive open-system core-flooding experiment and compared the results of the pre- and postflooded states of an experimental sandstone core sample from an ongoing field trial for carbon dioxide geosequestration. For the experiment, a rock core sample of 80 mL volume was taken from the 629 m Stuttgart Formation storage domain of a saline sandstone aquifer at the CCS research pilot plant Ketzin, Germany. Supercritical carbon dioxide and synthetical brine were injected under in situ reservoir p/T-conditions at an average flow rate of 0.1 mL/min for 256 h. X-ray computed microtomographic imaging was carried out before and after the core-flooding experiment at a spatial voxel resolution of 27 μm. No significant changes in microstructure were found at the tomographic imaging resolution including porosity and pore size distribution, except of an increase of depositional heterogeneous distribution of clay minerals in the pores. The digitized rock data were used as direct real microstructure input to the GeoDict software package, to simulate Navier-Stokes flow by a lattice Boltzmann equation solver. This procedure yielded 3D pressure and flow velocity fields, and revealed that the migration of clay particles decreased the permeability tensor probably due to clogging of pore openings. PMID:22924476

  16. Mars atmosphere. The imprint of atmospheric evolution in the D/H of Hesperian clay minerals on Mars.

    PubMed

    Mahaffy, P R; Webster, C R; Stern, J C; Brunner, A E; Atreya, S K; Conrad, P G; Domagal-Goldman, S; Eigenbrode, J L; Flesch, G J; Christensen, L E; Franz, H B; Freissinet, C; Glavin, D P; Grotzinger, J P; Jones, J H; Leshin, L A; Malespin, C; McAdam, A C; Ming, D W; Navarro-Gonzalez, R; Niles, P B; Owen, T; Pavlov, A A; Steele, A; Trainer, M G; Williford, K H; Wray, J J

    2015-01-23

    The deuterium-to-hydrogen (D/H) ratio in strongly bound water or hydroxyl groups in ancient martian clays retains the imprint of the water of formation of these minerals. Curiosity's Sample Analysis at Mars (SAM) experiment measured thermally evolved water and hydrogen gas released between 550° and 950°C from samples of Hesperian-era Gale crater smectite to determine this isotope ratio. The D/H value is 3.0 (±0.2) times the ratio in standard mean ocean water. The D/H ratio in this ~3-billion-year-old mudstone, which is half that of the present martian atmosphere but substantially higher than that expected in very early Mars, indicates an extended history of hydrogen escape and desiccation of the planet. PMID:25515119

  17. Monitoring nitrogen leaching for the evaluation of the Dutch minerals policy for agriculture in clay regions.

    PubMed

    Fraters, D; Boumans, L J; van Leeuwen, T C; de Hoop, W D

    2001-11-01

    This paper presents the results of the Dutch monitoring program for agriculture in the clay regions for the period 1996-2000 and evaluates the monitoring strategy. A wide range of farms (25 to 85%) had a NO3--N concentration in tile drainwater higher than the EU standard of 11.3 mg/l. The low figure is related to wet winters; the high, to dry winters. Arable farms are more prone to NO3- leaching than dairy farms. On arable farms, about 25% of the N surplus leached to groundwater and tile drainwater, on dairy farms this was about 15%. N in tile drainwater has shown to be the best indicator for monitoring the effects of farming practice changes in the clay regions. The average NO3--N concentration in tile drainwater was 18.8 and 3.2 mg/l in borehole water on farms where both were monitored. It is known that N use has a relationship with NO3- in tile drainwater and not with NH4+ and organic N. The presented results indicate that crop rotation and precipitation strongly influence NO3- concentration in tile drainwater. PMID:12805827

  18. Cesium and Strontium Uptake to Clay Minerals and Their Weathering Products in a Caustic Waste

    SciTech Connect

    Choi, Sunkyung; Amistadi, Mary Kay; Seraphin, Supapan; Chorover, Jon

    2004-03-28

    Weathering behavior and contaminant (Sr and Cs) uptake by specimen clays (illite, vermiculite, montmorillonite and kaolinite) and their secondary solid phase products were studied in batch systems under geochemical conditions characteristic of leaking tank waste at the Hanford Site in WA (0.05 M AlT, 2 M Na+, 1 M NO3 -, pH {approx}14, Cs+ and Sr2+ present as co-contaminants). Time series experiments were conducted from 0 to 369 days, with initial Cs+ and Sr2+ concentrations ranging from 10-5 to 10-3 M. Cesium sorption after 369 d reaction was the greatest in the order of vermiculite, illite, montmorillonite and kaolinite at 10-3 M Cs/Sr. In the case of Sr, vermiculite showed highest Sr sorption and was followed by kaolinite, montmorillonite and illite at highest loading Cs/Sr after 369 d. Secondary phase products were feldspathoid sodium aluminum nitrate silicate, sodium aluminum nitrate silicate hydrate, Na-Al chabazite and zeolite X in weathered clays. Discrete Sr single phases were found in kaolinite and illite systems after 369 d at 10-3 M Cs/Sr.

  19. Towards an Improved Understanding of Shock Effects in Recovered Samples: Application to Shocked Clay Minerals

    NASA Astrophysics Data System (ADS)

    Spaulding, Dylan; Stewart, Sarah; Hankin, Markos; Wizda, Lee

    2015-06-01

    Samples recovered from shock-compression experiments offer a unique opportunity to understand the response of materials to extreme conditions. Correct interpretation of such experiments requires understanding the independent roles of pressure and temperature upon both compression and release. Previous shock-recovery experiments have largely ignored the thermal history of the sample or have underestimated peak pressures due to strong impedance mismatch between the sample and its surroundings. Here, we present current efforts towards increasingly controlled shock recovery schemes for the study of devolatilization in phyllosilicate clays. Shock effects may influence how volatiles within such clays are preferentially incorporated or lost during planetary accretion as well as spectral observations and interpretations of the aqueous history of planetary surfaces. We present both equation-of-state, post-shock temperature and devolatilization data for Kaolinite and Montmorillonite (up to 21 and 23 GPa, respectively) as well as post-mortem sample analysis using a variety of methods. Performance of sample recovery designs are simulated using a 3D Eulerian hydrodynamic code (CTH) and compared to experiments in order to optimize and improve sample geometries.

  20. Clay minerals in primitive meteorites and interplanetary dust 2. Smectites and micas

    NASA Technical Reports Server (NTRS)

    Keller, L. P.; Zolensky, M. E.

    1991-01-01

    The classification is briefly summarized of stony meteorites and cosmic dust, and the mineralogy and chemistry is described of serpentine group minerals. The occurrence of smectites and micas in extraterrestrial materials is examined. The characterization of fine grained minerals in meteorites and IDPs relies heavily on electron beam instruments, especially the transmission electron microscope (TEM). Typically, phyllosilicates are identified by a combination of high resolution imaging of basal spacings, electron diffraction, and chemical analysis. Smectites can be difficult to differentiate from micas because the smectites lose their interlayer water and the interlayer partly collapse in the high vacuum of the TEM.

  1. Experimental Determination of Clay Mineral Reactions in Clastic Reservoir Rock Resulting from the Injection of Supercritical CO2

    NASA Astrophysics Data System (ADS)

    Mangini, S. A.; Shaw, C. A.; Skidmore, M. L.

    2013-12-01

    The Cretaceous Frontier Formation of the Powder River Basin, WY has been considered as a potential reservoir for storing anthropogenic CO2. The reservoir zones are composed of fine-grained quartz and potassium feldspar rich sandstones, cemented with clay minerals (kaolinite and interlayered illite and montmorillonite). The purpose of these experiments is to determine whether susceptible minerals such as illite, montmorillonite, and potassium feldspar undergo in-situ 'weathering' reactions when exposed to the high concentrations of carbonic acid generated by the dissolution of supercritical CO2 in formation water. The transformation of these minerals has the potential to: 1.) open up pore space through dissolution; 2.) reduce pore space and/or close pore throats by precipitating new minerals, or 3.) cause little change if the reactions take place slowly. Core samples of the Frontier Formation were obtained from the USGS Core Repository in Denver, CO and their physical and mineralogical properties analyzed. Porosity and permeability of the cores have been determined by helium porosimetry and gas permeability testing. Pore space distribution was analyzed by CT scan. Mineralogy was determined by thin section analysis, X-Ray diffraction, and Scanning Electron Microscopy. Ongoing experiments will expose the cores to CO2 saturated brine in a flow-through reactor at conditions similar to those found in the subsurface (100oC and 15MPa). Changes to the chemical composition of the brine will be determined by withdrawing samples at regular intervals during the experiment and analyzing their contents with ion chromatography and colorimetry. The physical and mineralogical properties of the cores will be analyzed after each experiment and compared to the initial conditions. We will report on the results of these experiments.

  2. Stratigraphic and climatic implications of clay mineral changes around the Paleocene/Eocene boundary of the northeastern US margin

    USGS Publications Warehouse

    Gibson, T.G.; Bybell, L.M.; Mason, D.B.

    2000-01-01

    Kaolinite usually is present in relatively small amounts in most upper Paleocene and lower Eocene neritic deposits of the northern US Atlantic Coastal Plain. However, there is a short period (less than 200,000 k.y.) in the latest Paleocene (upper part of calcareous nannoplankton Zone NP 9) when kaolinite-dominated clay mineral suites replaced the usual illite/smectite-dominated suites. During this time of global biotic and lithologic changes, kaolinite increased from less than 5% of the clay mineral suite to peak proportions of 50-60% of the suite and then returned to less than 5% in uppermost Paleocene/lowermost Eocene strata. This kaolinite pulse is present at numerous localities from southern Virginia to New Jersey. These sites represent both inner and middle neritic depositional environments and reflect input from several river drainage systems. Thus, it is inferred that kaolinite-rich source areas were widespread in the northeastern US during the latest Paleocene. Erosion of these source areas contributed the kaolinite that was transported and widely dispersed into shelf environments of the Salisbury embayment. The kaolinite increase, which occurred during a time of relatively high sea level, probably is the result of intensified weathering due to increased temperature and precipitation. The southern extent of the kaolinite pulse is uncertain in that uppermost Paleocene beds have not been identified in the southern Atlantic Coastal Plain. The late Paleocene kaolinite pulse that consists of an increase to peak kaolinite levels followed by a decrease can be used for detailed correlation between more upbasin and more downbasin sections in the Salisbury embayment. Correlations show that more upbasin Paleocene/Eocene boundary sections are erosionally truncated. They have varying portions of the kaolinite increase and, if present at all, discontinuous portions of the subsequent kaolinite decrease. As these truncated sections are disconformably overlain by lower Eocene strata, rapid erosional removal of large parts of the most kaolinite-rich P/E boundary clay deposits occurred by early Eocene time. Erosion of the kaolinite-rich P/E boundary beds was enhanced during times of sea-level fall when kaolinite-rich sediments were redeposited to produce kaolinite spikes in basal beds of lower and middle Eocene sequences that have little or no kaolinite elsewhere in the sequence. In contrast, more downbasin sites document only the upper, decreasing part of the kaolinite pulse. The absence of strata documenting the earlier kaolinite increase is attributed to slow sedimentation (condensed interval) as a result of a significant sea level rise that ponded most sediments in shallower waters, combined with the probable subsequent erosional removal of these thin downbasin deposits by oceanic currents.

  3. Mars, clays and the origins of life

    NASA Technical Reports Server (NTRS)

    Hartman, Hyman

    1989-01-01

    To detect life in the Martian soil, tests were designed to look for respiration and photosynthesis. Both tests (labeled release, LR, and pyrolytic release, PR) for life in the Martian soils were positive. However, when the measurement for organic molecules in the soil of Mars was made, none were found. The interpretation given is that the inorganic constituents of the soil of Mars were responsible for these observations. The inorganic analysis of the soil was best fitted by a mixture of minerals: 60 to 80 percent clay, iron oxide, quartz, and soluble salts such as halite (NaCl). The minerals most successful in simulating the PR and LR experiments are iron-rich clays. There is a theory that considers clays as the first organisms capable of replication, mutation, and catalysis, and hence of evolving. Clays are formed when liquid water causes the weathering of rocks. The distribution of ions such as aluminum, magnesium, and iron play the role of bases in the DNA. The information was stored in the distribution of ions in the octahedral and tetrahedral molecules, but that they could, like RNA and DNA, replicate. When the clays replicated, each sheet of clay would be a template for a new sheet. The ion substitutions in one clay sheet would give rise to a complementary or similar pattern on the clay synthesized on its surface. It was theorized that it was on the surface of replicating iron-rich clays that carbon dioxide would be fixed in the light into organic acids such as formic or oxalic acid. If Mars had liquid water during a warm period in its past, clay formation would have been abundant. These clays would have replicated and evolved until the liquid water was removed due to cooling of Mars. It is entirely possible that the Viking mission detected life on Mars, but it was clay life that awaits the return of water to continue its evolution into life based on organic molecules.

  4. Chemical and physical transformations of aluminosilicate clay minerals due to acid treatment and consequences for heterogeneous ice nucleation.

    PubMed

    Sihvonen, Sarah K; Schill, Gregory P; Lyktey, Nicholas A; Veghte, Daniel P; Tolbert, Margaret A; Freedman, Miriam Arak

    2014-09-25

    Mineral dust aerosol is one of the largest contributors to global ice nuclei, but physical and chemical processing of dust during atmospheric transport can alter its ice nucleation activity. In particular, several recent studies have noted that sulfuric and nitric acids inhibit heterogeneous ice nucleation in the regime below liquid water saturation in aluminosilicate clay minerals. We have exposed kaolinite, KGa-1b and KGa-2, and montmorillonite, STx-1b and SWy-2, to aqueous sulfuric and nitric acid to determine the physical and chemical changes that are responsible for the observed deactivation. To characterize the changes to the samples upon acid treatment, we use X-ray diffraction, transmission electron microscopy, and inductively coupled plasma-atomic emission spectroscopy. We find that the reaction of kaolinite and montmorillonite with aqueous sulfuric acid results in the formation of hydrated aluminum sulfate. In addition, sulfuric and nitric acids induce large structural changes in montmorillonite. We additionally report the supersaturation with respect to ice required for the onset of ice nucleation for these acid-treated species. On the basis of lattice spacing arguments, we explain how the chemical and physical changes observed upon acid treatment could lead to the observed reduction in ice nucleation activity. PMID:25211030

  5. Clay mineral weathering and contaminant dynamics in a caustic aqueous system I. Wet chemistry and aging effects

    SciTech Connect

    Choi, Sunkyung; Amistadi, Mary K.; Chorover, Jon

    2005-04-08

    Caustic high level radioactive waste induces mineral weathering reactions that can influence the fate of radionuclides released in the vicinity of leaking storage tanks. The uptake and release of CsI and SrII were studied in batch reactors of 2:1 layer-type silicates?illite (Il), vermiculite (Vm) and montmorillonite (Mt)?under geochemical conditions characteristic of leaking tank waste at the Hanford Site in WA (0.05 mAlT, 2 m Na*, 1 m NO3 *, pH *14, Cs and Sr present as co-contaminants). Time series (0 to 369 d) experiments were conducted at 298 K, with initial [Cs]0 and [Sr]0 concentrations from 10*5 to 10*3 mol kg*1. Clay mineral type affected the rates of (1) hydroxide promoted dissolution of Si, Al and Fe, (2) precipitation of secondary solids and (3) uptake of Cs and Sr. Initial Si release to solution followed the order Mt * Vm * Il. An abrupt decrease in soluble Si and/or Al after 33 d for Mt and Vm systems, and after 190 d for Il suspensions was concurrent with accumulation of secondary aluminosilicate precipitates. Strontium uptake exceeded that of Cs in both rate and extent, although sorbed Cs was generally more recalcitrant to subsequent desorption and dissolution. After 369 d reaction time, reacted Il, Vm and Mt solids retained up to 17, 47 and 14 mmol kg*1 (0.18, 0.24 and 0.02 *mol m*2) of Cs, and 0, 27 and 22 mmol kg*1 (0, 0.14 and 0.03 *molm*2) Sr, respectively, which were not removed in subsequent Mg exchange or oxalic acid dissolution reactions. Solubility of Al and Si decreased with initial Cs and Sr concentration in Mt and Il, but not in Vm. High co-contaminant sorption to the Vm clay, therefore, appears to diminish the influence of those ions on mineral transformation rates.

  6. Bioavailability of iron in geophagic earths and clay minerals, and their effect on dietary iron absorption using an in vitro digestion/Caco-2 cell model

    PubMed Central

    Seim, Gretchen L.; Ahn, Cedric I.; Bodis, Mary S.; Luwedde, Flavia; Miller, Dennis D.; Hillier, Stephen; Tako, Elad; Glahn, Raymond P.; Young, Sera L.

    2014-01-01

    Geophagy, the deliberate consumption of earth, is strongly associated with iron (Fe) deficiency. It has been proposed that geophagy may be practiced as a means to improve Fe status by increasing Fe intakes and, conversely, that geophagy may cause Fe deficiency by inhibiting Fe absorption. We tested these hypotheses by measuring Fe concentration and relative bioavailable Fe content of 12 samples of geophagic earth and 4 samples of pure clay minerals. Further, we assessed the impact of these samples on the bioavailability of Fe from an Fe-rich test meal (cooked white beans, WB). Fe concentrations were measured with inductively coupled plasma atomic emission spectroscopy. Fe bioavailability was determined using an in vitro digestion/Caco-2 cell model in which ferritin formation was used as an index of Fe bioavailability. Geophagic earth and clay mineral samples were evaluated with this model, both alone and in combination with WB (1:16 ratio, sample:WB). Median Fe concentration of the geophagic earth was 3485 (IQR 2462, 14571) μg/g and mean Fe concentration in the clay minerals was 2791 (± 1782) μg/g. All specimens had Fe concentrations significantly higher (p ≤ 0.005) than the Fe concentration of WB (77 μg/g). Ferritin formation (i.e. Fe uptake) in cells exposed to geophagic earths and clay minerals was significantly lower than in cells exposed to WB (p ≤ 0.05) and Fe uptake responses of 11 of the 16 samples were not significantly different from the blank, indicating no bioavailable Fe. When samples were combined with WB, 5 of 16 had mean ferritin levels that were significantly lower (p ≤ 0.05, one tail) than the WB alone, indicating that the samples inhibited Fe uptake from the WB. None of the ferritin responses of cells exposed to both WB and earth/clay were significantly higher than WB alone. Thus, although geophagic earths and mineral clays are high in total Fe, very little of this Fe is bioavailable. Further, some geophagic earth and clay mineral samples inhibit Fe absorption from foods. In vivo research is warranted to confirm these observations and to determine if geophagic earth samples can be a source of Fe and/or inhibit Fe absorption. PMID:23787405

  7. Clay-mineral transformation as an indicator of depositional and diagenetic conditions in Pennsylvanian black shales, Paradox Member of the Hermosa Foundation, Utah and Colorado

    SciTech Connect

    Tromp, D.E. ); Whitney, G. )

    1993-08-01

    The dominant clay minerals in the Paradox basin black shale facies include a detrital, aluminum-rich illite/smectite and a series of magnesium-rich, interstratified chlorite/smectite minerals. Black shales from the Gothic and Chimney Rock layers of the Paradox Member of the Hermosa Formation were sampled from 13 wells in southwestern Colorado and southeastern Utah. X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Inductively-Coupled Plasma (ICP), and Rock-Eval pyrolysis were used to determine the nature of a reaction believed to consume aluminum-rich detrital clays to precipitate magnesium-rich authigenic clays. The potential for magnesium enrichment in the clay assemblage was found to be influenced by the following processes: particle size as a function of distance from detrital source area, paleosalinity as a function of transgressive-regressive stage, and the presence of large amounts of organic matter. The basic reaction that forms chlorite/smectite or corrensite (perfectly ordered chlorite/smectite with 50% smectite layers) from detrital clays is Illite/Smectite (detrital) + Mg(aq)[sup 2+] + (OH)[sup [minus

  8. The Infrared Spectra Study of Dehydrated and Dehydroxylated Clay Samples

    NASA Astrophysics Data System (ADS)

    Che, C.; Glotch, T.; Cintrón, I.

    2008-12-01

    The OMEGA visible and near infrared imaging spectrometer detected phyllosilicates in ancient Noachian terrains of Mars-an observation later confirmed by CRISM imaging spectrometer. Detailed mapping showed that the phyllosilicates, most of which are clay minerals, are found in ancient, heavily cratered terrains. These clay-bearing deposits contain interbedded and buried craters, and it is possible the clay minerals were repeatedly subjected to high temperatures resulting from impact processes. We hypothesize that the dehydration and dehydroxylation of clay minerals subjected to impact was a widespread process on early Mars, and that dehydrated and dehydroxylated clay minerals may be still abundant on the surface of Mars. The objective of this study is to characterize the infrared spectral features of clay minerals when they are heated to increasingly higher temperatures. Using a Nicolet 6700 FTIR spectrometer, we have acquired mid-infrared reflectance (500cm-1-7000cm-1), far-infrared reflectance (60cm-1-500cm-1) and ATR (attenuated total reflectance)(500cm-1-4000cm-1) spectra of 13 clay samples at different temperatures(from 100°C to 900°C). All of the clay samples have been prepared to be very pure (<2μm size fraction) and they were heated for 24 hours at each temperature. The structures of clay minerals are well known because of their typical layer structure and complex relations with water and OH bonds. Our data show that the infrared spectra of clay minerals changed as the temperature increased, which helps us to understand the temperature-related processes including removal of water and OH groups, change of Si-O bond, even the complete destruction of clay layer structures. Differences among dehydration and dehydroxylation conditions for these clay minerals are also discussed in this work. In our future work, we will continue to collect the infrared spectra of more clay minerals and collect additional data for our samples, including VNIR reflectance, XRD, NMR, and emissivity spectra, which can provide insights into the crystal structures and help us to answer the very first question: is it possible that dehydrated and dehydroxylated clay minerals are an explanation for poorly crystalline or amorphous materials on Mars?

  9. Reduction and long-term immobilization of technetium by Fe(II) associated with clay mineral nontronite

    SciTech Connect

    Jaisi, Deb P.; Dong, Hailiang; Plymale, Andrew E.; Fredrickson, Jim K.; Zachara, John M.; Heald, S.; Liu, Chongxuan

    2009-06-20

    99Tc is formed mostly during nuclear reactions and is released into the environment during weapons testing and inadvertent waste disposal. The long half-life, high environmental mobility (as Tc(VII)O4-) and its possible uptake into the food chain cause 99Tc to be a significant environmental contaminant. In this study, we evaluated the role of Fe(II) in biologically reduced clay mineral, nontronite (NAu-2), in reducing Tc(VII)O4- to poorly soluble Tc(IV) species as a function of pH and Fe(II) concentration. The rate of Tc(VII) reduction by Fe(II) in NAu-2 was higher at neutral pH (pH 7.0) than at acidic and basic pHs when Fe(II) concentration was low (< 1 mmol/g). The effect of pH, however, was insignificant at higher Fe(II) concentrations. The reduction of Tc(VII) by Fe(II) associated with NAu-2 was also studied in the presence of common subsurface oxidants including iron and manganese oxides, nitrate, and oxygen, to evaluate the effect of the oxidants on the enhancement and inhibition of Tc(VII) reduction, and reoxidation of Tc(IV). Addition of iron oxides (goethite and hematite) to the Tc(VII)-NAu-2 system, where Tc(VII) reduction was ongoing, enhanced reduction of Tc(VII), apparently as a result of re-distribution of reactive Fe(II) from NAu-2 to more reactive goethite/hematite surfaces. Addition of manganese oxides stopped further Tc(VII) reduction, and in case of K+-birnessite, it reoxidized previously reduced Tc(IV). Nitrate neither enhanced reduction of Tc(VII) nor promoted reoxidation of Tc(IV). Approximately 11% of Tc(IV) was oxidized by oxygen. The rate and extent of Tc(IV) reoxidation was found to strongly depend on the nature of the oxidants and concentration of Fe(II). When the same oxidants were added to aged Tc reduction products (mainly NAu-2 and TcO2nH2O), the extent of Tc(IV) reoxidation decreased significantly relative to fresh Tc(IV) products. Increasing NAu-2 concentration also resulted in the decreased extent of Tc(IV) reoxidation. The results were attributed to the effect of NAu-2 aggregation that effectively retained Tc(IV) in the solid and decreased its vulnerability to reoxidation. Overall, our results implied that bioreduced clay minerals could play an important role in reducing Tc(VII) and in maintaining the long-term stability of reduced Tc(IV).

  10. Distribution of clay minerals on the Alaskan margin near Barrow Canyon revealed by Diffuse Spectral Reflectance measurements

    NASA Astrophysics Data System (ADS)

    Orsburn, C.; Ortiz, J. D.; Polyak, L.; Grebmeier, J. M.; Darby, D.

    2007-12-01

    Sediment clay mineral assemblages provide an excellent means of assessing the provenance of Arctic sediment due to the variety of sediment transport mechanisms at work and the existence of distinct weathering sources from differing bedrock geology. During HOTRAX Leg 1 aboard the USCG Ice breaker Healy (cruise HLY0501), we collected jumbo piston cores on the Alaskan margin near Barrow Canyon which provide detailed Holocene sedimentary records. Measurements of Diffuse Spectral Reflectance (DSR) were collected at 1cm resolution from the split surface of the cores using a Minolta CM-2600d UV/VIS spectrophotometer (400-700nm wavelength range; 10nm resolution; 3mm spot size). To interpret the resulting downcore records, we present a preliminary study using 28 coretop sediment samples collected by the Shelf-Basin Interaction program in 2004 arrayed in four transects across the shelf near Barrow Canyon. The samples were analyzed using an ASD Labspec Pro FR UV/VIS/NIR spectrometer (250-2500nm wavelength range, 2-10nm resolution; 20mm spot size). Our results indicate that the measurements from the two instruments are offset by constant factors, but can be easily compared. To estimate the clay mineralogy of the cores, we decomposed the matrix of DSR measurements from the coretop and downcore samples using principle component analysis and compared the resulting factor score patterns with mineral diffuse spectral reflectance signatures from known samples measured in our lab or available from version 5 of the USGS Digital Spectral Library. The three leading modes extracted by principle component analysis of the downcore samples are applicable to the coretops. We infer that the first principle component mode relates to smectite, the second to chlorite, and the third to a mixture of illite and goethite (herein referred to as illite - goethite). The geographic and bathymetric trends in the coretop data indicate that (1) the smectite and illite - goethite components both increase with depth and reach greater values in the two western transects than in the two eastern transects closest to the coast and Barrow Canyon, (2) the smectite and illite- goethite components are anticorrelated in the two western transects, but not in the two eastern transects, (3) chlorite decreases with depth and is highest in the two transects closest to Barrow Canyon. These results suggest that the chlorite on the Alaskan margin is transported by nearshore currents from the Bering Straight and then by bottom currents flowing through the Barrow Canyon. Accordingly, we interpret downcore chlorite peaks inferred from DSR measurements in our sediment cores as evidence of times of enhanced input of Pacific water to the Alaskan Margin.

  11. Lead exchange into zeolite and clay minerals: A [sup 29]Si, [sub 27]Al, [sup 23]Na solid-state NMR study

    SciTech Connect

    Liang, J.J.; Sherriff, B.L. )

    1993-08-01

    Chabazite, vermiculite, montmorillonite, hectorite, and kaolinite were used to remove Pb, through ion exchange, from 0.01 M aqueous Pb(NO[sub 3])[sub 2] solutions. These minerals contained 27 (Na-chabazite), 16, 9, 9, and 0.5 wt % of Pb, respectively, after equilibration with the solutions. Ion exchange reached equilibrium within 24 h for Na-chabazite and vermiculite, but in less than 5 min for montmorillonite and hectorite. Na-chabazite took up more Pb than natural (Ca, Na)-chabazite (7 wt % Pb), whereas no such difference was observed in different cation forms of the clay minerals. Calcite impurities, associated with the clay minerals, effectively removed Pb from the aqueous solutions by the precipitation of cerussite (PbCO[sub 3]). [sup 29]Si, [sup 27]Al, and [sup 23]Na magic angle spinning (MAS) nuclear magnetic resonance (NMR), [sup 23]Na double rotation (DOR) NMR, and [sup 23]Na variable-temperature MAS NMR were used to study the ion exchange mechanisms. In Na-chabazite, cations in all three possible sites take part in the fast chemical exchange. The chemical exchange passes from the fast exchange regime to the slow regime at [minus]80 to [minus]100[degrees]C. One site contains a relatively low population of exchangeable cations. The other two more shielded sites contain most of the exchangeable cation. The exchangeable cations in chabazite and vermiculite were found to be close to the SiO[sub 4] and AlO[sub 4] tetrahedra, while those in the other clay minerals were more distant. Two sites (or groups of sites) for exchangeable cations were observed in hectorite. Lead tended to occupy the one which corresponds to the [minus]8 ppM peak on the [sup 23]Na MAS NMR spectrum. The behavior of the exchangeable cations in the interlayer sites was similar in all the clay minerals studied. 27 refs., 7 figs., 4 tabs.

  12. Europium retention onto clay minerals from 25 to 150 °C: Experimental measurements, spectroscopic features and sorption modelling

    NASA Astrophysics Data System (ADS)

    Tertre, E.; Berger, G.; Simoni, E.; Castet, S.; Giffaut, E.; Loubet, M.; Catalette, H.

    2006-09-01

    The sorption of Eu(III) onto kaolinite and montmorillonite was investigated up to 150 °C. The clays were purified samples, saturated with Na in the case of montmorillonite. Batch experiments were conducted at 25, 40, 80 and 150 °C in 0.5 M NaClO 4 solutions to measure the distribution coefficients (Kd) of Eu as a trace element (<10 -6 mol/L) between the solution and kaolinite. For the Na-montmorillonite, we used Kd results from a previous study [Tertre, E., Berger, G., Castet, S., Loubet, M., Giffaut, E., 2005. Experimental study of adsorption of Ni 2+, Cs + and Ln 3+ onto Na-montmorillonite up to 150 °C. Geochim. Cosmochim. Acta69, 4937-4948] obtained under exactly the same conditions. The number and nature of the Eu species sorbed onto both clay minerals were investigated by time resolved laser fluorescence spectroscopy (TRLFS) in specific experiments in the same temperature range. We identified a unique inner-sphere complex linked to the aluminol sites in both clays, assumed to be dbnd AlOEu 2+ at the edge of the particles, and a second exchangeable outer-sphere complex for montmorillonite, probably in an interlayer position. The Kd values were used to adjust the parameters of a surface complexation model (DLM: diffuse layer model) from 25 to 150 °C. The number of Eu complexes and the stoichiometry of reactions were constrained by TRLFS. The acidity constants of the amphoteric aluminol sites were taken from another study [Tertre, E., Castet, S., Berger, G., Loubet, M., Giffaut, E. Acid/base surface chemistry of kaolinite and Na-montmorillonite at 25 and 60 °C: experimental study and modelling. Geochim. Cosmochim. Acta, in press], which integrates the influence of the negative structural charge of clays on the acid/base properties of edge sites as a function of temperature and ionic strength. The results of the modelling show that the observed shift of the sorption edge towards low pH with increasing temperature results solely from the contribution of the dbnd AlOEu 2+ edge complexes. Finally, we successfully tested the performance of our model by confronting the predictions with experimental Kd data. We used our own data obtained at lower ionic strength (previous study) or higher suspension density and higher starting concentration (TRLFS runs, this study), as well as published data from other experimental studies [Bradbury, M.H., Baeyens, B., 2002. Sorption of Eu on Na and Ca-montmorillonite: experimental investigations and modeling with cation exchange and surface complexation. Geochim. Cosmochim. Acta66, 2325-2334; Kowal-Fouchard, A., 2002. Etude des mécanismes de rétention des ions U(IV) et Eu(III) sur les argiles: influence des silicates. Ph.D. Thesis, Université Paris Sud, France, 330p].

  13. Clay Minerals And Sr-Nd Isotopes Constraint On Sediments Provenance And Transport Pathways In The Eastern South China Sea

    NASA Astrophysics Data System (ADS)

    Yang, Q.; Zhou, H.; Zhang, F.

    2008-12-01

    Mineralogy and Sr-Nd isotopic composition of the <2μm fraction of 178 surface sediment samples collected by grab sampler in the eastern South China Sea(116°45'-121°14'E,12°- 22°N) were used to identify the sediment provenance and delineate its transport pathways. The clay mineral assemblages mainly consist of illite, chlorite, smectite and kaolinite with an average content of 62.33%, 17.43%, 11.63%, 8.53% respectively. From NE to SW of the survey area, the contents of illite and chlorite are gradually decreased, while the contents of smectite and kaolinite show a trend of gradually increase. A high illite zone extends intermittently along NNE to the north of 16.5°N, while the high smectite content zone occurs in the east of the study area, i.e., in the open sea to the west coast of the Philippines, and smectite shows a trend of gradual decrease from east toward west to the south of 16.5°N. 87Sr/86Sr and 143Nd/144Nd isotopic compositions of the aluminum silicate phase in the clay fractions (<2μm) range from 0.71058 to 0.73050 and from 0.512040 to 0.512468 respectively. The 87Sr/86Sr ratios in the northern continental shelf and slope to the north of 16.5°N are relatively high, majority of 87Sr/86Sr ratios are little higher than the average ratio of the crust (0.720), and turn out to be gradually decreased toward the abyssal area in the south, while the 143Nd/144Nd ratios simply show the opposite variation trend with 87Sr/86Sr. The 87Sr/86Sr ratio for sediments in the south of 16.5°N shows a trend of gradual increase from east toward west, and the minimum value along the coast of Luzon Island, while the 143Nd/144Nd ratio also show the opposite variation trend. Locally in areas around the Luzon Straits the 143Nd/144Nd ratio shows a trend of gradual decrease while the 87Sr/86Sr ratio shows a trend of gradual increase from SE toward NW. Through a coupling approach based on clay minerals and Sr-Nd isotopes, it can be concluded that the terrigenous materials occurring approximately to the north of 16.5°N in the eastern South China Sea mainly originate from the Taiwan Islands and the Taiwan Straits. Continued supply of sediment fed from the Taiwan orogen are transported southward via the Penghu Canyon into the Manila Trench due to the influence of the gravity flow of sediments. However, this gravity flow of sediments was blocked by the seamount on the seabed around 16.5°N, and got settled down in the central sea basin. While the volcanic materials occurring to the south of 16.5°N mainly result from volcanic ashes from the volcanoes on Luzon Island, and were transported into South China Sea mainly via both wind and ocean currents.

  14. Characterization of the Waukesha Illite: A mixed-polytype illite in the Clay Mineral Society repository

    USGS Publications Warehouse

    Grathoff, Georg H.; Moore, D.M.

    2002-01-01

    The Waukesha Illite is an excellent example of the illites found in argillaceous rocks, typical for Paleozoic shales that have undergone significant burial diagenesis during their geologic history. It consists of a mixture of detrital 2M1, interpreted to be a residuum of karstification within Silurian carbonates, and diagenetic 1M and 1Md illite. The chemistry and the age of the illite polytypes are different. Extrapolating to 100%, the 1M and 1Md polytypes have an apparent diagenetic age between 295 and 325 Ma. The chemistry of the 1M polytype could not be determined because of its low abundance. The approximate chemical composition of the 1Md polytype is 0.67 K, 3.6 Si, and 1.9 Al per half unit cell. The 2M1 polytype has an apparent detrital age between 440 and 520 Ma, and an approximate chemical composition per half unit cell of 0.78 K, 3.4 Si, and 2.1 Al, all within our margin of error. X-ray diffraction (XRD) results of both random powder and oriented preparations both indicate that the Waukesha Illite consists of a mixture of illites. The XRD patterns of the random powder preparation indicate it is a physical mixture of three different illite polytypes. This result was confirmed using 3 different methods: (1) by measuring illite polytype-specific reflections; (2) by mixing illite polytype reference samples; and (3) by mixing WILDFIRE calculated XRD patterns. Decomposition of the illite 001 XRD peak from oriented preparations also indicates mixtures of illites. However, the proportions of the three illitic components derived from the oriented 001 peak decomposition differ from those results derived from the analysis of the random powder data. Therefore, the shape of the 001 reflection of the Waukesha Illite cannot be explained by mixing the three different illite polytypes.

  15. Clay mineral assemblages in high-resolution Plio-Pleistocene interval (0-50 mbsf) at ODP Site 188-1165, Prydz Bay, Antarctica

    NASA Astrophysics Data System (ADS)

    Junttila, J.; Ruikka, M.; Strand, K.

    2003-04-01

    ODP Leg 188 Site 1165 was drilled on the Wild Drift on the Continental Rise off Prydz Bay, East Antarctica to a total depth of 999.1 mbsf. It recovered terrigenous and hemipelagic sediments of early Miocene to Pleistocene age. Of special interest is the sediment column between 0 and 50 mbsf which consists of well-preserved section of Pliocene-Pleistocene-age sediments which was then sampled with 10 cm intervals. Multiproxy study of this interval could show the intervals of expansions of the ice sheet across the continental shelves and Antarctic cryospheric evolution, particularly during the “middle” Pliocene warm period (3.15 to 2.85 Ma) which may provide an indication of how Earth may respond to future global warming. According to the existing age model, the 50 mbsf stratigraphic sequence of Site 1165 reaches back to ~4.9 Ma. Throughout this interval, the clay mineral content is characterized by major fluctuations of individual clay minerals, particularly smectite and chlorite. The smectite concentration varies mainly between 0% and 30%. Illite fluctuates less; concentrations are mainly 50% to 80%, and kaolinite varies mainly between 10 and 20%. Chlorite concentrations are mainly 0% to 10%. We assume that the short-term fluctuations of clay mineral assemblages could be caused by repeated advance and retreat of grounded ice masses across the shelf, resulting from changes of the Antarctic ice volume presumably parallel to the situation on the Antarctic Peninsula. Short-term cyclic changes in clay mineral assemblages deposited at Site 1165 occur throughout the Pliocene and Quaternary independent of changes in the clay content. In this poster we will give a closer look into two windows within this 50m sediment sequence. The first window is from 10-16 mbsf where a prominent change from Pliocene to Pleistocene occur. The second one is from 28-34mbsf which indicates shift from warmer to colder conditions during middle Pliocene. For instance, the noticeable change detected both by magnetostratigraphic and spectrographic methods at ~34 mbsf is clearly indicated in the composition of the clay-mineral suite. At this level, smectite decreases whereas kaolinite increases. Illite and chlorite also show variability. In particular, there is a slight but persistent increase in chlorite. Smectite may delivered by bottom-current transport along the continental rise and the decrease of smectite might be a consequence of climate-induced changes in depositional processes.

  16. Adsorption of dissolved aluminum on sapphire-c and kaolinite: implications for points of zero charge of clay minerals

    PubMed Central

    2014-01-01

    We have studied the impact of dissolved aluminum on interfacial properties of two aluminum bearing minerals, corundum and kaolinite. The effect of intentionally adding dissolved aluminum on electrokinetic potential of basal plane surfaces of sapphire was studied by streaming potential measurements as a function of pH and was complemented by a second harmonic generation (SHG) study at pH 6. The electrokinetic data show a similar trend as the SHG data, suggesting that the SHG electric field correlates to zeta-potential. A comparable study was carried out on kaolinite particles. In this case electrophoretic mobility was measured as a function of pH. In both systems the addition of dissolved aluminum caused significant changes in the charging behavior. The isoelectric point consistently shifted to higher pH values, the extent of the shift depending on the amount of aluminum present or added. The experimental results imply that published isoelectric points of clay minerals may have been affected by this phenomenon. The presence of dissolved aluminum in experimental studies may be caused by particular pre-treatment methods (such as washing in acids and subsequent adsorption of dissolved aluminum) or even simply by starting a series of measurements from extreme pH (causing dissolution), and subsequently varying the pH in the very same batch. This results in interactions of dissolved aluminum with the target surface. A possible interpretation of the experimental results could be that at low aluminum concentrations adatoms of aluminum (we will refer to adsorbed mineral constituents as adatoms) can form at the sapphire basal plane, which can be rather easily removed. Simultaneously, once the surface has been exposed to sufficiently high aluminum concentration, a visible change of the surface is seen by AFM which is attributed to a surface precipitate that cannot be removed under the conditions employed in the current study. In conclusion, whenever pre-treatment or the starting point of an experiment favor the dissolution of aluminum, dissolved Al may remain in the experimental system and interact with the target surfaces. The systems are then no longer pristine and points of zero charge or sorption data are those of aluminum-bearing systems. PMID:25045321

  17. Potential application of microbial iron redox cycles in nitrate removal and their effects on clay mineral properties

    NASA Astrophysics Data System (ADS)

    Zhao, L.; Dong, H.; Kukkadapu, R. K.; Briggs, B. R.; Zeng, Q.

    2014-12-01

    Phyllosilicates that are ubiquitous in subsurface can serve as an iron source for microbial respiration. The objective of this research is to determine the ability of the phyllosilicate Fe to remove nitrate in subsurface undergoing microbial-driven redox cycles. In this study, thus, a well-characterized reference clay (NAu-2; nontronite), was subjected to redox cycles in a system containing dissimilatory Fe(III)-reducing bacteria, Shewanella putrefaciens CN32, and nitrate-dependent Fe(II)-oxidizing bacteria, Pseudogulbenkiania sp. Strain 2002. Three redox cycles were conducted in bicarbonate- and PIPES-buffered medium. The extents of Fe(III) reduction, Fe(II) oxidation, nitrate reduction, and its various intermediate products were measured by wet chemical methods. For each cycle, Electron Energy Loss Spectroscopy and Mossbauer spectroscopy confirmed Fe oxidation state. Mineralogical changes were identified by using X-ray diffraction (XRD), 57Fe-Mössbauer spectroscopy, and infrared absorption spectroscopy. For all three cycles, nitrate was completely reduced to nitrogen gas under both bicarbonate- and PIPES- buffered conditions. As redox cycle increased, bio-reduction extents of Fe(III) in NAu-2 decreased by 33% and 48% in PIPES- and bicarbonate-buffered medium, respectively; however, bio-oxidation extents increased by 66% and 55% in the same medium, respectively. Despite the change of OH-stretching vibration band and OH-bending vibration bands in NAu-2 structure along Fe redox cycles, XRD data showed interlayer spacing of NAu-2 to be constant along the same Fe redox cycle. 57Fe-Mössbauer spectroscopy indicated complex reduction and re-oxidation pathways. For example, a distinct Fe(II) doublet and a Fe2.5+ feature due to interfacial Fe(II)-Fe(III) electron transfer on clay mineral are prominent in their RT spectra. Both these Fe(II) are partially oxidized by Fe(II)-oxidizing bacteria. The result of this study shows that Fe in biogenically reduced or oxidized NAu-2 could serve as a renewable iron source for multiple biogenic redox cycles to remove nitrate contaminant in soils and groundwater systems.

  18. CLAYFORM: a FORTRAN 77 computer program apportioning the constituents in the chemical analysis of a clay or other silicate mineral into a structural formula

    USGS Publications Warehouse

    Bodine, M.W., Jr.

    1987-01-01

    The FORTRAN 77 computer program CLAYFORM apportions the constituents of a conventional chemical analysis of a silicate mineral into a user-selected structure formula. If requested, such as for a clay mineral or other phyllosilicate, the program distributes the structural formula components into appropriate default or user-specified structural sites (tetrahedral, octahedral, interlayer, hydroxyl, and molecular water sites), and for phyllosilicates calculates the layer (tetrahedral, octahedral, and interlayer) charge distribution. The program also creates data files of entered analyses for subsequent reuse. ?? 1987.

  19. Insights into the Mechanism of Fe(II) Adsorption and Oxidation at Fe-Clay Mineral Surfaces from First-Principles Calculations

    SciTech Connect

    Alexandrov, Vitali Y.; Rosso, Kevin M.

    2013-10-02

    Interfacial reactivity of redox-active iron-bearing mineral surfaces plays a crucial role in many environmental processes including biogeochemical cycling of various elements and contaminants. Herein, we apply density-functional-theory (DFT) calculations to provide atomistic insights into the heterogeneous reaction between aqueous Fe(II) and the Fe-bearing clay mineral nontronite Fe2Si4O10(OH)2 by studying its adsorption mechanism and interfacial Fe(II)-Fe(III) electron transfer (ET) at edge and basal surfaces. We find that edge-bound Fe(II) adsorption complexes at different surface sites (ferrinol, silanol and mixed) may coexist on both (010) and (110) edge facets, with complexes at ferrinol FeO(H) sites being the most energetically favorable and coupled to proton transfer. Calculation of the ET activation energy suggests that interfacial ET into dioctahedral Fe(III) sheets is probable at the clay edges and occurs predominantly but not exclusively through the complexes adsorbed at ferrinol sites and might also involve mixed sites. No clear evidence is found for complexes on basal surface that are compatible with ET through the basal sheet despite this experimentally hypothesized ET interface. This study suggests a strong pH-dependence of Fe(II) surface complexation at basal versus edge facets and highlights the importance of the protonation state of bridging ligands and proton coupled electron transfer to facilitate ET into Fe-rich clay minerals.

  20. Synergy between polyaniline and OMt clay mineral in Langmuir-Blodgett films for the simultaneous detection of traces of metal ions.

    PubMed

    de Barros, Anerise; Ferreira, Mariselma; Constantino, Carlos José Leopoldo; Bortoleto, José Roberto Ribeiro; Ferreira, Marystela

    2015-04-01

    We report on Langmuir-Blodgett (LB) films made with emeraldine salt polyaniline (PAni-ES) and organophilic montmorillonite clay mineral (OMt), where synergy between the components was reached to yield an enhanced performance in detecting trace levels of cadmium (Cd(2+)), lead (Pb(2+)) and copper (Cu(2+)). Detection was carried out using square wave anodic stripping (SWAS) voltammetry with indium tin oxide (ITO) electrodes modified with LB films of PAni-ES/OMt nanocomposite, whose data were compared to those obtained with electrodes coated with neat PAni-ES and neat OMt LB films. The enhanced performance in the nanocomposite may be attributed to the stabilizing and ordering effect promoted by OMt in PAni-ES Langmuir films, which then led to more homogeneous LB films. According to X-ray diffraction data, the stacking of OMt layers was preserved in the LB films and therefore the PAni-ES chains did not cause clay mineral exfoliation. Instead, OMt affected the polaronic state of PAni-ES as indicated in UV-vis, Raman and FTIR spectra, also consistent with the changes observed for the Langmuir films. Taken together these results do indicate that semiconducting polymers and clay minerals may be combined for enhancing the electrical properties of nanostructures for sensing and related applications. PMID:25761908

  1. Reduction and long-term immobilization of technetium by Fe(II) associated with clay mineral nontronite.

    SciTech Connect

    Jaisi, D. P.; Dong, H.; Plymale, A. E.; Fredrickson, J. K.; Zachara, J. M.; Heald, S.; Liu, C.; Miami Univ.; PNNL

    2009-01-01

    {sup 99}Tc is formed mostly during nuclear reactions and is released into the environment during weapons testing and inadvertent waste disposal. The long half-life, high environmental mobility (as Tc(VII)O{sub 4}{sup -}) and its possible uptake into the food chain cause {sup 99}Tc to be a significant environmental contaminant. In this study, we evaluated the role of Fe(II) in biologically reduced clay mineral, nontronite (NAu-2), in reducing Tc(VII)O{sub 4}{sup -} to poorly soluble Tc(IV) species as a function of pH and Fe(II) concentration. The rate of Tc(VII) reduction by Fe(II) in NAu-2 was higher at neutral pH (pH 7.0) than at acidic and basic pHs when Fe(II) concentration was low (< 1 mmol/g). The effect of pH, however, was insignificant at higher Fe(II) concentrations. The reduction of Tc(VII) by Fe(II) associated with NAu-2 was also studied in the presence of common subsurface oxidants including iron and manganese oxides, nitrate, and oxygen, to evaluate the effect of these oxidants on the enhancement and inhibition of Tc(VII) reduction, and reoxidation of Tc(IV). Addition of iron oxides (goethite and hematite) to the Tc(VII)-NAu-2 system, where Tc(VII) reduction was ongoing, enhanced reduction of Tc(VII), apparently as a result of re-distribution of reactive Fe(II) from NAu-2 to more reactive goethite/hematite surfaces. Addition of manganese oxides stopped further Tc(VII) reduction, and in case of K{sup +}-birnessite, it reoxidized previously reduced Tc(IV). Nitrate neither enhanced reduction of Tc(VII) nor promoted reoxidation of Tc(IV). Approximately 11% of Tc(IV) was oxidized by oxygen. The rate and extent of Tc(IV) reoxidation was found to strongly depend on the nature of the oxidants and concentration of Fe(II). When the same oxidants were added to aged Tc reduction products (mainly NAu-2 and TcO{sub 2} {center_dot} nH{sub 2}O), the extent of Tc(IV) reoxidation decreased significantly relative to fresh Tc(IV) products. Increasing NAu-2 concentration also resulted in the decreased extent of Tc(IV) reoxidation. The results were attributed to the effect of NAu-2 aggregation that effectively retained Tc(IV) in the solid and decreased its vulnerability to reoxidation. Overall, our results implied that bioreduced clay minerals could play an important role in reducing Tc(VII) and in maintaining the long-term stability of reduced Tc(IV).

  2. Stable Isotope Systematics of Abiotic Nitrite Reduction Coupled with Anaerobic Iron Oxidation: The Role of Reduced Clays and Fe-bearing Minerals

    NASA Astrophysics Data System (ADS)

    Grabb, K. C.; Buchwald, C.; Hansel, C. M.; Wankel, S. D.

    2014-12-01

    Under anaerobic conditions, it is widely assumed that nitrate (NO3-) and nitrite (NO2-) reduction is primarily the result of microbial respiration. However, it has also been shown that abiotic reduction of nitrate and nitrite by reduced iron (Fe(II)), whether mineral-bound or surface-associated, may also occur under certain environmentally relevant conditions. With a range of experimental conditions, we investigated the nitrogen and oxygen stable isotope systematics of abiotic nitrite reduction by Fe(II) in an effort to characterize biotic and abiotic processes in the environment. While homogenous reactions between NO2- and Fe(II) in artificial seawater showed little reduction, heterogeneous reactions involving Fe-containing minerals showed considerable nitrite loss. Specifically, rapid nitrite reduction was observed in experiments that included reduced clays (illite, Na-montmorillonite, and nontronite) and those that exhibited iron oxide formation (ferrihydrite, magnetite and/or green rust). While these iron oxides and clay minerals offer both a source of reduced iron in the mineral matrix as well as a surface for Fe(II) activation, control experiments with corundum as a non-Fe containing mineral surface showed little NO2- loss, implicating a more dominant role of structural Fe in the clays during nitrite reduction. The isotope effects for 15N and 18O (15ɛ and 18ɛ) ranged from 5 to 14‰ for 15ɛ and 5 to 17‰ for 18ɛ and were typically coupled such that 15ɛ ~ 18ɛ. Reactions below pH 7 were slower and the 18ɛ was affected by oxygen atom exchange with water. Although little data exist for comparison with the dual isotopes of microbial NO2- reduction, these data serve as a benchmark for evaluating the role of abiotic processes in N reduction, particularly in sediment systems low in organic carbon and high in iron.

  3. Evaluation of the endotoxin binding efficiency of clay minerals using the Limulus Amebocyte lysate test: an in vitro study

    PubMed Central

    2014-01-01

    Endotoxins are part of the cell wall of Gram-negative bacteria. They are potent immune stimulators and can lead to death if present in high concentrations. Feed additives, which bind endotoxins in the gastrointestinal tract of animals, could help to prevent their negative impact. The objective of our study was to determine the potential of a bentonite (Bentonite 1), a sodium bentonite (Bentonite 2), a chemically treated smectite (Organoclay 1) and a modified attapulgite (Organoclay 2) to bind endotoxins in vitro. Polymyxin B served as positive control. The kinetic chromogenic Limulus Amebocyte lysate test was adapted to measure endotoxin activity. Firstly, a single sorption experiment (10 endotoxin units/mL (EU/mL)) was performed. Polymyxin B and organoclays showed 100% binding efficiency. Secondly, the adsorption efficiency of sorbents in aqueous solution with increasing endotoxin concentrations (2,450 – 51,700 EU/mL) was investigated. Organoclay 1 (0.1%) showed a good binding efficiency in aqueous solution (average 81%), whereas Bentonite 1 (0.1%) obtained a lower binding efficiency (21-54%). The following absorbent capacities were calculated in highest endotoxin concentration: 5.59 mg/g (Organoclay 1) > 3.97 mg/g (Polymyxin B) > 2.58mg/g (Organoclay 2) > 1.55 mg/g (Bentonite 1) > 1.23 mg/g (Bentonite 2). Thirdly, a sorption experiment in artificial intestinal fluid was conducted. Especially for organoclays, which are known to be unspecific adsorbents, the endotoxin binding capacity was significantly reduced. In contrast, Bentonite 1 showed comparable results in artificial intestinal fluid and aqueous solution. Based on the results of this in vitro study, the effect of promising clay minerals will be investigated in in vivo trials. PMID:24383578

  4. Minerals

    MedlinePlus

    Minerals are important for your body to stay healthy. Your body uses minerals for many different jobs, including building bones, making ... regulating your heartbeat. There are two kinds of minerals: macrominerals and trace minerals. Macrominerals are minerals your ...

  5. Mineral catalysis of the formation of dimers of 5'-AMP in aqueous solution: The possible role of montmorillonite clays in the prebiotic synthesis of RNA

    NASA Astrophysics Data System (ADS)

    Ferris, James P.; Ertem, Gözen; Agarwal, Vipin

    1989-03-01

    The reaction of the 5'-AMP with water soluble carbodiimide (EDAC) in the presence of Na+-montmorillonite 22A results in the formation of 2',5'-(pA)2 (18.9%), 3',5'-(pA)2 (11%), and AppA (4.8%). When poly(U) is used in place of the clay the product yields are 2',5'-(pA)2 (15.5%), 3',5'-(pA)2 (3.7%) and AppA (14.9%). The 3',5'-cyclic dinucleotide, 3',5'-c(pA)2, is also formed when poly(U) is used. AppA is the principal reaction product when neither clay nor poly(U) is present in the reaction mixture. Products which contain the phophodiester bond are formed at different ionic strengths, pH and temperatures using Na+-montmorillonite. Phosphodiester bond formation was not observed when Cu2+-montmorillonite was used or when DISN was used in the place of EDAC. The extent catalysis of phophodiester bond formation varied with the particular clay mineral used. Those Na+-clays which bind 5'-AMP more strongly are better catalysts. Cu2+-montmorillonite, which binds 5'-AMP strongly, exhibits no catalytic activity.

  6. Biodegradation and adsorption of C1- and C2-phenanthrenes and C1- and C2-dibenzothiophenes in the presence of clay minerals: effect on forensic diagnostic ratios.

    PubMed

    Ugochukwu, Uzochukwu C; Head, Ian M; Manning, David A C

    2014-07-01

    The impact of modified montmorillonites on adsorption and biodegradation of crude oil C1-phenanthrenes, C1-dibenzothiophenes, C2-phenanthrenes and C2-dibenzothiophenes was investigated in aqueous clay/oil microcosm experiments with a hydrocarbon degrading microorganism community. Consequently, the effect on C1-dibenzothiophenes/C1-phenanthrenes, C2-dibenzothiophenes/C2-phenanthrenes, 2+3-methyldibenzothiophene/4-methyldibenzothiophene and 1-methyldibenzothiophene/4-methyldibenzothiophene ratios commonly used as diagnostic ratios for oil forensic studies was evaluated. The clay mineral samples were treated to produce acid activated montmorillonite, organomontmorillonite and homoionic montmorillonite which were used in this study. The different clay minerals (modified and unmodified) showed varied degrees of biodegradation and adsorption of the C1-phenanthrenes, C1-dibenzothiophenes, C2-phenanthrenes and C2-dibenzothiophenes. The study indicated that as opposed to biodegradation, adsorption has no effect on the diagnostic ratios. Among the diagnostic ratios reviewed, only C2-dibenzothiophenes/C2-phenanthrenes ratio was neither affected by adsorption nor biodegradation making this ratio very useful in forensic studies of oil spills and oil-oil correlation. PMID:24275986

  7. An EXAFS study on the effects of natural organic matter and the expandability of clay minerals on cesium adsorption and mobility

    NASA Astrophysics Data System (ADS)

    Fan, Q. H.; Tanaka, M.; Tanaka, K.; Sakaguchi, A.; Takahashi, Y.

    2014-06-01

    The relationship between cesium (Cs) adsorption on clay minerals with various expandabilities and Cs mobility in environment was investigated using sequential extraction, batch adsorption, X-ray diffraction (XRD), generalized adsorption model (GAM), and Cs LIII-edge extended X-ray absorption fine structure (EXAFS) analyses with molecular simulations using the density functional theory (DFT). In particular, the difference between the affinities of illite (non-expansion) and vermiculite (intermediate expansion) for Cs and the effect of humic acid (HA) addition on the Cs/clay mineral system were highlighted in this study. These two factors affect Cs mobility and bioavailability in surface soil and sediments. The batch adsorption results showed that Cs adsorption was inhibited to some extent in the ternary clay + HA + Cs system because of (i) the blocked access of Cs to the frayed edge site (FES) and type II site [inner-sphere (IS) complex in GAM] by HA, and (ii) the reduced availability of the interlayer site in vermiculite. EXAFS analysis further confirmed that the adsorbed Cs in clay minerals was drastically changed by the sequential addition of HA. In addition, the dominant IS complex in the illite + Cs and illite + Cs + HA systems (in which HA was added after Cs adsorption on illite) can be converted to the outer-sphere (OS) complex largely in the illite + HA + Cs system (in which HA was added prior to Cs adsorption). These results are consistent with the sequential extraction and GAM results. The IS complex of dehydrated Cs+ mainly formed at the FES and interlayer site on illite (non-expansion) without resulting in any illite structural changes. However, on vermiculite (intermediate expansion), the dehydrated Cs+ can be adsorbed as an IS complex associated with the siloxane group of the di-trigonal cavity in the tetrahedral SiO4 sheet. This adsorption is accompanied by collapse of the layer, which can be easily coated by HA molecules to prevent Cs fixation. However, a nearly complete OS complex was observed at the planar site of montmorillonite (large expansion). These processes were confirmed by sequential extraction, batch adsorption, XRD, and EXAFS, which clearly showed that Cs mobility in soil highly depends on clay mineral expandability, natural organic matter (NOM), and the coupling of both effects. The atomic-scale information given by EXAFS is consistent with the distribution data from adsorption experiments, GAM, sequential extraction, and DFT. These results can be used as a basis for a clearer understanding of Cs behavior in natural systems.

  8. Elucidating the Physical and Chemical Structural Changes of Proteins on Clay Mineral Surfaces using Large-scale Molecular Dynamics Simulations in Tandem with NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Andersen, A.; Govind, N.; Washton, N.; Reardon, P.; Chacon, S. S.; Burton, S.; Lipton, A.; Kleber, M.; Qafoku, N. P.

    2014-12-01

    Carbon cycling among the three major Earth's pools, i.e., atmosphere, terrestrial systems and oceans, has received increased attention because the concentration of CO2 in the atmosphere has increased significantly in recent years reaching concentrations greater than 400 ppm that have never been recorded before, warming the planet and changing the climate. Within the terrestrial system, soil organic matter (SOM) represents an important sub-pool of carbon. The associations of SOM with soil mineral interfaces and particles, creating micro-aggregates, are believed to regulate the bioavailability of the associated organic carbon by protecting it from transformations and mineralization to carbon dioxide. Nevertheless, the molecular scale interactions of different types of SOM with a variety of soil minerals and the controls on the extent and rate of SOM transformation and mineralization are not well documented in the current literature. Given the importance of SOM fate and persistence in soils and the current knowledge gaps, the application of atomistic scale simulations to study SOM/mineral associations in abiotic model systems offers rich territory for original and impactful science. Molecular modeling and simulation of SOM is a burgeoning and challenging avenue for aiding the characterization of these complex compounds and chemical systems and for studying their interactions in self-assembled aggregates composed of different organic matter compounds and with mineral surfaces of different types and common in soils, which are thought to contribute to their reactive properties including recalcitrance potential and resistance to mineralization. Here, we will discuss our large-scale molecular dynamics simulation efforts to explore the interaction of proteins with clay minerals (i.e., phyllosilicates such as kaolinite, smectite and micas), including the potential physical and chemical structural changes of proteins, protein adsorption by polar and permanently charged mineral surfaces and variably charged edges, and the potential role of amphiphilic proteins in providing adsorptive layers for SOM-mineral interfaces. Our efforts at characterizing these systems through combined modeling and simulation and NMR will also be discussed.

  9. Geotechnical evaluation of Turkish clay deposits: a case study in Northern Turkey

    NASA Astrophysics Data System (ADS)

    Kalkan, Ekrem; Bayraktutan, M. Salih

    2008-09-01

    Clay deposits in Oltu-Narman basins (Erzurum, northern Turkey) have been studied to determine their engineering properties and to evaluate their uses for geotechnical applications. These deposits are concentrated in two different stratigraphic horizons namely the Late Oligocene and the Early Miocene sequences. Clay-rich fine-grained sedimentary units are deposited in shallow marine and lagoonar mixed environments. Their clay minerals originated by the alteration of Eocene calc-alkaline island-arc volcanics, preferably from pyroclastics (trachite and andesite flow), which form the basement for the Oltu depression. Smectite group clay minerals are found abundant in clay deposits. The experimental results show that the clay soils have high plasticity behaviors and low hydraulic conductivity properties. The optimum water content, the free swell, and the swelling pressure of clay samples decreased and the maximum dry unit weight of clay samples increased under high temperature. Consequently, it is concluded that the expanding of clay soils is an important soil problem that cannot be avoided in the significant parts of Oltu city and its villages. However, the soils of clay-rich layers in the outcrops-section of clay deposits can be successfully used to build compacted clay liners for landfill systems and to construct vertical and horizontal barriers for protection of ground water and for preventing soil pollution in geotechnical applications.

  10. CO2-Brine-Iron-bearing Clay Mineral Interactions: Surface Area Changes and Fracture-Filling Potentials in Geologic CO2 Sequestration

    NASA Astrophysics Data System (ADS)

    Jun, Y.; Hu, Y.

    2011-12-01

    Geologic carbon dioxide sequestration (GCS) is a promising option to reduce anthropogenic CO2 emission from coal-fired power plants. The injected CO2 in GCS sites can induce dissolution of rocks and secondary mineral formation, potentially change the physical properties of the geological formations, and thus influence the transport and injectivity of CO2. However, most of the relevant studies are based on hydrological transport, using simulation models rather than studying actual interfacial chemical reactions. The mechanisms and kinetics of interfacial reactions among supercritical CO2 (scCO2)-saline water-rock surfaces at the molecular scale and their impacts on CO2 leakage have not been well understood. This research investigated the effects of various environmental factors (such as temperature, pressure, salinity, and different metal ion and organic-containing brine) on the dissolution and surface morphological changes of clay minerals. In this work, iron-bearing clay mineral, biotite [K(Mg,Fe)3AlSi3O10(OH,F)2], was used for model clay minerals in potential GCS sites. Both fluid/solid chemistry analysis and interfacial topographic studies were conducted to investigate the dissolution/precipitation on clay mineral surfaces under GCS conditions in high salinity systems. Using atomic force microscopy (AFM) and scanning electron microscopy (SEM), the interfacial surface morphology changes were observed. Shortly after a CO2 pressure of 102 atm is applied at 95oC, in situ pH of solutions was 3.15 ± 0.10. The early intrinsic dissolution rates of biotite were 8.4 ± 2.8 × 10-13 and 11.2 ± 3.0 × 10-13 mol Si m-2s-1 in water and NaCl solution, respectively. At the early stage of reaction, fast growth of fibrous illite on biotite basal planes was observed. After 22-70 h reaction, the biotite basal surface cracked, resulting in illite detaching from the surfaced. Later, the cracked surface layer was released into solution, thus the inner layer was exposed as a renewed flat basal surface (96-120 h). The cracking and detachment of the biotite surface layer increased the surface area in contact with solution and accelerated biotite dissolution. In control experiments with water under the same temperature and pressure, neither macroscopic fibrous illite nor cracks were observed. On the other hand, on the edge surfaces or fractured surfaces of biotite, significant amounts of Al-substituted goethite and kaolinite were formed, which can be further investigated as caprock self-healing potentials of iron-bearing clay minerals. This study provides important fundamental information for a better understanding of porosity and permeability changes owing to the clay mineral's surface morphological evolution by geochemical reactions, and this also helps designing a more accurate reactive transport models under GCS conditions.

  11. The role of clay minerals and fulvic acid to the complexation of Na, Mg, and Ca in stream flows from adjacent forested head watersheds composed of different vegetation

    NASA Astrophysics Data System (ADS)

    Terajima, Tomomi; Moriizumi, Mihoko; Nakamura, Tomohiro

    2010-05-01

    In order to understand the complexation and flow process in metal elements under a fresh water environment, discharges of Na, Mg, and Ca were measured in streams of adjacent forested head watersheds composed of coniferous evergreen- and deciduous broad leaf- trees. Total elements (T-Na, T-Mg, and T-Ca) and ions (Na+, Mg2+, and Ca2+) in stream flows which passed through 0.45 μm filters were measured with an ICP and Ion-chromatograph. The remainders of total elements and ions were equated with complex compounds. Then the discharges of Si and fulvic acid, which respectively are the representatives of ligands by clay minerals and humic substances, provided the relationship between the compound discharges and the complexation process of the above metal elements. Even if Na, Mg, and Ca are believed to be mostly free ions in fresh water environments, the rates of the compounds to the total elements ranged 10 to 40 % in the coniferous watershed and 20 to 60 % in the deciduous watersheds. The compounds sometimes occupied more than half of the total elements; this was predominant in the deciduous watershed. These mean that the discharge of compounds is not negligible in watershed hydrology. Possible complexation processes in metal elements are #1) Hydration, #2) Adsorption or substitution with clay minerals, #3) Mineral complex, #4) Adsorption with humic substances as represented by fulvic acid, and #5) Chelate with organic acids as oxalate, formic acid, and pyrrole. Under fresh water environments, #2 and #4 must be the most potential processes of the complexation in metal elements. The relationship between the compounds, Si, and fulvic acid, therefore, supplies useful information to presume the status of the compounds. The compounds-Si relations in both watersheds showed linear correlations (r=0.79 to 0.99) for a stream base flow and stream flow in a small rainstorm. The linear correlations, however, occurred only for the stream flow in the compounds-Si relations at a big rain storm in the deciduous watershed (r=0.89 to 1.00) and also for the storm flow in the compound-fulvic acid relations (r=0.95 to 0.99). These things mean that the metal elements possibly flowed out as organic and/or inorganic complexes and the complexation could have been promoted in the deciduous watershed during rain storms. Thick organic soil, broadly distributing in the deciduous watershed, seems to be reasonable for promoting such complexation due to subsurface water movement in the soil through the contact of the metal elements with clay minerals and fulvic acid. In contrast, the much rainwater flows down below the surface within the loose litter and root-permeated zone developing predominantly in the coniferous watershed, where small clay minerals and humic substances occurs; which represents the rare contact of the metal elements with the clay minerals and fulvic acid in such flow paths. This would be the reason for the small and restrained complexation in the coniferous watershed at the big rain storm. The hydrochemical process in slope-stream systems can be controlled by the complexation affected by both the flow path of rainwater and the distribution of clay minerals and humic substances in soils.

  12. Colorimetric Humidity and Solvent Recognition Based on a Cation-Exchange Clay Mineral Incorporating Nickel(II)-Chelate Complexes.

    PubMed

    Hosokawa, Hitoshi; Mochida, Tomoyuki

    2015-12-01

    Solvatochromic nickel(II) complexes with diketonato and diamine ligands were incorporated into a saponite clay by ion exchange, and their colorimetric humidity- and solvent-recognition properties were investigated. These powders exhibit color change from red to blue-green depending on humidity, and the detection range can be controlled by modifying the metal complex. The humidity response takes advantage of the humidity-dependent water content in clay and the coordination of water molecules to the metal complex in equilibrium. The addition of organic solvents to the powders causes a color change to occur, varying from red to blue-green depending on the donor number of the solvent, thereby enabling solvent recognition. In the clay, the affinity of less sterically hindered complexes to water or solvent molecules is decreased compared with that in solution because the cationic complexes interact with the anionic layers in the clay. Incorporating diethylene glycol into the materials produced thermochromic powders. PMID:26542108

  13. Synthesis and structural characterization of ferrous trioctahedral smectites: Implications for clay mineral genesis and detectability on Mars

    NASA Astrophysics Data System (ADS)

    Chemtob, Steven M.; Nickerson, Ryan D.; Morris, Richard V.; Agresti, David G.; Catalano, Jeffrey G.

    2015-06-01

    Widespread detections of phyllosilicates in Noachian terrains on Mars imply a history of near-surface fluid-rock interaction. Ferrous trioctahedral smectites are thermodynamically predicted products of basalt weathering on early Mars, but to date only Fe3+-bearing dioctahedral smectites have been identified from orbital observations. In general, the physicochemical properties of ferrous smectites are poorly studied because they are susceptible to air oxidation. In this study, eight Fe2+-bearing smectites were synthesized from Fe2+-Mg-Al silicate gels at 200°C under anoxic conditions. Samples were characterized by inductively coupled plasma optical emission spectrometry, powder X-ray diffraction, Fe K-edge X-ray absorption spectroscopy (XAS), Mössbauer spectroscopy, and visible/near-infrared (VNIR) reflectance spectroscopy. The range of redox states was Fe3+/ΣFe = 0 to 0.06 ± 0.01 as determined by both XAS and, for short integration times, Mössbauer. The smectites have 060 distances (d(060)) between 1.53 and 1.56 Å, indicating a trioctahedral structure. d(060) and XAS-derived interatomic Fe-(Fe,Mg,Al) distance scaled with Fe content. Smectite VNIR spectra feature OH/H2O absorption bands at 1.4 and 1.9 µm, (Fe2+,Mg,Al)3-OH stretching bands near 1.4 µm, and Fe2+Fe2+Fe2+-OH, MgMgMg-OH, AlAl(Mg,Fe2+)-OH, and AlAl-OH combination bands at 2.36 µm, 2.32 µm 2.25 µm, and 2.20 µm, respectively. The spectra for ferrous saponites are distinct from those for dioctahedral ferric smectites, permitting their differentiation from orbital observations. X-ray diffraction patterns for synthetic high-Mg ferrosaponite and high-Mg ferrian saponite are both consistent with the Sheepbed saponite detected by the chemistry and mineralogy (CheMin) instrument at Gale Crater, Mars, suggesting that anoxic basalt alteration was a viable pathway for clay mineral formation on early Mars.

  14. The formation of high temperature clay minerals from basalt alteration during hydrothermal discharge on the East Pacific Rise axis at 21°N

    NASA Astrophysics Data System (ADS)

    Haymon, Rachel M.; Kastner, Miriam

    1986-09-01

    Aluminous, high-temperature clay minerals form from alteration of tholeiitic basaltic glass and calcic plagioclase during hydrothermal venting on the crest of the East Pacific Rise at 21°N. The clay alteration assemblages are layered crusts (up to 1 mm thick) completely replacing glass and calcic plagioclase adjacent to surfaces exposed to hydrothermal fluids. The interiors of the affected basalt samples have unaltered appearances and oxygen isotopic compositions just slightly heavier than that of MORB. The surficial alteration crusts are mixtures of beidellitic smectite (aluminous, dioctahedral), randomly interstratified mixed-layer Al-rich chlorite/smectite, minor chlorite, an x-ray amorphous aluminosilicate material, and possible minor serpentine (amesite). A δ 18O value of +4.1 ± 0.2%. (SMOW) is determined for the beidellitic smectite. Assuming that this smectite equilibrated with hydrothermal fluid having an oxygen isotope value between that of seawater (0%.) and 350°C hydrothermal fluid from EPR, 21°N vents (+1.6%.), an equilibration temperature between 290°C and 360°C is calculated for the beidellitic smectite. This is substantially higher than any previously reported temperature for an oceanic smectite. The mixed-layer Al-rich chlorite/smectite has a δ 18O value of +3.5%., which corresponds to equilibration at 295°-360°C. The aluminous composition of the alteration assemblage is uncommon for clay minerals produced by submarine hydrothermal basalt alteration. We suggest that this assemblage is largely the product of high-temperature interaction between basalt glass + plagioclase and Mg-poor, acidic hydrothermal fluids, with possibly some contribution of Mg from bottom seawater, and that the aluminous clays either incorporate Al 3+ remobilized from basalt by lowpH hydrothermal fluids, or are residual phases remaining after intense alteration of basaltic glass + plagioclase.

  15. Optical constants using two particle size distributions: On-going laboratory efforts to quantitatively address clay abundance on Mars

    NASA Astrophysics Data System (ADS)

    Roush, T. L.; Bishop, J. L.; Brown, A. J.; Blake, D.; Bristow, T.

    2013-12-01

    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 of pure end-members are needed. We report on the final stages of our on-going effort to enable the quantitative evaluation of the abundance of hydrated-hydroxylated silicates when they are contained in mixtures. We include several 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. We used scanning electron microscope images to characterize the grain size distribution, of each sample. Using the grain size distribution, we have derived initial estimates of the optical constants of these materials and compare them to values estimated for the same samples, but using the mean particle size of the sieve fraction. We discuss the results of our calculations for these materials and their implications for modeling the physical mixtures and eventual comparison to Martian spectra.

  16. Deglacial Record in the Illinois River Valley Explains Asynchronous Phases of Meltwater Pulses and Clay Mineral Excursions in the Gulf of Mexico

    NASA Astrophysics Data System (ADS)

    Wang, H.

    2014-12-01

    One prominent event of the Bølling/Allerød (B/A) interstadial was the large meltwater release to global oceans. The Laurentide Ice Sheet (LIS) is usually considered the main source. But, the large LIS meltwater discharge conflicts with the marine record showing an active North Atlantic meridional overturning circulation (AMOC) during the B/A interval. Continuous dune-lacustrine successions in the Illinois River Valley (IRV) have shown complete records of the last deglacial chronozones. Their grain-size distributions and accurate B/A age 14C dates of plant fossils from 15 m deep lacustrine sediment in the IRV suggest that most of the IRV and parts of the adjacent upland were inundated by water. The inundation was caused by a sediment dam interpreted to have been constructed and followed by a breach at the confluence of the Mississippi and Illinois Rivers during the B/A interval due to sediment mobilization by the large meltwater release. The grain size distributions correlate with meltwater pulses and mineralogical excursions in sediments from the Gulf of Mexico (GOM) very well. The blockage and release of illite and chlorite rich fine-grained sediments from the Lake Michigan basin changed the relative abundance of clay minerals and thus the ratio of smectite/(illite + chlorite) in the sediment of the GOM. This finding explains why the meltwater episodes from the LIS and the associated detrital discharges are not synchronous in the sediments in the GOM. The finding also ties meltwater pulses and associated detrital discharges in the GOM closely to the LIS discharges via the Mississippi River Valley on chronozonal scales. Three arguments can be made from this result: 1) unaffected AMOC during B/A interval resulted potentially from the hyperpycnal inflow into the GOM floor; 2) limited volume of the meltwater discharge did not significantly influence the AMOC; and 3) the freshwater input into the GOM from the LIS at this particular location did not significantly influence the AMOC.

  17. Spatial Abundance and Distribution of Potential Microbes and Functional Genes Associated with Anaerobic Mineralization of Pentachlorophenol in a Cylindrical Reactor

    NASA Astrophysics Data System (ADS)

    Li, Zhi-Ling; Nan, Jun; Huang, Cong; Liang, Bin; Liu, Wen-Zong; Cheng, Hao-Yi; Zhang, Chunfang; Zhang, Dongdong; Kong, Deyong; Kanamaru, Kyoko; Kobayashi, Tetsuo; Wang, Ai-Jie; Katayama, Arata

    2016-01-01

    Functional interplays of microbial activity, genetic diversity and contaminant transformation are poorly understood in reactors for mineralizing halogenated aromatics anaerobically. Here, we investigated abundance and distribution of potential microbes and functional genes associated with pentachlorophenol (PCP) anaerobic mineralization in a continuous-flow cylindrical reactor (15 cm in length). PCP dechlorination and the metabolite (phenol) were observed at segments 0-8 cm from inlet, where key microbes, including potential reductive dechlorinators (Dehalobacter, Sulfurospirillum, Desulfitobacterium and Desulfovibrio spp.) and phenol degraders (Cryptanaerobacter and Syntrophus spp.), as well as putative functional genes, including putative chlorophenol reductive dehalogenase (cprA) and benzoyl-CoA reductase (bamB), were highly enriched simultaneously. Five types of putative cprAs, three types of putative bamBs and seven types of putative nitrogenase reductase (nifHs) were determined, with their copy numbers decreased gradually from inlet to outlet. Distribution of chemicals, bacteria and putative genes confirmed PCP dechlorination and phenol degradation accomplished in segments 0-5 cm and 0-8 cm, respectively, contributing to a high PCP mineralization rate of 3.86 μM d-1. Through long-term incubation, dechlorination, phenol degradation and nitrogen fixation bacteria coexisted and functioned simultaneously near inlet (0-8 cm), verified the feasibility of anaerobic mineralization of halogenated aromatics in the compact reactor containing multiple functional microbes.

  18. Spatial Abundance and Distribution of Potential Microbes and Functional Genes Associated with Anaerobic Mineralization of Pentachlorophenol in a Cylindrical Reactor

    PubMed Central

    Li, Zhi-Ling; Nan, Jun; Huang, Cong; Liang, Bin; Liu, Wen-Zong; Cheng, Hao-Yi; Zhang, Chunfang; Zhang, Dongdong; Kong, Deyong; Kanamaru, Kyoko; Kobayashi, Tetsuo; Wang, Ai-Jie; Katayama, Arata

    2016-01-01

    Functional interplays of microbial activity, genetic diversity and contaminant transformation are poorly understood in reactors for mineralizing halogenated aromatics anaerobically. Here, we investigated abundance and distribution of potential microbes and functional genes associated with pentachlorophenol (PCP) anaerobic mineralization in a continuous-flow cylindrical reactor (15 cm in length). PCP dechlorination and the metabolite (phenol) were observed at segments 0–8 cm from inlet, where key microbes, including potential reductive dechlorinators (Dehalobacter, Sulfurospirillum, Desulfitobacterium and Desulfovibrio spp.) and phenol degraders (Cryptanaerobacter and Syntrophus spp.), as well as putative functional genes, including putative chlorophenol reductive dehalogenase (cprA) and benzoyl-CoA reductase (bamB), were highly enriched simultaneously. Five types of putative cprAs, three types of putative bamBs and seven types of putative nitrogenase reductase (nifHs) were determined, with their copy numbers decreased gradually from inlet to outlet. Distribution of chemicals, bacteria and putative genes confirmed PCP dechlorination and phenol degradation accomplished in segments 0–5 cm and 0–8 cm, respectively, contributing to a high PCP mineralization rate of 3.86 μM d−1. Through long-term incubation, dechlorination, phenol degradation and nitrogen fixation bacteria coexisted and functioned simultaneously near inlet (0–8 cm), verified the feasibility of anaerobic mineralization of halogenated aromatics in the compact reactor containing multiple functional microbes. PMID:26750760

  19. Spatial Abundance and Distribution of Potential Microbes and Functional Genes Associated with Anaerobic Mineralization of Pentachlorophenol in a Cylindrical Reactor.

    PubMed

    Li, Zhi-Ling; Nan, Jun; Huang, Cong; Liang, Bin; Liu, Wen-Zong; Cheng, Hao-Yi; Zhang, Chunfang; Zhang, Dongdong; Kong, Deyong; Kanamaru, Kyoko; Kobayashi, Tetsuo; Wang, Ai-Jie; Katayama, Arata

    2016-01-01

    Functional interplays of microbial activity, genetic diversity and contaminant transformation are poorly understood in reactors for mineralizing halogenated aromatics anaerobically. Here, we investigated abundance and distribution of potential microbes and functional genes associated with pentachlorophenol (PCP) anaerobic mineralization in a continuous-flow cylindrical reactor (15 cm in length). PCP dechlorination and the metabolite (phenol) were observed at segments 0-8 cm from inlet, where key microbes, including potential reductive dechlorinators (Dehalobacter, Sulfurospirillum, Desulfitobacterium and Desulfovibrio spp.) and phenol degraders (Cryptanaerobacter and Syntrophus spp.), as well as putative functional genes, including putative chlorophenol reductive dehalogenase (cprA) and benzoyl-CoA reductase (bamB), were highly enriched simultaneously. Five types of putative cprAs, three types of putative bamBs and seven types of putative nitrogenase reductase (nifHs) were determined, with their copy numbers decreased gradually from inlet to outlet. Distribution of chemicals, bacteria and putative genes confirmed PCP dechlorination and phenol degradation accomplished in segments 0-5 cm and 0-8 cm, respectively, contributing to a high PCP mineralization rate of 3.86 μM d(-1). Through long-term incubation, dechlorination, phenol degradation and nitrogen fixation bacteria coexisted and functioned simultaneously near inlet (0-8 cm), verified the feasibility of anaerobic mineralization of halogenated aromatics in the compact reactor containing multiple functional microbes. PMID:26750760

  20. ABUNDANCE OF TRACE AND MINOR ELEMENTS IN ORGANIC AND MINERAL FRACTIONS OF COAL

    EPA Science Inventory

    The report gives results of subjecting 27 U.S. coals to float/sink, acid, and ion-exchange treatments. From these treatments, coal fractions were obtained and analyzed to determine the organic and mineral associations of 45 elements. Of the elements studied, B, Be, Br, Ge, and Sb...

  1. Minerals

    MedlinePlus

    ... Sledding, Skiing, Snowboarding, Skating Crushes What's a Booger? Minerals KidsHealth > For Kids > Minerals Print A A A Text Size What's in ... commercials for breakfast cereal always mention vitamins and minerals ? But when you think of minerals, food isn' ...

  2. Clay-mineral assemblages in Upper Cretaceous shales in the Torreon Wash and Star Lake coal areas, southeastern San Juan Basin, New Mexico. Open file report (final)

    SciTech Connect

    Bodine, M.W. Jr.

    1983-12-01

    This project was undertaken to characterize the mineralogy and chemical composition of clay mineral assemblages in Upper Cretaceous shales in the southeastern part of the San Juan Basin in northwestern New Mexico and to determine their relations with episodes of coal deposition. The shales represent a range of depositional environments from marine, through near-shore mixed marine and continental, into fluvial and aeolean continental. Coal accumulation in the Torreon Wash and Star Lake areas occurs in both mixed marine and continental and fluvial continental facies.

  3. Comparative 40Ar/39Ar and K-Ar dating of illite-type clay minerals: A tentative explanation for age identities and differences

    NASA Astrophysics Data System (ADS)

    Clauer, Norbert; Zwingmann, Horst; Liewig, Nicole; Wendling, Raymond

    2012-10-01

    The 40K/40Ar (K-Ar) and 40Ar/39Ar dating methods are applied here to the same, very small, micrometric illite-type particles that crystallized under low-temperature (< 175 °C) hydrothermal conditions in deeply buried Rotliegend (Permian) gas-bearing sandstones of NW Germany. Four samples with a total of fifteen size fractions from < 2 to 20-40 μm yield K-Ar ages that range from 166.0 ± 3.4 to 214.0 ± 5.9 Ma. The same size fractions dated by the 40Ar/39Ar method give total-gas ages ranging from 173.3 ± 2.0 to 228.8 ± 1.6 Ma. Nearly all 40Ar/39Ar total-gas ages are slightly older, which cannot be explained by the recoil effect only, the impact of which being amplified by the inhomogeneous shape of the clay minerals and their crystallographic characteristics, with varied crystallinity indices, and a particle width about 10 times large than thickness. The 40Ar/39Ar data outline some advantages, such as the plateaus obtained by incremental step heating of the various size fractions, even if not translatable straight as ages of the illite populations; they allow identification of two generations of authigenic illite that formed at about 200 and 175 Ma, and one detrital generation. However, 40Ar/39Ar dating of clay minerals remains challenging as technical factors, such as the non-standardized encapsulation, may have potential unexpected effects. Both dating methods have their limitations: (1) K-Ar dating requires relatively large samples (ca. 10-20 mg) incurring potential sample homogeneity problems, with two aliquots required for K and Ar analysis for an age determination, also inducing a higher analytical uncertainty; (2) an identified drawback of 40Ar/39Ar dating is Ar recoil and therefore potential loss that occurs during neutronic creation of 39Ar from 39K, mostly in the finer mineral particles. If all the recoiled 39Ar is redistributed into adjacent grains/minerals, the final 40Ar/39Ar age of the analyzed size fraction remains theoretically identical, but it is not systematic in clay-type material. The finest grain sizes (e.g., < 0.2 μm) are usually least contaminated with detrital components and can be dated by the K-Ar method without special preparation. Alternatively, such fine fractions are most susceptible to 39Ar recoil, and are, therefore, only datable by the 40Ar/39Ar method using an encapsulation technique that still needs to be technically evaluated. In this study, 39Ar recoil during irradiation was quantified by encapsulation; it ranged from about 20% of the total 39Ar for the < 0.2 μm fractions to ca. 10% for the 2-6 μm fractions. Basic interpolation of this 39Ar recoil confirms that grain size increasing minimizes the recoil effect, but how it proceeds has still to be explained. Despite recent developments in 40Ar/39Ar dating, the conventional K-Ar method is still a valuable tool for clay dating due to a convenient and straightforward use supported by a standardized and well-controlled technical approach. The present comparison of the two Ar-dating methods as applied to clay material shows that neither method is presently outdated, and that they are even of reciprocal use. Both methods have distinct application fields in clay geochronology and complementary application fields in clay crystallography.

  4. Mineral catalysis of the formation of the phosphodiester bond in aqueous solution: The possible role of montmorillonite clays

    NASA Astrophysics Data System (ADS)

    Ferris, James P.; Ertem, Gözen; Kamaluddin; Agarwal, Vipin; Hua, Lu Lin

    The binding of adenosine to Na+-montmorillonite 22A is greater than 5'-AMP, at neutral pH. Adenine derivatives bind more strongly to the clay than the corresponding uracil derivatives. These data are consistent with the protonation of the adenine by the acidic clay surface and a cationic binding of the protonated ring to the anionic clay surface. Other forces must be operative in the binding of uracil derivatives to the clay since the uracil ring system is not basic. The reaction of the 5'-AMP with water soluble carbodiimide in the presence of Na+-montmorillonite results in the formation of 2',5'-pApA (18.9%), 3',5'-pApA (11%), and AppA (4.8%). When poly(U) is used in place of the clay the product yields are 2',5',-pApA (15.5%), 3',5'-pApA (3.7%) and AppA (14.9%). The cyclic nucleotide, c(pA)2 is also formed when poly(U) is used. AppA is the principal reaction product when neither clay nor poly(U) is present in the reaction mixture. When 2'-deoxy-5'-AMP reacts with carbodiimide in the presence of Na+-montmorillonite 22A the products are dpApA (4.8%), dAppApA (4.5%) and dAppA (17.4%). Cyclic 3',5'-dAMP is the main product (14%) of the reaction of 2'-deoxy-3'-AMP.

  5. Common clay and shale

    USGS Publications Warehouse

    Virta, R.L.

    2003-01-01

    Part of the 2002 industrial minerals review. The production, consumption, and price of shale and common clay in the U.S. during 2002 are discussed. The impact of EPA regulations on brick and structural clay product manufacturers is also outlined.

  6. Abundance and diversity of total and nitrifying prokaryotes as influenced by biochemical quality of organic inputs combined with mineral nitrogen

    NASA Astrophysics Data System (ADS)

    Muema, Esther; Vanlauwe, Bernard; Röhl, Carolin; Cadisch, Georg; Rasche, Frank

    2014-05-01

    Ammonia-oxidizing bacteria and archaea (AOB, AOA) co-exist in soil, but they respond differently to distinct fertilization strategies in agricultural soils. Accordingly, effects of organic inputs and combination with mineral nitrogen (N) on AOB and AOA remain poorly understood. The aim of this study was to compare soil amendment with contrasting quality of organic inputs (i.e., high quality Tithonia diversifolia (TD; C/N ratio: 13, Lignin: 8.9 %; Polyphenols: 1.7 %), intermediate quality Calliandra calothyrsus (CC; 13; 13; 9.4) and low quality Zea mays (ZM; 59; 5.4; 1.2)), and combination with mineral N on the abundance (i.e., DNA-based gene quantification) and community structure (i.e., T-RFLP analysis) of total bacterial and archaea (16S rRNA gene), as well as AOB and AOA (targeting the amoA gene) communities in a Humic Nitisol. Soils (0-15 cm depth) were sampled prior to the onset of the rainy season in March 2012 in a 10 years old field experiment established in the central highlands of Kenya in 2002. Since the start of the experiment, organic inputs were applied annually at a rate of 4 Mg C ha-1 and mineral N twice a year as calcium ammonium nitrate (5Ca(NO3)2NH4NO3) at a rate of 120 kg N ha-1 growing season-1. Quality of organic inputs posed only a significant effect on the AOB community structure between TD versus ZM and CC versus ZM. Moreover, TD significantly increased the size of AOB over ZM input, while higher abundances for total bacteria, total archaea and AOA were measured in ZM and TD over CC. This was explained by high and available N in TD, but low lignin and polyphenol contents in TD and ZM as opposed to CC. AOB responded sensitively (i.e., complete community structure separation) to mineral N, specifically when combined with low quality ZM. Hence, AOB community was specifically responsive to quality of organic inputs and combination of low organic input with mineral N over AOA and total prokaryotic communities in the studied soil. The results presented were however, generated on one occasion soil sampling representing the effect of continuous organic and inorganic fertilizer application for ten years. We therefore recommend for prospective research, further investigations to rule out the temporal (short-term) variations of microbial decomposer dynamics at different crops growth stages during a cropping season as well as comparing different soil types.

  7. Mineral catalysis of the formation of the phosphodiester bond in aqueous solution - The possible role of montmorillonite clays

    NASA Technical Reports Server (NTRS)

    Ferris, James P.; Ertem, Gozen; KAMALUDDIN; Agarwal, Vipin; Hua, Lu Lin

    1989-01-01

    The possible role of montmorillonite clays in the spontaneous formation on the primitive earth of the phosphodiester bond in the presence of water was investigated in experiments measuring the binding of various nucleosides and nucleotides with Na(+)-montmorillonite 22A and the reactions of these compounds with a water-soluble carbodiimide. It was found that, at neutral pH, adenine derivatives bind stronger than the corresponding uracil derivatives, consistent with the protonation of the adenine by the acidic clay surface and a cationic binding of the protonated ring to the anionic clay surface. The reaction of the 5-prime-AMP with carbodiimide resulted in the formation of 2-prime,5-prime-pApA (18.9 percent), 3-prime,5-prime-pApA (11 percent), and AppA (4.8 percent). The yields of these oligomers obtained when poly(U) was used in place of the clay were 15.5 percent, 3.7 percent, and 14.9 percent AppA, respectively.

  8. Silica-clay nanocomposites.

    PubMed

    Letaief, Sadok; Ruiz-Hitzky, Eduardo

    2003-12-21

    A new class of porous nanocomposite materials have been prepared by reaction of alkoxysilanes with alkylammonium-exchanged phyllosilicates (clay minerals), using a sol-gel procedure which produces the complete delamination of these layered solids. PMID:14703825

  9. Common clay and shale

    USGS Publications Warehouse

    Virta, R.L.

    2004-01-01

    Part of the 2003 industrial minerals review. The legislation, production, and consumption of common clay and shale are discussed. The average prices of the material and outlook for the market are provided.

  10. Structure, dynamics, and function of the hammerhead ribozyme in bulk water and at a clay mineral surface from replica exchange molecular dynamics.

    PubMed

    Swadling, Jacob B; Wright, David W; Suter, James L; Coveney, Peter V

    2015-03-01

    Compared with proteins, the relationship between structure, dynamics, and function of RNA enzymes (known as ribozymes) is far less well understood, despite the fact that ribozymes are found in many organisms and are often conceived as "molecular fossils" of the first self-replicating molecules to have arisen on Earth. To investigate how ribozymal function is governed by structure and dynamics, we study the full hammerhead ribozyme in bulk water and in an aqueous clay mineral environment by computer simulation using replica-exchange molecular dynamics. Through extensive sampling of the major conformational states of the hammerhead ribozyme, we are able to show that the hammerhead manifests a free-energy landscape reminiscent of that which is well known in proteins, exhibiting a "funnel" topology that guides the ribozyme into its globally most stable conformation. The active-site geometry is found to be closely correlated to the tertiary structure of the ribozyme, thereby reconciling conflicts between previously proposed mechanisms for the self-scission of the hammerhead. The conformational analysis also accounts for the differences reported experimentally in the catalytic activity of the hammerhead ribozyme, which is reduced when interacting with clay minerals as compared with bulk water. PMID:25647546

  11. Natural abundance measurements of 13C indicate increased deep soil carbon mineralization after forest disturbance

    NASA Astrophysics Data System (ADS)

    Diochon, Amanda; Kellman, Lisa

    2008-07-01

    Northern forest soils represent globally important stores of carbon (C), yet there is no consensus about how they are altered by the widespread practice of harvesting that dominates many forested landscapes. Here we present the first study to systematically investigate the utility of δ 13C and C content depth profiles to infer temporal changes in belowground carbon cycling processes following disturbance in a pure C3 ecosystem. We document carbon concentration and δ 13C depth profile enrichment trends consistent with a kinetic fractionation arising from soil organic carbon (SOC) humification across a northern forest chronosequence (1, 15, 45, 80 and 125+ yrs). Reduced soil C storage that coincided with observed soil profile δ 13C-enrichment patterns which intensified following clearcut harvesting, pointed to losses of SOC in the deeper (>20 cm) mineral soil. This study suggests the δ 13C approach may assist in identifying mechanisms responsible for soil C storage changes in disturbed C3 forest ecosystems.

  12. Comment on "Evaluation of X-ray diffraction methods for determining the crystal growth mechanisms of clay minerals in mudstones, shales and slates," by L. N. Warr and D. R. Peacor

    USGS Publications Warehouse

    Eberl, D.D.; Srodon, J.; Drits, V.A.

    2003-01-01

    A recent paper by Warr and Peacor (2002) suggested that our use of the Bertaut-Warren-Averbach technique (MudMaster computer program) for studying changes in crystallite thickness distributions (CTDs) of clay minerals during diagenesis and very low-grade metamorphism is not reliable because it is dependent on many variables which can not be fully controlled. Furthermore, the authors implied that the measured shapes of CTDs cannot be used with confidence to deduce crystal growth mechanisms and histories for clays, based on our CTD simulation approach (using the Galoper computer program). We disagree with both points, and show that the techniques are powerful, reliable and useful for studying clay mineral alteration in rocks. ?? 2003 Schweiz. Mineral. Petrogr. Ges.

  13. Dioxin congener patterns in commercial catfish from the United States and the indication of mineral clays as the potential source.

    PubMed

    Huwe, J K; Archer, J C

    2013-01-01

    Since 1991 the US Department of Agriculture (USDA) has conducted annual surveys of pesticide residues in foods under the Agricultural Marketing Service's Pesticide Data Program (PDP). To assess chemical residues in domestically marketed catfish products, 1479 catfish samples were collected during the 2008-2010 PDPs. A subset of 202 samples was analysed for 17 toxic polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs). The average pattern of the individual PCDD/F congener concentrations in the catfish was rather unique in that it had almost no measurable amounts of polychlorinated dibenzofurans (PCDFs), but all PCDDs were present. This pattern was more dominant in the domestically produced catfish products than in the imported products (China/Taiwan). Comparison of the pattern to known sources of PCDD/Fs showed strong similarities to the pattern of PCDD/Fs found in kaolin clays which have often been used as anti-caking agents in animal feeds. To investigate whether catfish feeds may be the source of the PCDD/Fs found in the catfish, archived catfish feed data from a US Food and Drug Administration (USFDA) database were examined. In 61 out of 112 feed samples, the PCDD concentrations were 50 times higher than the PCDF concentrations and resembled the pattern found in the catfish products and in clays mined in the south-eastern United States. Although the source of PCDD/Fs in domestically marketed catfish products cannot be definitively established, mined clay products used in feeds should be considered a likely source and, given the wide concentration range of PCDD/Fs that has been found in clays, a critical control point for PCDD/Fs entrance to the food supply. PMID:23234292

  14. Prospecting for clay minerals within volcanic successions: Application of electrical resistivity tomography to characterise bentonite deposits in northern Sardinia (Italy)

    NASA Astrophysics Data System (ADS)

    Longo, V.; Testone, V.; Oggiano, G.; Testa, A.

    2014-12-01

    Electrical resistivity tomography (ERT) is applied to prospect for and characterise a bentonitic clay deposit in northern Sardinia. Sardinian bentonites derived from the hydrothermal alteration of thick successions of pyroclastic flows and epiclastites are associated with the Oligo-Miocene calc-alkaline volcanic cycle. The alteration of these rocks is generally controlled by faults that control the local circulation of hydrothermal fluids. Two-dimensional ERT investigations were performed close to a faulted area to define the location, thickness and lateral continuity of the clayey body, and determine how it relates to faulting and stratigraphy. A line-based three-dimensional ERT data acquisition was carried out in a selected area to estimate the available clay reserves. The reliability of these resistivity models was assessed by comparison with local borehole data. Finally, the interpretation of the ERT results was optimised through synthetic modelling of the electrical resistivity imaging technique. The results define the extent and geometry of the bentonitic deposit with good accuracy and outline the scenarios where the ERT method may provide optimal results when prospecting for clay deposits.

  15. Common clay and shale

    USGS Publications Warehouse

    Virta, R.L.

    2000-01-01

    Part of the 1999 Industrial Minerals Review. The clay and shale market in 1999 is reviewed. In the U.S., sales or use of clay and shale increased from 26.4 million st in 1998 to 27.3 million st in 1999, with an estimated 1999 value of production of $143 million. These materials were used to produce structural clay products, lightweight aggregates, cement, and ceramics and refractories. Production statistics for clays and shales and for their uses in 1999 are presented.

  16. Quantifying mineral abundances of complex mixtures by coupling spectral deconvolution of SWIR spectra (2.1-2.4 μm) and regression tree analysis

    USGS Publications Warehouse

    Mulder, V.L.; Plotze, Michael; de Bruin, Sytze; Schaepman, Michael E.; Mavris, C.; Kokaly, Raymond F.; Egli, Markus

    2013-01-01

    This paper presents a methodology for assessing mineral abundances of mixtures having more than two constituents using absorption features in the 2.1-2.4 μm wavelength region. In the first step, the absorption behaviour of mineral mixtures is parameterised by exponential Gaussian optimisation. Next, mineral abundances are predicted by regression tree analysis using these parameters as inputs. The approach is demonstrated on a range of prepared samples with known abundances of kaolinite, dioctahedral mica, smectite, calcite and quartz and on a set of field samples from Morocco. The latter contained varying quantities of other minerals, some of which did not have diagnostic absorption features in the 2.1-2.4 μm region. Cross validation showed that the prepared samples of kaolinite, dioctahedral mica, smectite and calcite were predicted with a root mean square error (RMSE) less than 9 wt.%. For the field samples, the RMSE was less than 8 wt.% for calcite, dioctahedral mica and kaolinite abundances. Smectite could not be well predicted, which was attributed to spectral variation of the cations within the dioctahedral layered smectites. Substitution of part of the quartz by chlorite at the prediction phase hardly affected the accuracy of the predicted mineral content; this suggests that the method is robust in handling the omission of minerals during the training phase. The degree of expression of absorption components was different between the field sample and the laboratory mixtures. This demonstrates that the method should be calibrated and trained on local samples. Our method allows the simultaneous quantification of more than two minerals within a complex mixture and thereby enhances the perspectives of spectral analysis for mineral abundances.

  17. Trace element abundance determinations by Synchrotron X Ray Fluorescence (SXRF) on returned comet nucleus mineral grains

    NASA Technical Reports Server (NTRS)

    Flynn, G. J.; Sutton, S. R.

    1989-01-01

    Trace element analyses were performed on bulk cosmic dust particles by Proton Induced X Ray Emission (PIXE) and Synchrotron X Ray Fluorescence (SXRF). When present at or near chondritic abundances the trace elements K, Ti, Cr, Mn, Cu, Zn, Ga, Ge, Se, and Br are presently detectable by SXRF in particles of 20 micron diameter. Improvements to the SXRF analysis facility at the National Synchrotron Light Source presently underway should increase the range of detectable elements and permit the analysis of smaller samples. In addition the Advanced Photon Source will be commissioned at Argonne National Laboratory in 1995. This 7 to 8 GeV positron storage ring, specifically designed for high-energy undulator and wiggler insertion devices, will be an ideal source for an x ray microprobe with one micron spatial resolution and better than 100 ppb elemental sensitivity for most elements. Thus trace element analysis of individual micron-sized grains should be possible by the time of the comet nucleus sample return mission.

  18. Fluid-rock interaction controlling clay-mineral crystallization in quartz-rich rocks and its influence on the seismicity of the Carboneras fault area (SE Spain)

    NASA Astrophysics Data System (ADS)

    Jimenez-Espinosa, R.; Abad, I.; Jimenez-Millan, J.; Lorite-Herrera, M.

    2009-04-01

    The Carboneras Fault zone is one of the longest fault in the Betic Cordillera (SE Spain) and it would be a good candidate to generate large magnitude earthquakes (Gracia et al., 2006). Seismicity in the region is characterised by low to moderate magnitude events, although large destructive earthquakes have occurred, which reveals significant earthquake and tsunami hazards (Masana et al., 2004). Due to the internal architecture of the fault zone, shear lenses of post-orogenic sediments of Miocene and Pliocene age including marls and sandstones sequences are juxtaposed to the predominant slaty gouges of the Alpine basement. Microcataclasites and gouges of the quartz-rich post-orogenic sediments are also developed as cm- to m-scale bands, allowing the comparison between the deformed materials and their protoliths. Red, yellow and white sandstones and their respective cataclasites can be identified. This communication is concerned with the clay mineral crystallization events in these materials and its possible influence on the seismicity model of the region. The presence of phyllosilicates in fault zones as either neoformed or inherited clays is commonly related with fluid circulation and a mechanically weak fault behaviour (e.g., Wang, 1984). A critical factor for the understanding of the mechanical role of clays in fault rocks is to determine the timing of formation of mineral assemblages and microstructure of fault rocks and protolith. The effects of post-faulting alteration limit inferences about fault behaviour that can be made from exhumed rocks. The Carboneras fault zone provides good opportunities to study mineral processes enhanced by deformation, given that it is located in a region of arid climate and shows outcroppings of quartzitic rocks included in slaty rocks. Combined XRD, optical microscopy and SEM analyses reveal that deformed quartzitic rocks are enriched in phyllosilicates, increasing especially the amount of chlorite. The samples strongly damaged are characterised also by the presence of dolomite and gypsum. The deformation is highly localized, developing phyllosilicate-rich bands highly foliated due to the presence of fine-sized aligned clays (chlorite and mica). In some undeformed lenses of the cataclastic rocks, variable-sized patches of phyllosilicates containing random oriented stacks of chlorite and mica are developed. BSE images reveal that the stacks are made of two intergrown compositional types of chlorite. These results lead to conclude that limited clay growth during faulting occurred. The absence of significant compositional differences between undeformed and deformed phyllosilicates suggests that whereas fluids were present during strike-slip faulting, fluids were not preferentially focused along the quartz-rich rocks of the fault zone by phyllosilicates avoiding the development of the synkinematic clay alteration process. However, clays played an important role for the mechanical behaviour of the quartzitic rocks in the fault zone. Deformation is highly localized in chlorite-rich sandstones. These sandstones show substantial clay crystallization which texture can be related with a hydrothermal origin before strike-slip faulting, likely associated with the volcanic activity of the area leading to form of chlorite/mica patches. These data indicate that, although elevated fluid pressure confined by clay fabric cannot be appealed for the mechanical behaviour of the sandstones of the Carboneras fault, clay fabrics developed during deformation dominated the fault-weakening mechanism. We consider that lubricating properties of phyllosilicates in the quartzitic rocks were an important factor controlling movement mechanisms promoting the predominance of creep as regards seismic stick-slip (Bedrosian et al., 2004) reducing the possibility of larger seismogenic events that nucleate on localized fault planes developed within quartzitic rocks contained within the fault zone. Finally the crystallization of dolomite and gypsum in the highly damaged areas of the microcataclasites could be related with recent low-temperature and high-salinity water circulation episodes, suggesting that cataclasis may control pathways and focus circulation of the current aquifer systems. References Bedrosian, P.A., Unsworth, M.J., Egbert, G.D., Thuerber, C.H. (2004): Geophysical images of creeping segment of the San Andreas Fault: Implications for the role of crustal fluids in the earthquake process. Tectonophysics, 385, 137-158. Gracia, E., Palla, R., Soto, J.I., Comas, M., Moreno, X., Masana, E., Santanach, P., Diez, S., García, M., Dañobeitia, J. & HITS scientific party (2006): Active faulting offshore SE Spain (Alboran Sea): Implications for earthquake hazard assessment in the Southern Iberian Margin. Earth and Planetary Science Letters, 241, 734-749. Masana E., Martínez-Díaz, J.J., Hernández-Enrile, J.L. & Santanach, P. (2004): The Alhama de Murcia fault (SE Spain), a seismogenic fault in a diffuse plate boundary: seismotectonic implications for the Ibero-Magrebian region. J. Geophys. Res., 109, 1-17. Wang, C.Y. (1984): On the constitution of the San Andreas fault zone in central California. J. Geophys. Res., 89, 5858-5866.

  19. Modeling near-infrared reflectance spectra of clay and sulfate mixtures and implications for Mars

    NASA Astrophysics Data System (ADS)

    Stack, K. M.; Milliken, R. E.

    2015-04-01

    High-resolution mapping by visible and near-infrared orbital spectrometers has revealed a diversity of hydrated mineral deposits on the surface of Mars. Quantitative analysis of mineral abundances within these deposits has the potential to distinguish depositional and diagenetic processes. Such analysis can also provide important constraints on the nature of putative global and local-scale mineralogical transitions on Mars. However, the ability of models to extract quantitative mineral abundances from spectra of mixtures relevant to sedimentary rocks remains largely untested. This is particularly true for clay and sulfate minerals, which often occur as fine-grained components of terrestrial sedimentary rocks and are known to occur in a number of sedimentary deposits on Mars. This study examines the spectral properties of a suite of mixtures containing the Mg-sulfate epsomite mixed with varying proportions of smectitic clay (saponite, nontronite, and montmorrilonite). The goal of this work is to test the ability of checkerboard (linear) and intimate (non-linear) mixing models to obtain accurate estimates of mineral abundances under ideal and controlled laboratory conditions. The results of this work suggest that: (1) spectra of clay-sulfate mixtures can be reproduced by checkerboard and intimate mixing models to within 2% absolute reflectance or single scattering albedo, (2) clay and epsomite abundance can be modeled to within 5 wt.% when particle diameter is optimized, and (3) the lower threshold for modeling clay in spectra of clay-epsomite mixtures is approximately 10 wt.%, below which the models often fail to recognize the presence of clay.

  20. TEM/AEM characterization of fine-grained clay minerals in very-low-grade rocks: Evaluation of contamination by EMPA involving celadonite family minerals

    SciTech Connect

    Li, Gejing; Peacor, D.R.; Coombs, D.S.; Kawachi, Y.

    1996-12-31

    Recent advances in transmission electron microscopy (TEM) and analytical electron microscopy (AEM) have led to many new insights into the structural and chemical characteristics of very fine-grained, optically homogeneous mineral aggregates in sedimentary and very low-grade metamorphic rocks. Chemical compositions obtained by electron microprobe analysis (EMPA) on such materials have been shown by TEM/AEM to result from beam overlap on contaminant phases on a scale below resolution of EMPA, which in turn can lead to errors in interpretation and determination of formation conditions. Here we present an in-depth analysis of the relation between AEM and EMPA data, which leads also to the definition of new mineral phases, and demonstrate the resolution power of AEM relative to EMPA in investigations of very fine-grained mineral aggregates in sedimentary and very low-grade metamorphic rocks.

  1. Mycotoxins modify the barrier function of Caco-2 cells through differential gene expression of specific claudin isoforms: Protective effect of illite mineral clay.

    PubMed

    Romero, Alejandro; Ares, Irma; Ramos, Eva; Castellano, Víctor; Martínez, Marta; Martínez-Larrañaga, María-Rosa; Anadón, Arturo; Martínez, María-Aránzazu

    2016-04-15

    Aflatoxin B1 (AFB1), fumonisin B1 (FB1), ochratoxin A (OTA) and T-2 toxin (T2) are mycotoxins that commonly contaminate the food chain and cause various toxicological effects. Their global occurrence is regarded as an important risk factor for human and animal health. In this study, the results demonstrate that, in human Caco-2 cells, AFB1, FB1, OTA and T2 origin cytotoxic effects, determining cell viability through MTT assay and LDH leakage, and decrease trans-epithelial electrical resistance (TEER). The decrease in barrier properties is concomitant with a reduction in the expression levels of the tight junction constituents claudin-3, claudin-4 and occludin. The protective effect of mineral clays (diosmectite, montmorillonite and illite) on alterations in cell viability and epithelial barrier function induced by the mycotoxins was also evaluated. Illite was the best clay to prevent the mycotoxin effects. Illite plus mycotoxin co-treatment completely abolished AFB1 and FB1-induced cytotoxicity. Also, the decreases in the gene expression of claudins and the reduction of TEER induced by mycotoxins were reversed by the illite plus mycotoxin co-treatment. In conclusion, these results demonstrated that mycotoxins AFB1, FB1, T2 and OTA disrupt the intestinal barrier permeability by a mechanism involving reduction of claudin isoform expressions, and illite counteracts this disruption. PMID:27153755

  2. Arsenic mineralization, source, distribution, and abundance in the Kutahya region of the western Anatolia, Turkey.

    PubMed

    Dogan, Meral; Dogan, A Umran

    2007-04-01

    Environmental exposure to arsenic (As) in the Kutahya region of the western Anatolia, Turkey has been reported to cause various types of arsenic-associated skin disorders (Dogan, Dogan, Celebi, & Baris, 2005). A geological and mineralogical study was conducted to find the sources and distribution of the As. Geogenic (background) levels were measured in samples collected from various sources in the Gediz, Simav, Tavsanli, Emet, Yoncali, Yenicekoy, and Muratdagi areas of the Kutahya region. Based on this analysis, we determined that natural sources are a domineering factor affecting the distribution of As, which was found: (1) mainly in evaporitic minerals, including colemanite (269-3900 ppm) and gypsum (11-99,999 ppm), but also in alunite (7-10 ppm) and chert (54-219 ppm); (2) in secondary epithermal gypsum, which has a high concentration of As in the form of realgar and orpiment along fracture zones of Mesozoic and Cenozoic carbonate aquifers; (3) in rocks, including limestone/dolomite (3-699 ppm) and travertine (5-4736 ppm), which are relatively more enriched in As than volcanics (2-14 ppm), probably because of secondary enrichment through hydrological systems; (4) in coal (1.9-46.5 ppm) in the sedimentary successions of the Tertiary basins; (5) in thermal waters, where As is unevenly distributed at concentrations varying from 0.0-0.9 mg/l. The highest As concentrations in thermal water (Gediz and Simav) correlate to the higher pH (7-9.3) and T (60-83 degrees C) conditions and to the type of water (Na-HCO3-SO4 with high concentration of Ca, Mg, K, SiO2, and Cl in the water). Changes in pH can be related to some redox reactions, such as the cation exchange reactions driving the dissolution of carbonates and silicates. Fe-oxidation, high pH values (7-9.3), presence of other trace metals (Ni, Co, Pb, Zn, Al), increased salinity (Na, Cl), high B, Li, F, and SiO, high Fe, SO4 (magnetite, specularite-hematite, gypsum), and graphite, and the presence of U, Fe, Cu, Pb, Zn, and B, especially in the Emet, Gediz, and Simav areas, are the typical indicators for the geothermally affected water with high As content. A sixth source of As in this region is the ground (0.0-10.7 mg/l) and the surface waters (0.0022-0.01 mg/l), which are controlled by water-rock interaction, fracture system, and mixing/dilution of thermal waters. The high As concentration in groundwater corresponds to the areas where pathological changes are greatest in the habitants. Arsenic in ground water also effects ecology. For example, only Juriperus oxycedrus and J. varioxycedrus types of vegetation are observed in locations with the highest concentration of As in the region. Branches and roots of these plants are enriched in As. PMID:17288006

  3. Ball clay

    USGS Publications Warehouse

    Virta, Robert L.

    2010-01-01

    The article reports on the global market performance of ball clay in 2009 and presents an outlook for its 2010 performance. Several companies mined ball call in the country including Old Hickey Clay Co., Kentucky-Tennessee Clay Co., and H.C. Spinks Clay Co. Information on the decline in ball clay imports and exports is also presented.

  4. Comparison of the sorption behaviors and mechanisms of perfluorosulfonates and perfluorocarboxylic acids on three kinds of clay minerals.

    PubMed

    Zhao, Lixia; Bian, Jingna; Zhang, Yahui; Zhu, Lingyan; Liu, Zhengtao

    2014-11-01

    The sorption of four perfluoroalkyl acids (PFAAs) [perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), perfluorooctanoic acid (PFOA) and perfluorohexanoic acid (PFHxA)] on three typical minerals [montmorillonite (MM), kaolinite (KL) and hematite (HM)] was studied. The sorption of PFOS and PFHxS was much stronger than PFOA and PFHxA. The sorption of each PFAA on the minerals followed an order of HM>KL>MM, even though MM was positively while KL and HM were negatively charged, implying that the sorption is driven by some other interactions besides electrostatic attraction. The sorption decreased with an increase in pH and a decrease in ionic strength of the solution, and their impacts on PFOS were much stronger than other three PFAAs. Surface complexing and hydrogen-bonding could make great contributions to the sorption of PFOS on the minerals. The results are important for understanding the transport and fate of PFAAs in sediment and ground water. PMID:25113183

  5. Minerals

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Fish require the same minerals or inorganic elements as terrestrial animals for tissue formation, osmoregulation and various metabolic functions. Those required in large quantities are termed macro- or major minerals and those required in small quantities are called micro- or trace minerals. Fish ca...

  6. Clay mineral analysis of the Hirabayashi NIED drill core on the Nojima fault that ruptured in the 1995 Kobe Earthquake, southwest Japan

    NASA Astrophysics Data System (ADS)

    Matsuda, T.; Omura, K.; Ikeda, R.; Awaji, D.

    2002-12-01

    A 1800-m-deep borehole was drilled at Nojima Hirabayashi and penetrated the Nojima fault that was activated at the time of the 1995 Hyogo-ken Nanbu Earthquake (Kobe Earthquake) in Japan. Three possible fracture zones were detected at depths of about 1140 m, 1300 m, and 1800 m. At first, we analyzed the mode of distribution of rocks, minerals and chemical elements in them. There is a foliated blue-gray gouge at a depth of 1140 m. So we infer that this is the central fault plane, and began our fracture zone analysis there, as follows. The degree of fracturing is evidently greater in the hanging wall than in the footwall. We estimated the relative amounts of minerals qualitatively, and we detected not only quartz, orthoclase, plagioclase, biotite and hornblende in the parent rock (granodiorite), but also kaolinite, smectite, laumontite, stilbite, calcite, ankerite and siderite, which are related to hydrothermal alteration. Biotite notably disappears in both the hanging wall and footwall across the central fault plane, although it disappears over a significantly greater distance in the hanging wall than in the footwall. Equally, we estimated the amounts of major chemical elements quantitatively. Al2O3, Fe2O3, MnO, TiO2, and P2O5 all decrease throughout this interval, except at a few points. H2O_{ and CO2 increase throughout the interval. Na2O increases in the region adjacent to the central fault plane, while MgO and CaO increase in the hanging wall and decrease in the footwall. SiO2 and K2O decrease in the hanging wall and increase in the footwall. Next, we particularly investigated about the clay minerals such as smectite. From the drill core, we separated the clay-size fraction and analyzed it by X-Ray Diffractometer (XRD). Incidentally, particle-size separations are based on Stokes_fs law. We prepared oriented samples for XRD and to make it, we used the glass slide method. We measured it both in the air-dried and ethylene glycol-solvated conditions. We analyzed the other fracture zones along this fault in the same way. As a result, about the mode of distribution of rocks minerals and chemical elements, the fracture zone at 1140 m depth is very similar to the fracture zone at 1800 m depth and differs significantly from the fracture zone at 1300 m depth. But, the results of the clay minerals are different among each fracture zone. In air-dried condition, d (001) of smectite are 15 angstrom (at 1140 m depth), 14 angstrom (at 1300 m depth), 14~12 angstrom (at 1800 m depth), respectively (In ethylene glycol-solvated conditions, they are all 17 angstrom). It may suggest the existence of different fluid circulation between shallower and deeper fracture zones.

  7. Infrared spectroscopic studies of the effect of elevated temperature on the association of pyroglutamic acid with clay and other minerals

    NASA Technical Reports Server (NTRS)

    Macklin, J. W.; White, D. H.

    1985-01-01

    Fourier transform i.r. measurements of L-pyroglutamic acid dispersed in a matrix of a clay, silica or alumina have been obtained at various temperatures between 25 and 220 degrees C. The i.r. spectrum of L-pyroglutamic acid varies in a manner dependent upon the matrix material and shows considerable change as the temperature of the mixtures is increased. The differences in the spectrum at elevated temperatures are explained in terms of a chemical reaction between hydroxyl groups in the matrix and the carboxylic acid. The i.r. spectra of trimethylsilyl derivatives of L-pyroglutamic acid and aluminum pyroglutamate were also measured to assist the understanding of spectra and interpretation of the spectral changes dependent upon increasing temperature.

  8. Simulation of Clay Mineral Dehydration Along the NanTroSEIZE Transect, SW Japan: Implications for Fault Properties and Fluid Flow

    NASA Astrophysics Data System (ADS)

    Saffer, D. M.; Harris, R. N.; Underwood, M.

    2012-12-01

    At subduction zones, fluids are expelled as porous sediments on the incoming oceanic plate are either subducted or offscraped and accreted. In the upper ~8-10 km, the dominant sources of fluid are tectonically-driven compaction and burial, and the dehydration of hydrous (smectite family) clays. Potentially elevated pore fluid pressure associated with fluid release has been invoked to explain: (1) zones of anomalously low seismic velocity in the outer forearc (LVZ's) located ~13-30 km and ~31-55 km from the trench; (2) high amplitude negative polarity seismic reflectors along major fault zones; and (3) a transition to unstable fault slip. Here, we incorporate the results of existing thermal modeling and Integrated Ocean Drilling Program (IODP) drilling along the NanTroSEIZE transect, offshore SW Japan, to simulate the magnitude and distribution of fluid release from clay dehydration in 2-D. The thermal models define the temperature structure of the margin, and the drilling results provide constraints on the abundance of hydrous clays in the sediment inputs. The regionally averaged wedge geometry and incoming sediment thickness used in our model are defined from seismic reflection data. We simulate smectite transformation by tracking sediments as they are progressively buried and heated in the subduction complex. The reaction progress is then computed from temperatures and exposure time. We evaluate two thermal models: a "hot" scenario, which is consistent with surface heat flow data, and a "cold" scenario that provides a probable lower bound on subsurface temperatures. For our initial suite of simulations, we consider an average bulk smectite abundance of 45 wt%. We then explore the spatial relationships between the locus of clay dehydration and geophysical signatures interpreted to reflect pore fluid and dehydration processes. Finally, we track the evolution of residual pore fluid chemistry due to consolidation and introduction of fresh water from the dehydration reaction. Simulated peak clay dehydration occurs 8-10 km landward of the trench in the hot scenario, and ~17-20 km landward in the cold scenario, well updip of the high reflectivity fault zones and LVZ's. Within the underthrusting sediments, the simulated reaction is 80% complete by ~15 km and ~25 km landward of the trench for the hot and cold scenarios, respectively. Our results indicate that that the geophysical observations do not map the locus of dehydration. We suggest that compaction disequilibrium is a more plausible explanation for both the high reflectivity and LVZ's. Simulated pore water freshening in the upper wedge is negligible in the outer 26 km of the forearc, and reaches a maximum of ~17% by 75 km landward of the trench. In contrast, simulated pore water freshening in the lower wedge and underthrust sediment begins within ~5-8 km of the trench, and reaches ~65% by 30 km landward. Near the trench, deeply sourced fluids will be diluted by mixing with fluids from the hanging wall. Progressive freshening of the deeply sourced fluids, in combination with decreasing compactive sources in the wedge, should lead to less mixing and thus larger signals of deeply sourced fluid flow farther landward.

  9. Ball clay

    USGS Publications Warehouse

    Virta, R.L.

    2006-01-01

    In 2005, four companies including H.C. Spinks Clay, Kentucky-Tennessee Clay, Old Hickory Clay and Unimin mined ball clay in four states. Based on a preliminary survey of the ball clay industry, production reached 1.32 Mt valued at $53.3 million. Tennessee was the leading ball clay producer state with 61% of domestic production, followed by Texas, Mississippi and Kentucky.

  10. Modelling of the physico-chemical behaviour of clay minerals with a thermo-kinetic model taking into account particles morphology in compacted material.

    NASA Astrophysics Data System (ADS)

    Sali, D.; Fritz, B.; Clément, C.; Michau, N.

    2003-04-01

    Modelling of fluid-mineral interactions is largely used in Earth Sciences studies to better understand the involved physicochemical processes and their long-term effect on the materials behaviour. Numerical models simplify the processes but try to preserve their main characteristics. Therefore the modelling results strongly depend on the data quality describing initial physicochemical conditions for rock materials, fluids and gases, and on the realistic way of processes representations. The current geo-chemical models do not well take into account rock porosity and permeability and the particle morphology of clay minerals. In compacted materials like those considered as barriers in waste repositories, low permeability rocks like mudstones or compacted powders will be used : they contain mainly fine particles and the geochemical models used for predicting their interactions with fluids tend to misjudge their surface areas, which are fundamental parameters in kinetic modelling. The purpose of this study was to improve how to take into account the particles morphology in the thermo-kinetic code KINDIS and the reactive transport code KIRMAT. A new function was integrated in these codes, considering the reaction surface area as a volume depending parameter and the calculated evolution of the mass balance in the system was coupled with the evolution of reactive surface areas. We made application exercises for numerical validation of these new versions of the codes and the results were compared with those of the pre-existing thermo-kinetic code KINDIS. Several points are highlighted. Taking into account reactive surface area evolution during simulation modifies the predicted mass transfers related to fluid-minerals interactions. Different secondary mineral phases are also observed during modelling. The evolution of the reactive surface parameter helps to solve the competition effects between different phases present in the system which are all able to fix the chemical elements mobilised by the water-minerals interaction processes. To validate our model we simulated the compacted bentonite (MX80) studied for engineered barriers for radioactive waste confinement and mainly composed of Na-Ca-montmorillonite. The study of particles morphology and reactive surfaces evolutions reveals that aqueous ions have a complex behaviour, especially when competitions between various mineral phases occur. In that case, our model predicts a preferential precipitation of finest particles, favouring smectites instead of zeolites. This work is a part of a PhD Thesis supported by Andra, the French Radioactive Waste Management Agency.

  11. Amplification of plasmid DNA bound on soil colloidal particles and clay minerals by the polymerase chain reaction.

    PubMed

    Cai, Peng; Huang, Qiao-yun; Lu, Yan-du; Chen, Wen-li; Jiang, Dai-hua; Liang, Wei

    2007-01-01

    Polymerase chain reaction (PCR) was used to amplify a 600-base pair (bp) sequence of plasmid pGEX-2T DNA bound on soil colloidal particles from Brown soil (Alfisol) and Red soil (Ultisol), and three different minerals (goethite, kaolinite, montmorillonite). DNA bound on soil colloids, kaolinite, and montmorillonite was not amplified when the complexes were used directly but amplification occurred when the soil colloid or kaolinite-DNA complex was diluted, 10- and 20-fold. The montmorillonite-DNA complex required at least 100-fold dilution before amplification could be detected. DNA bound on goethite was amplified irrespective of whether the complex was used directly, or diluted 10- and 20-fold. The amplification of mineral-bound plasmid DNA by PCR is, therefore, markedly influenced by the type and concentration of minerals used. This information is of fundamental importance to soil molecular microbial ecology with particular reference to monitoring the fate of genetically engineered microorganisms and their recombinant DNA in soil environments. PMID:18232226

  12. Microtektites and Associated Minerals in the Iridium-Rich Layer of Marine Clay From the Central North Pacific Ocean

    NASA Astrophysics Data System (ADS)

    Leung, I. S.

    2014-12-01

    Our study is based on a sample derived from a deep sea core (GPC3) from the mid-Pacific Ocean floor north of the Hawaiian Islands, provided by Jim Broda, Woods Hole Oceanographic Institution. The 65 Ma K/T boundary layer was identified by measurements of magnetic susceptibility (Doh, 1987) and Ir anomaly (Kyte et al., 1995) which peaked at a down-hole depth of 2055-2056 cm. Our sample of red clay was about 5 cubic cm in size. After wet-sieving for the size fraction greater than 38 microns, we hand-picked grains of interest under a binocular microscope. We found 40 microtektites (glass spherules, mostly devitrified), 12 olive-green aggregates composed of talc/magnetite, and 3 green and blue crystals of silicon carbide (SiC). There are many quartz grains having decorated deformation lamellae or mosaic structures. The olive-green talc/magnetite particles have textures and composition similar to materials found in chondritic meteorites, whereas, SiC crystals are known to occur in carbonaceous chondrites. These particles seem to implicate an affinity to meteorites. Ir-rich deposits world-wide are believed to have settled from dust produced by the Chicxulub Impact, but what object from space created the impact crater is rather uncertain. Our results reported here cannot rule out the possiblilty of impact by comets, because the nature of cometary dust particles are not very well known.

  13. U, Th, Pb and REE abundances and Pb 207/Pb 206 ages of individual minerals in returned lunar material by ion microprobe mass analysis.

    NASA Technical Reports Server (NTRS)

    Andersen, C. A.; Hinthorne, J. R.

    1972-01-01

    Results of ion microprobe analyses of Apollo 11, 12 and 14 material, showing that U, Th, Pb and REE are concentrated in accessory minerals such as apatite, whitlockite, zircon, baddeleyite, zirkelite, and tranquillityite. Th/U ratios are found to vary by over a factor of 40 in these minerals. K, Ba, Rb and Sr have been localized in a K rich, U and Th poor glass phase that is commonly associated with the U and Th bearing accessory minerals. Li is observed to be fairly evenly distributed between the various accessory phases. The phosphates have been found to have REE abundance patterns (normalized to the chondrite abundances) that are fairly flat, while the Zr bearing minerals have patterns that rise steeply, by factors of ten or more, from La to Gd. All the accessory minerals have large negative Eu anomalies. Radiometric age dates (Pb 207/Pb 206) of the individual U and Th bearing minerals compare favorably with the Pb 207/Pb 206 age of the bulk rocks.

  14. Clays as prebiotic photocatalysts

    NASA Technical Reports Server (NTRS)

    Coyne, L. M.; Lawless, J.; Lahav, N.; Sutton, S.; Sweeney, M.

    1981-01-01

    Clay minerals catalyze peptide bond formation in fluctuating environments. A number of plausible mechanisms have been proposed and tested. The possibility that clays may actually be energizing the reaction by means of electronic excitation, creating mobile or trapped holes and electrons in the lattice, is explored. It has been discovered that clays emit light upon dehydration. The correlation between dehydration-induced, or thermoluminescent, processes and the yield of glycine oligomers after treatments known to affect the luminescent yields is being tested, in an effort to understand the catalytic mechanism

  15. Clay Play

    ERIC Educational Resources Information Center

    Rogers, Liz; Steffan, Dana

    2009-01-01

    This article describes how to use clay as a potential material for young children to explore. As teachers, the authors find that their dialogue about the potential of clay as a learning medium raises many questions: (1) What makes clay so enticing? (2) Why are teachers noticing different play and conversation around the clay table as compared to…

  16. Early diagenesis and clay mineral adsorption as driving factors of metal pollution in sediments: the case of Aveiro Lagoon (Portugal).

    PubMed

    Martins, Maria Virgínia Alves; Mane, Miguel Ângelo; Frontalini, Fabrizio; Santos, José Francisco; da Silva, Frederico Sobrinho; Terroso, Denise; Miranda, Paulo; Figueira, Rubens; Laut, Lazaro Luiz Mattos; Bernardes, Cristina; Filho, João Graciano Mendonça; Coccioni, Rodolfo; Dias, João M Alveirinho; Rocha, Fernando

    2015-07-01

    This work aims to define the factors driving the accumulation of metals in the sediment of the lagoon of Aveiro (Portugal). The role of initial diagenetic processes in controlling trace metal retention in surface sediment is traced by mineralogy, magnetic susceptibility and geochemical analyses. Although several studies have focused on the metal distribution in this polihaline and anthropized coastal lagoon, most of them have been solely focused on the total metal concentrations. This study instead represents the first attempt to evaluate in a vast area of the Aveiro Lagoon the role of biogeochemical processes in metal availability and distribution in three extracted phases: exchangeable cations adsorbed by clay and elements co-precipitated with carbonates (S1), organic matter (S2) and amorphous Mn hydroxides (S3). According to the sediment guideline values, the sediment is polluted by, for instance, As and Hg in the inner area of the Murtosa Channel, Pb in the Espinheiro Channel, Aveiro City canals and Aveiro Harbour, and Zn in the northern area of the Ovar Channel. These sites are located near the source areas of pollutants and have the highest total available concentrations in each extracted phase. The total available concentrations of all toxic metals are however associated, firstly, with the production of amorphous Mn hydroxides in most of the areas and, secondly, with adsorption by organic compounds. The interplay of the different processes implies that not all of the sites near pollution sources have polluted surface sediment. The accumulation of metals depends on not only the pollution source but also the changing in the redox state of the sediments that may cause alterations in the sediment retention or releasing of redox-sensitive metals. Results of this work suggest that the biogeochemical processes may play a significant role in the increase of the pollutants in the sediment of the Aveiro Lagoon. PMID:25666475

  17. Ball clay

    USGS Publications Warehouse

    Virta, R.L.

    2011-01-01

    The article discusses the latest developments in the global ball clay mining industry, particularly in the U.S., as of June 2011. It cites several firms that are involved in ball clay mining in the U.S., including HC Spins Clay Co. Inc., the Imerys Group and Old Hickory Clay Co. Among the products made from ball clay are ceramic tiles, sanitaryware, as well as fillers, extenders and binders.

  18. Kaoping River - Sea sediments from source to sink traced with clay mineralogy

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Fan, D.; Liu, J. T.; Chang, Y. P.

    2014-12-01

    River bed sediments were collected from the main stream and major tributaries of the Kaoping River in Taiwan for clay mineralogy study. Marine sediments from boreholes on the seafloor off Taiwan in the northeastern South China Sea were also examined for comparison. The results show that the clay mineral composition of the Kaoping River display a similar pattern through the whole truck steam, with illite being dominant, chlorite being lesser abundant, and very scare kaolinite and smectite. Clay mineralogy shows some differences, like Smectite only examined in Qishan lake, one of the upper tributaries, which corresponed to the heterogeneous source rocks. The illite crystallity and the illite chemical weathering index both show rapid mechanical denudation. Compared with the other famous rivers in the world, clay mineral composition of sediments is influenced by the source and weathering based on the different gradients and environment. The data from marine sediments does not show obvious basin-wide differences, reflecting a distinct character of Taiwan source.

  19. Sorption of N2 and EGME vapors on some soils, clays, and mineral oxides and determination of sample surface areas by use of sorption data

    USGS Publications Warehouse

    Chiou, C.T.; Rutherford, D.W.; Manes, M.

    1993-01-01

    Vapor sorption isotherms of ethylene glycol monoethyl ether (EGME) at room temperature and isotherms of N2 gas at liquid nitrogen temperature were determined for various soils and minerals. The N2 monolayer capacities [Qm (N2)] were calculated from the BET equation and used to determine the surface areas. To examine whether EGME is an appropriate adsorbate for determination of surface areas, the apparent EGME monolayer capacities [Qm (EGME)ap] were also obtained by use of the BET equation. For sand, aluminum oxide, kaolinite, hematite, and synthetic hydrous iron oxide, which are relatively free of organic impurity and expanding/solvating minerals, the Qm (EGME)ap values are in good conformity with the corresponding Qm (N2) values and would give surface areas consistent with BET (N2) values. For other samples (Woodburn soil, a natural hydrous iron oxide, illite, and montmorillonite), the Qm (EGME)ap values overestimate the Qm (N2) values from a moderate to a large extent, depending on the sample. A high-organic-content peat shows a very small BET (N2) surface area; the EGME/ peat isotherm is linear and does not yield a calculation of the surface area. Large discrepancies between results of the two methods for some samples are attributed to the high solubility of polar EGME in soil organic matter and/ or to the cation solvation of EGME with solvating clays. The agreement for other samples is illustrative of the consistency of the BET method when different adsorbates are used, so long as they do not exhibit bulk penetration and/or cation solvation. ?? 1993 American Chemical Society.

  20. In situ optical measurements of Chang'E-3 landing site in Mare Imbrium: 1. Mineral abundances inferred from spectral reflectance

    NASA Astrophysics Data System (ADS)

    Zhang, Hao; Yang, Yazhou; Yuan, Ye; Jin, Weidong; Lucey, Paul G.; Zhu, Meng-Hua; Kaydash, Vadim G.; Shkuratov, Yuriy G.; Di, Kaichang; Wan, Wenhui; Xu, Bin; Xiao, Long; Wang, Ziwei; Xue, Bin

    2015-09-01

    The visible and near-infrared imaging spectrometer on board the Yutu Rover of Chinese Chang'E-3 mission measured the lunar surface reflectance at a close distance (~1 m) and collected four spectra at four different sites. These in situ lunar spectra have revealed less mature features than that measured remotely by spaceborne sensors such as the Moon Mineralogy Mapper instrument on board the Chandrayaan-1 mission and the Spectral Profiler on board the Kaguya over the same region. Mineral composition analysis using a spectral lookup table populated with a radiative transfer mixing model has shown that the regolith at the landing site contains high abundance of olivine. The mineral abundance results are consistent with that inferred from the compound measurement made by the on board alpha-particle X-ray spectrometer.

  1. Radiocesium sorption in relation to clay mineralogy of paddy soils in Fukushima, Japan.

    PubMed

    Nakao, Atsushi; Ogasawara, Sho; Sano, Oki; Ito, Toyoaki; Yanai, Junta

    2014-01-15

    Relationships between Radiocesium Interception Potential (RIP) and mineralogical characteristics of the clay fraction isolated from 97 paddy soils (Hama-dori, n = 25; Naka-dori, n = 36; Aizu, n = 36) in Fukushima Prefecture, Japan were investigated to clarify the mineralogical factors controlling the (137)Cs retention ability of soils (half-life 30.1 y). Of all the fission products released by the Fukushima accident, (137)Cs is the most important long-term contributor to the environmental contamination. The RIP, a quantitative index of the (137)Cs retention ability, was determined for the soil clays. The composition of clay minerals in the soil clays was estimated from peak areas obtained using X-ray diffraction (XRD) analyses. The predominant clay mineral was smectite in soils from Hama-dori and Aizu, while this was variable for those from Naka-dori. Native K content of the soil clays was found to be an indicator of the amount of micaceous minerals. The average RIP for the 97 soil clays was 7.8 mol kg(-1), and ranged from 2.4 mol kg(-1) to 19.4 mol kg(-1). The RIP was significantly and positively correlated with native K content for each of the geographical regions, Hama-dori (r = 0.76, p < 0.001), Naka-dori (r = 0.43, p < 0.05), and Aizu (r = 0.76, P < 0.001), while it was not related to the relative abundance of smectite. The linear relationship between RIP and native K content not only indicate a large contribution of micaceous minerals to the (137)Cs retention ability of the soil clays, but also could be used to predict the (137)Cs retention ability of soil clays for other paddy fields in Fukushima and other areas. PMID:24055668

  2. Ball clay

    USGS Publications Warehouse

    Virta, R.L.

    2013-01-01

    Four companies — H.C. Spinks Clay Co., Inc., Imerys, Old Hickory Clay Co. and Unimin Corp. — mined ball clay in five U.S. states in 2012. Production, on the basis of preliminary data, was 900 kt (992,000 st), with an estimated value of $42.3 million. This was a slight increase in tonnage from 886 kt (977,000 st), with a value of $40.9 million in 2011. Tennessee was the leading ball clay producing state, with 63 percent of domestic production, followed by Texas, Mississippi, Kentucky and Indiana. Reported ball clay production from Indiana probably was fire clay rather than ball clay. About 69 percent of total ball clay production was airfloat, 20 percent was crude and 11 percent was water-slurried.

  3. Fire clay

    USGS Publications Warehouse

    Virta, R.L.

    2011-01-01

    The article discusses the latest developments in the fire clay industry, particularly in the U.S., as of June 2011. It claims that the leading fire clay producer in the U.S. is the state of Missouri. The other major producers include California, Texas and Washington. It reports that the use of heavy clay products made of fire clay like brick, cement and lightweight aggregate has increased slightly in 2010.

  4. Clay Houses

    ERIC Educational Resources Information Center

    Pedro, Cathy

    2011-01-01

    In this article, the author describes a project designed for fourth-graders that involves making clay relief sculptures of houses. Knowing the clay houses will become a family heirloom makes this lesson even more worth the time. It takes three classes to plan and form the clay, and another two to underglaze and glaze the final products.

  5. Common clay and shale

    USGS Publications Warehouse

    Virta, R.L.

    2001-01-01

    Part of the 2000 annual review of the industrial minerals sector. A general overview of the common clay and shale industry is provided. In 2000, U.S. production increased by 5 percent, while sales or use declined to 23.6 Mt. Despite the slowdown in the economy, no major changes are expected for the market.

  6. Octachlorodibenzodioxin formation on Fe(III)-montmorillonite clay.

    PubMed

    Gu, Cheng; Li, Hui; Teppen, Brian J; Boyd, Stephen A

    2008-07-01

    Polychlorinated dibenzo-p-dioxins (PCDDs) are ubiquitous and highly toxic environmental contaminants found in surface and subsurface soils and in clay deposits. Interestingly, the congener profiles of such PCDDs are inexplicably dissimilar to those of known anthropogenic (e.g., pesticide manufacture, waste incineration) or natural (e.g., forest fire) sources. Characteristic features of soil or clay-associated PCDDs are the dominance of octachlorodibenzo-p-dioxin (OCDD) as the most abundant congener and very low levels of polychlorinated dibenzofurans (PCDFs). These propensities led to the hypothesis of in situ PCDD formation in soils and geologic clay deposits. In this study, we demonstrate the formation of OCDD on the naturally occurring and widely distributed clay mineral montmorillonite under environmentally relevant conditions. When pentachlorophenol (PCP)was mixed with Fe(III)-montmorillonite, significant amounts of OCDD were rapidly (minutes to days) formed (approximately 5 mg OCDD/kg clay) at ambient temperature in the presence of water. This reaction is initiated by single electron transfer from PCP to Fe(III)-montmorillonite thereby forming the PCP radical cation. Subsequent dimerization, dechlorination, and ring closure reactions result in formation of OCDD. This study provides the first direct evidence for clay-catalyzed formation of OCDD supporting the plausibility of its in situ formation in soils. PMID:18678002

  7. Fire clay

    USGS Publications Warehouse

    Virta, R.L.

    2013-01-01

    Four companies mined fire clay in three states in 2012. Production, based on a preliminary survey of the fire clay industry, was estimated to be 230 kt (254,000 st) valued at $6.98 million, an increase from 215 kt (237,000 st) valued at $6.15 million in 2011. Missouri was the leading producing state, followed by Colorado and Texas, in decreasing order by quantity. The number of companies mining fire clay declined in 2012 because several common clay producers that occasionally mine fire clay indicated that they did not do so in 2012.

  8. Abundances and distribution of minerals and elements in high-alumina coal fly ash from the Jungar Power Plant, Inner Mongolia, China

    USGS Publications Warehouse

    Dai, S.; Zhao, L.; Peng, S.; Chou, C.-L.; Wang, X.; Zhang, Y.; Li, D.; Sun, Y.

    2010-01-01

    The fly ash from the Jungar Power Plant, Inner Mongolia, China, is unique because it is highly enriched in alumina (Al2O3>50%). The fly ash mainly consists of amorphous glass and mullite and trace amounts of corundum, quartz, char, calcite, K-feldspar, clay minerals, and Fe-bearing minerals. The mullite content in fly ash is as high as 37.4% because of high boehmite and kaolinite contents in feed coal. Corundum is a characteristic mineral formed during the combustion of boehmite-rich coal.Samples from the economizer were sieved into six size fractions (<120, 120-160, 160-300, 300-360, 360-500, and >500 mesh) and separated into magnetic, mullite+corundum+quartz (MCQ) and glass phases for mineralogical and chemical analysis. The corundum content increases but amorphous glass decreases with decreasing particle size. Fractions of small particle sizes are relatively high in mullite, probably because mullite was formed from fine clay mineral particles under high-temperature combustion condition. Similarly, fine corundum crystals formed in the boiler from boehmite in feed coal. The magnetic phase consists of hematite, magnetite, magnesioferrite, and MgFeAlO4 crystals. The MCQ phase is composed of 89% mullite, 6.1% corundum, 4.5% quartz, and 0.5% K-feldspar.Overall, the fly ash from the power plant is significantly enriched in Al2O3 with an average of 51.9%, but poor in SiO2, Fe2O3, CaO, MgO, Na2O, P2O5, and As. Arsenic, TiO2, Th, Al2O3, Bi, La, Ga, Ni, and V are high in mullite, and the magnetic matter is enriched in Fe2O3, CaO, MnO, TiO2, Cs, Co, As, Cd, Ba, Ni, Sb, MgO, Zn, and V. The remaining elements are high in the glass fraction. The concentration of K2O, Na2O, P2O5, Nb, Cr, Ta, U, W, Rb, and Ni do not clearly vary with particle size, while SiO2 and Hg decrease and the remaining elements clearly increase with decreasing particle size. ?? 2009 Elsevier B.V.

  9. Iodide uptake by negatively charged clay interlayers?

    PubMed

    Miller, Andrew; Kruichak, Jessica; Mills, Melissa; Wang, Yifeng

    2015-09-01

    Understanding iodide interactions with clay minerals is critical to quantifying risk associated with nuclear waste disposal. Current thought assumes that iodide does not interact directly with clay minerals due to electrical repulsion between the iodide and the negatively charged clay layers. However, a growing body of work indicates a weak interaction between iodide and clays. The goal of this contribution is to report a conceptual model for iodide interaction with clays by considering clay mineral structures and emergent behaviors of chemical species in confined spaces. To approach the problem, a suite of clay minerals was used with varying degrees of isomorphic substitution, chemical composition, and mineral structure. Iodide uptake experiments were completed with each of these minerals in a range of swamping electrolyte identities (NaCl, NaBr, KCl) and concentrations. Iodide uptake behaviors form distinct trends with cation exchange capacity and mineral structure. These trends change substantially with electrolyte composition and concentration, but do not appear to be affected by solution pH. The experimental results suggest that iodide may directly interact with clays by forming ion-pairs (e.g., NaI(aq)) which may concentrate within the interlayer space as well as the thin areas surrounding the clay particle where water behavior is more structured relative to bulk water. Ion pairing and iodide concentration in these zones is probably driven by the reduced dielectric constant of water in confined space and by the relatively high polarizability of the iodide species. PMID:26057987

  10. Enzyme-clay interactions and their impact on transformations of natural and anthropogenic organic compounds in soil

    SciTech Connect

    Naidja, A.; Huang, P.M.; Bollag, J.M.

    2000-06-01

    Soil is a living system in which enzymes are present either free in solution or bound to clay and clay-humus complexes. Enzyme-clay interactions play a key role in transforming organic compounds in soil environments where the decomposition and synthetic processes are largely catalyzed by enzymes. Scientific evidence indicates that mineral colloids take part in the catalysis of degradative and synthetic reactions of organic compounds. Such information is essential to understanding the role of mineral colloids, the hidden half of the enzyme-mineral colloid complexes, in catalytic reactions. Despite the abundant literature on the enzyme interactions with pure crystalline aluminosilicates, the nature of enzyme association with soil constituents, including both clean and coated clay minerals and other mineral colloids, and the effect on soil processes still remain unclear. This study integrates the existing information, including recent findings on enzyme-mineral colloid interactions and their effect on natural and anthropogenic organic compound transformation in soil. Further, the study focuses on the catalytic role of enzyme-clay complex surfaces in toxic industrial and agricultural compound bioremediation in soil and water environments.

  11. Mineralogy and instrumental neutron activation analysis of seven National Bureau of Standards and three Instituto de Pesquisas Tecnologicas clay reference samples

    USGS Publications Warehouse

    Hosterman, John W.; Flanagan, F.J.; Bragg, Anne; Doughten, M.W.; Filby, R.H.; Grimm, Catherine; Mee, J.S.; Potts, P.J.; Rogers, N.W.

    1987-01-01

    The concentrations of 3 oxides and 29 elements in 7 National Bureau of Standards (NBS) and 3 Instituto de Pesquisas Techno16gicas (IPT) reference clay samples were etermined by instrumental neutron activation analysis. The analytical work was designed to test the homogeneity of constituents in three new NBS reference clays, NBS-97b, NBS-98b, and NBS-679. The analyses of variance of 276 sets of data for these three standards show that the constituents are distributed homogeneously among bottles of samples for 94 percent of the sets of data. Three of the reference samples (NBS-97, NBS-97a, and NBS-97b) are flint clays; four of the samples (NBS-98, NBS-98a, NBS-98b, and IPT-32) are plastic clays, and three of the samples (NBS-679, IPT-28, and IPT-42) are miscellaneous clays (both sedimentary and residual). Seven clays are predominantly kaolinite; the other three clays contain illite and kaolinite in the approximate ratio 3:2. Seven clays contain quartz as the major nonclay mineral. The mineralogy of the flint and plastic clays from Missouri (NBS-97a and NBS-98a) differs markedly from that of the flint and plastic clays from Pennsylvania (NBS-97, NBS-97b, NBS-98, and NBS-98b). The flint clay NBS-97 has higher average chromium, hafnium, lithium, and zirconium contents than its replacement, reference sample NBS-97b. The differences between the plastic clay NBS-98 and its replacement, NBS-98b, are not as pronounced. The trace element contents of the flint and plastic clays from Missouri, NBS-97a and NBS-98a, differ significantly from those of the clays from Pennsylvania, especially the average rare earth element (REE) contents. The trace element contents of clay sample IPT-32 differ from those of the other plastic clays. IPT-28 and IPT-42 have some average trace element contents that differ not only between these two samples but also from all the other clays. IPT-28 has the highest summation of the average REE contents of the 10 samples. The uranium content of NBS-98a, 46 parts per million, is very much higher than that of the other clays. Plots of average REE contents of the flint and plastic clays, normalized to chondritic abundances, show that the clays from Missouri differ from the same types of clay from Pennsylvania. The plot of REE contents for the miscellaneous clays shows that the normalized means for the elements lanthanum through samarium for IPT-28 are much greater than those for the other miscellaneous clays. The means for the elements europium through lutetium are similar for all three miscellaneous clays.

  12. Fire clay

    USGS Publications Warehouse

    Virta, R.L.

    2006-01-01

    In 2005, six companies mined fire clay in Missouri, Ohio and South Carolina. Production was estimate to be 300 kt with a value of $8.3 million. Missouri was the leading producer state followed by Ohio and South Carolina. For the third consecutive year, sales and use of fire clays have been relatively unchanged. For the next few years, sales of fire clay is forecasted to remain around 300 kt/a.

  13. Clay Minerals in Response to the Mid-Pliocene Global Warmth in Polar Regions (ODP, Site 911, Yermak Plateau, Arctic Ocean and Site 1165, Prydz Bay, Antarctica)

    NASA Astrophysics Data System (ADS)

    Junttila, J.; Strand, K.

    2005-12-01

    The Mid-Pliocene global warmth (MPGW), a period when the global average temperatures were significantly warmer than the present, was possibly caused by higher CO2 levels than today and significantly stronger ocean thermohaline circulation due to drastic climatic changes in the Southern Ocean. In the Northern Hemisphere, MPGW could have been one decisive trigger for the intensification of glaciation at 2.7 Ma. Some recent studies in the East Antarctica have shown that the East Antarctic Ice Sheet (EAIS) may have varied from a polythermal, dynamic condition to a predominantly cold stable state as recently as the Pliocene period, including MPGW. This presentation may illuminate the Mid-Pliocene climate conditions of the Arctic Ocean and the dynamics of the EAIS based on a clay mineral study. Research of this kind, integrated with other proxies, can provide some indication of how the Earth may respond to the future global warming The Ocean Drilling Program (ODP) Site 911 was drilled on the Yermak Plateau, Arctic Ocean to a depth of 505.8 meters below the seafloor (mbsf). It contained sediments from the Pliocene to Pleistocene ages. ODP Site 1165 was drilled on the Wild Drift on the Continental Rise off Prydz Bay, East Antarctica, to a total depth of 999.1 mbsf. Of special interest is the sediment column between 0 and 50 mbsf, which consists of a well-preserved section of Pliocene- to Pleistocene-age sediments. The Pliocene sediments at Site 911 have higher smectite content and lower kaolinite and chlorite contents compared to the Pleistocene samples. This may indicate more active sea-ice conditions for smectite transportation from the Kara and Laptev Seas during the Pliocene compared to the Pleistocene sea-ice transportation conditions. The Mid-Pliocene sediments at Site 1165 show increasing smectite contents and decreasing illite contents and suggest that the EAIS at that time may have been more dynamic than that during the Plio-Pleistocene transition, to which the results were compared.

  14. Analytical Characterization of Natural Clay

    NASA Astrophysics Data System (ADS)

    El-Sheikhy, Refat; Al-Shamrani, Mosleh

    2010-10-01

    The current paper introduces the study of morphology and electronic microscopy characterization of one type of the smectite Saudi nano clay montmorillonite type. During the last decade, nanotechnology achieved a recognized progress in many fields based mainly on synthesized materials. Much attention is devoted to produce natural nano particles. It was found that the clay is one of the rare materials which have platelets of nano scale size. The nano clay minerals are found in different types. It is investigated that the nano clay minerals have super properties which can not be found in the other materials. The Kingdom of Saudi Arabia has many zones having different types of good nano clays. These nano clays are found in certain mixtures with other different materials such as Mg, Ca, Fe and others. By developing an innovated technique we could extract Saudi Arabian nano clay with high grade purity. The results are very interesting. The produced nano clay particles are with good quality and super properties. It can be used in many fields of nanocomposites.

  15. Investigating the Influence of Clay Mineralogy on Stream Bank Erodibility

    NASA Astrophysics Data System (ADS)

    Ambers, R. K.; Stine, M. B.

    2005-12-01

    Soil scientists concerned with erosion of agricultural fields and geotechnical engineers concerned with the mechanical behavior of soils under different conditions have both examined the role of clay mineralogy in controlling soil/sediment properties. Fluvial geomorphologists studying stream channel erosion and stability have focused more on the effects of particle-size distribution, vegetation and rooting. The clay mineralogy of bed and bank sediment has the potential to influence cohesiveness and erodibility, however. The goal of this study is to determine the influence of clay mineralogy on the erodibility of natural stream bank sediment, utilizing techniques drawn from pedology and soil mechanics. Bank samples were collected from eleven sites in small watersheds in central and western Virginia. To obtain sediment containing a range of different clay minerals, watersheds with different types of bedrock were chosen for sampling. Rock types included mafic to felsic metamorphic and igneous rocks, shale, sandstone, and limestone. Where stream bank materials were clearly stratified, different layers were sampled separately. X-ray diffraction of the clay-fraction of the sediment indicates the presence of kaolinite, illite, vermiculite, and mixed-layer clay minerals in various abundances in the different samples. Clay content is 9-46%, as determined by the hydrometer method, and textures range from silty clay and silt loam to clay loam and sandy loam. Organic mater contents range from 1-5% by the loss-on-ignition method. Bulk density of intact sediment samples averages 1.5 g/cc. Liquid limits range from 23-41 with one sample having a value of 65; plasticity indices range from 15-22. While these tests predict that the samples would show a range of mechanical behaviors, the channel morphology at the sampling sites was not strikingly different, all having steep cut banks eroded primarily by scour with no evidence of mass movement and most having a width/depth ratio around 4.5. The ASTM pinhole test for identifying dispersive clay soils is being adapted to measure erodibility of intact and remolded sediment samples in the laboratory to look for more subtle differences in behavior under erosive conditions. Factors such as the extent and method of sample compaction are being taken into account in order to standardize the method.

  16. Effect of Overpressure Caused By Clay Dehydration on the Triggering of Fault Slip

    NASA Astrophysics Data System (ADS)

    Lin, W. S.; Liu, C. W.; Chang, H. Y.

    2014-12-01

    Many investigations currently show that the pore fluid pressure has been observed to influence the thrust fault strength and slip behavior and updip limit of the seismogenic zone. Clay dehydration is one key control on overpressure generation under undrained condition in thermal pressurization processes. Increasing pressure and temperature with depth depending on the local geological setting and conditions can cause clay dehydration which has been proposed as an explanation for the generation of overpressure. However, study about the effect of excess pore pressure caused by clay dehydration on the triggering of earthquake is seldom addressed in Taiwan. The fault zones in Taiwan like the Chelungpu Fault, clay minerals are abundant in the fault gouge. Therefore, to quantify the effect of overpressure caused by clay dehydration on the triggering of earthquake under undrained condition, we adopt the chemical kinetic model to calculate the amount of water expelled from clay dehydration; derive the three-dimensional governing equation of groundwater flow with clay dehydration varied with pressure and temperature, and simplify a one-dimensional analytical solution of overpressure in fault zones; follow the Coulomb-Mohr frictional failure model of earthquake occurrence to evaluate the influence of the pore pressure on the change of effective Coulomb stress. The results show that the overpressure is greater than the value of 0.01 MPa in fault zones derived from one-dimensional analytical solution. However, Coulomb stress increases of ≥0.01 MPa have been shown to be associated with seismicity rate increase and in many cases triggering earthquakes. Therefore the result denotes that the triggering of earthquake will be progressed. The result could prove to be a feasible examining tool for evaluation of overpressure influence on triggering of earthquake, especially when considering faults with abundant clay minerals of smectite.

  17. A review of conditions affecting the radiolysis due to40K on nucleic acid bases and their derivatives adsorbed on clay minerals: Implications in prebiotic chemistry

    NASA Astrophysics Data System (ADS)

    Mosqueira, F. G.; Albarrán, G.; Negrón-Mendoza, A.

    1996-02-01

    This paper describes the possible effects of ionizing radiation arising from long-lived soluble radionuclides within clays, in particular40K, at the epoch of the emergence of life on Earth. The free dispersion of soluble radionuclides constitutes an effectivein situ irradiation mechanism that might have acted upon adsorbed nucleic bases and their derivatives on clays, inducing chemical changes on these organic molecules. Several types of well documented reactions for radiolysis of nucleic acid bases and their derivatives are known, even at low doses (i.e., 0.1 Gy). For example, estimates with a dose rate calculated from40K from deep sea clays at 3.8 Ga ago, indicates that over a period of 1000 years the amount of organic material transformated is 1.8 × 10-7 moles/kg-clay. Although ionizing radiation may also induce synthetic reactions with prebiological interest, all in all these considerations indicate that nucleic acid bases and their derivatives adsorbed on clays were exposed for long periods to degradation conditions. Such situation promotes decomposition of organic molecules rather than protection of them and enhancement of further polymerization, as it has been usually taken for granted.

  18. Rare earth element abundances in rocks and minerals from the Fiskenaesset Complex, West Greenland. [comparison with lunar anorthosites

    NASA Technical Reports Server (NTRS)

    Henderson, P.; Fishlock, S. J.; Laul, J. C.; Cooper, T. D.; Conard, R. L.; Boynton, W. V.; Schmitt, R. A.

    1976-01-01

    The paper reports activation-analysis determinations of rare-earth-element (REE) and other trace-element concentrations in selected rocks, plagioclase, and mafic separates from the Fiskenaesset Complex. The REE abundances are found to be very low and atypical in comparison with other terrestrial anorthosites. The plagioclases are shown to be characterized by a deficiency in heavy RE elements relative to light ones and a positive Eu anomaly, while the mafic separates are enriched in heavy rare earths and have no Eu anomaly, except in one sample. It is found that the bulk and trace-element abundances of the plagioclases are similar to those observed in some lunar anorthosites, but the degree of Eu anomaly is less in the plagioclases. The data are taken as confirmation of the idea that fractionation processes were involved in the origin of the Complex, and it is concluded that the Complex may have been produced from a magma generated by partial melting of a garnet-bearing source.

  19. Clay alteration of volcaniclastic material in a submarine geothermal system, Bay of Plenty, New Zealand

    NASA Astrophysics Data System (ADS)

    Hocking, Michael W. A.; Hannington, Mark D.; Percival, Jeanne B.; Stoffers, Peter; Schwarz-Schampera, Ulrich; de Ronde, C. E. J.

    2010-04-01

    The Calypso Hydrothermal Vent Field (CHVF) is located along an offshore extension of the Taupo Volcanic Zone (TVZ), an area of abundant volcanism and geothermal activity on the North Island of New Zealand. The field occurs within a northeast-trending submarine depression on the continental shelf approximately 10-15 km southwest of the White Island volcano in the Bay of Plenty. The graben has been partially filled by tephra from regional subaerial volcanic eruptions, and active hydrothermal venting occurs at several locations along its length. The vents occur at water depths of 160 to 190 m and have temperatures up to 201 °C. Recovered samples from the vent field include variably cemented and veined volcaniclastic sediments containing an assemblage of clay minerals, amorphous silica, barite, As-Sb-Hg sulfides, and abundant native sulfur. The volcanic glass has been altered primarily to montmorillonite and mixed-layer illite-montmorillonite; illite, and possibly minor talc and mixed-layer chlorite-smectite or chlorite-vermiculite are also present. A hydrothermal versus diagenetic origin for the smectite is indicated by the presence of both illite and mixed-layer clays and by the correlation between the abundance of clay minerals and the abundance of native sulfur in the samples. The mineralization and alteration of the volcanic host rocks are similar to that observed in near-neutral pH geothermal systems on land in the TVZ (e.g., Broadlands-Ohaaki). However, the clay minerals in the CHVF have a higher concentration of Mg in the dioctahedral layer and a higher interlayer Na content than clay minerals from Broadlands-Ohaaki, reflecting the higher concentrations of Mg and Na in seawater compared to meteoric water. Minerals formed at very low pH (e.g., kaolinite and alunite), typical of steam-heated acid-sulfate type alteration in the TVZ geothermal environment, were not found. Mixing with seawater likely prevented the formation of such low-pH mineral assemblages. The occurrence of illite and mixed-layer illite-smectite close to the seafloor in the CHVF, rather than at depth as in the Broadlands system, is interpreted to reflect the higher pressures associated with submarine venting. This allows hotter fluids to be discharged before they boil, and thus minerals that are encountered mainly at depth in subaerial geothermal systems can form close to the seafloor.

  20. Mineral Composition and Abundance of the Rocks and Soils at Gusev and Meridiani from the Mars Exploration Rover Mini-TES Instruments

    NASA Technical Reports Server (NTRS)

    Christensen, P. R.; Wyatt, M. B.; Glotch, T. D.; Rogers, A. D.; Anwar, S.; Arvidson, R. E.; Bandfield, J. L.; Blaney, D. L.; Budney, C.; Calvin, W. M.

    2005-01-01

    The Miniature Thermal Emission Spectrometer (Mini-TES) has provided remote measurements of mineralogy, thermophysical properties, and atmospheric temperature profile and composition of the outcrops, rocks, spherules, and soils surrounding the Spirit and Opportunity Rovers. The mineralogy of volcanic rocks provides insights into the composition of the source regions and the nature of martian igneous processes. Carbonates, sulfates, evaporites, and oxides provide information on the role of water in the surface evolution. Oxides, such as crystalline hematite, provide insight into aqueous weathering processes, as would the occurrence of clay minerals and other weathering products. Diurnal temperature measurements can be used to determine particle size and search for the effects of sub-surface layering, which in turn provide clues to the origin of surficial materials through rock disintegration, aeolian transport, atmospheric fallout, or induration. In addition to studying the surface properties, Mini-TES spectra have also been used to determine the temperature profile in the lower boundary layer, providing evidence for convective activity, and have determined the seasonal trends in atmospheric temperature and dust and cloud opacity.

  1. Fire clay

    USGS Publications Warehouse

    Virta, R.L.

    2012-01-01

    Five companies mined fire clay in four states in 2011. Production, based on a preliminary survey of the fire clay industry, was estimated to be 240 kt (265,000 st), valued at $7.68 million, an increase from 216 kt (238,000 st), valued at $6.12 million in 2010. Missouri was the leading producing state, followed by Texas, Washington and Ohio, in decreasing order by quantity.

  2. Sr-Nd isotope composition and clay mineral assemblages in eolian dust from the central Philippine Sea over the last 600 kyr: Implications for the transport mechanism of Asian dust

    NASA Astrophysics Data System (ADS)

    Seo, Inah; Lee, Yong Il; Yoo, Chan Min; Kim, Hyung Jeek; Hyeong, Kiseong

    2014-10-01

    Dust transport to the tropical/subtropical northwestern Pacific over the past 600 kyr was investigated using radiogenic isotopes (87Sr/86Sr and ɛNd), together with the clay mineral composition, of eolian dust preserved in a sediment core obtained from the Philippine Sea (12°30'N, 134°60'E). These data revealed the influence of two prevailing dust sources, namely, the Asian deserts and nearby volcanic arcs (e.g., the Luzon Arc), with average contributions of around 70% and 30%, respectively, from each. The clay mineral composition of the core resembled dust from the central Asian deserts (CADs; e.g., the Taklimakan Desert) as in the north-central Pacific, but published aerosol data collected near the study site during winter/spring have the mineralogical signature of dust originating from the East Asian deserts (EADs). These data indicate that the relative contribution of EAD dust increases with the northeasterly surface winds associated with the East Asian Winter Monsoon (EAWM) during winter/spring, but the Prevailing Westerlies and Trade Winds that carry dust from the CADs is the dominant transport agent in the overall dust budget of the study site. The results of this study contradict the prevailing view that direct dust transport by the EAWM winds in spring dominates the annual flux of eolian dust in the northwest Pacific.

  3. Smart Clays: SAFOD Samples Confirm the Key Role of Newly-formed Clays in Shallow Fault Zones

    NASA Astrophysics Data System (ADS)

    Schleicher, A.; van der Pluijm, B.; Warr, L. N.

    2013-12-01

    Analysis of fault rocks from drill-cores of the San Andreas Fault Observatory at Depth (SAFOD) project in Parkfield (CA) confirm our original hypothesis that active clay growth can occur locally at shallow conditions and that such clay localization affect fault mechanics and fault creep in particular. SAFOD fault rocks contain a variety of newly formed clay minerals including smectite, illite-smectite and chlorite-smectite, as well as illite and chlorite. Brecciated host rock fragments are abundantly coated by polished and/or striated thin-films of hydrated clay minerals, creating an interconnected and pervasive network of displacement surfaces. Ar encapsulation dating of mixed-layer nanocoatings demonstrates recent crystallization and reveal an 'older' fault strand (~8 Ma) at 3066 m measured depth and a 'younger' fault strand (~4 Ma) at 3296 m measured depth. Today, the younger strand is the site of active creep behavior, demonstrating continued (re)activation of clay-weakened zones. Recent experimental work on aseismically creeping segments of SAFOD samples showed frictional strengths that are significantly weaker than neighboring wall rocks, offering independent validation of our model. Using a range of analytical methods that include X-ray diffraction, X-ray goniometry, elemental analysis and electron microscopy, we determined the location and nature of smectitic clay minerals in borehole samples, to assess the extent of smectitic phases in space and depth, any fault zone fabric development, and the swelling behavior of smectitic phases within the fault zone. Beyond the occurrence of illite-smectite in these relatively shallow fault rocks, the localized concentration of chlorite-smectite can extend the role of smectitic clays to depths down to ~10 km. We conclude that ultrathin hydrous clay films, or nanocoatings, on displacement surfaces play a key role in influencing weak fault and creep behavior along the San Andreas Fault at Parkfield, and likely in shallow faults systems elsewhere. These results indicate that scenarios involving talc/serpentine phases or locally enhanced fluid pressure as explanations for mechanically weak crustal faults are not required.

  4. Clay petrology of the Upper Triassic/Lower Jurassic terrestrial strata of the Newark Supergroup, Connecticut Valley, U.S.A.

    NASA Astrophysics Data System (ADS)

    April, Richard H.

    1981-08-01

    The clay mineralogy of the Newark Supergroup (Upper Triassic/Lower Jurassic) in the Connecticut Valley was studied by X-ray diffraction analysis. Clay minerals identified in 126 samples are illite, chlorite, smectite, kaolinite, vermiculite, expandable chlorite, mixed-layer illite/smectite, mixed-layer chlorite/smectite, and mixed-layer chlorite/vermiculite. In general, the rocks are illitic with subordinate amounts of chlorite. However, the various lithofacies in the Newark Supergroup are characterized by distinct clay-mineral assemblages. Red beds of floodplain origin contain clays mainly of detrital nature with 2M illite most abundant. Subordinate amounts of chlorite, smectite, vermiculite, kaolinite and mixed-layer illite/smectite are also present. An interstratified chlorite/vermiculite occurs in red mudstone underlying basalt flows. Lacustrine gray beds are generally characterized by the clay-mineral assemblage 1Md illite + chlorite with minor amounts of smectite ane expandable chlorite. An interstratified chlorite/smectite predominates in gray mudstone associated with perennial lake cycles in the East Berlin Formation. Black shales of deeper lacustrine origin contain the assemblage 1Md ifillite + trioctahedral smectite and traces of chlorite. Illite and smectite also occur as mixed-layer phases. In many respects, the distribution of clay minerals in the Connecticut Valley can be likened to the general scheme proposed for the Permo-Triassic basins of Europe and Africa. These display both vertical and horizontal variations in clay-mineral assemblages that reflect the chemical and spatiotemporal evolution of intrabasin depositional and diagenetic environments. Chemical data indicate that magnesium, especially, was concentrated in the black muds of large perennial lakes that intermittently occupied the Connecticut rift valley. Pore waters derived from these sediments played an important role in the development of Mg-rich 2 : 1 and interstratified clay minerals during early diagenesis.

  5. Chemical disaggregation of kaolinitic claystones (tonsteins and flint clays)

    USGS Publications Warehouse

    Triplehorn, D.M.; Bohor, B.F.; Betterton, W.J.

    2002-01-01

    The coarse, non-clay fraction of many flint-like kaolinitic claystones often contains mineral grains diagnostic of the claystone's origin and, in the case of tonsteins (altered volcanic ashes), may also provide minerals suitable for radiometric dating. Separation of the non-clay mineral fraction is often difficult because flint clays and flint-like clays resist slaking in water and thus are difficult to disaggregate. Chemical disaggregation of resistant kaolinitic claystones may be achieved by immersion in either hydrazine monohydrate or DMSO for periods ranging from one day to several weeks. Generally, hydrazine monohydrate works more quickly and efficiently than DMSO to disaggregate most kaolinitic claystones and flint clays.

  6. Probability of adsorption of peptide (CR3-1, S2) chains on clay minerals by coarse-grained Monte Carlo simulation

    NASA Astrophysics Data System (ADS)

    Pandey, Ras B.; Heinz, Hendrik; Farmer, Barry L.; Jones, Sharon; Drummy, Lawrence F.; Naik, Rajesh R.

    2009-03-01

    A coarse-grained description is used to study the structure and dynamics of peptide chains (CR3-1, S2) in presence of a clay surface on a cubic lattice. A peptide chain is represented by the specific sequence of amino acids. Specificity of residues is captured via an interaction matrix based on the insight gained from the atomistic simulation, i.e., each residue interacts with surrounding residues, solvent, and the clay surface with a unique interaction potential. We use a standard LJ potential with its coefficient controlled by the interaction matrix. Simulations are performed with a number of peptide chains. Along with the global energy and dynamics of peptides, we keep track of mobility, energy (total and adsorption), and correlation with the local structure from the density profiles of each residue. Based on the analysis of local and global quantities, we are able to assess the probability of adsorption of peptides to clay surface in agreement with experiment. The probability of adsorption of S2 is found to be much higher than that of CR3-1 in which S2 is anchored by Lysine. The procedure is complementary to biopanning experiments since it allows screening a large number of peptides (more than 10E+5) on the surface to estimate their binding potential.

  7. Ball clay

    USGS Publications Warehouse

    Virta, R.L.

    2012-01-01

    Four companies — H.C. Spinks Clay Co., Inc., Imerys Group, Old Hickory Clay Co., and Unimin Corp. — mined ball clay in four states in 2011. Production, on the basis of preliminary data, was 940 kt (1.04 million st) with an estimated value of $44.2 million. This is a 3-percent increase in tonnage from 912 kt (1.01 million st) with a value of $41.3 million that was produced in 2010. Tennessee was the leading producing state with 63 percent of domestic production, followed by Texas, Mississippi and Kentucky. About 69 percent of production was airfloat, 20 percent was crude and 11 percent was water-slurried.

  8. Relations between clay mineralogy and depositional environment in the Atchafalaya basin and Terrebonne Marsh areas, south-central Louisiana

    SciTech Connect

    Stewart, K.D. ); Patrick, D.M. )

    1990-09-01

    The analyses of nearly 200 vibracore samples taken from Holocene sediments in south-central Louisiana revealed strong statistical relations between clay mineral composition and depositional environment and lithology The samples selected for study were representative of the major depositional environments, which are: backswamp, channel fill, crevasse channel, inland swamp, interdistributary bay, lacustrine or lacustrine delta, marsh, and natural levee. The dominant clay minerals from most to least abundant in both the Atchafalaya basin and Terrebonne Marsh areas were: smectite (70%), illite (18%), kaolinite (10%), and chlorite (1%). The higher concentrations of smectite occurred in the inland swamp (86%) and backswamp (83%), and the lower concentrations were found in the crevasse channel (44%) and lacustrine delta (58%). Generally, the percent smectite was inversely proportional to the relative depositional energy of the environment. The percent illite ranged from a low of 8 in the inland swamp to a high of 37 in the crevasse channel. Kaolinite was most abundant in the lacustrine delta (14%), and least abundant in the inland swamp (5%). Chlorite was 2% or less in most environments; however, the crevasse channel exhibited a concentration of 8%. In terms of lithology, the highest concentration of smectite (78%) occurred in deposits classed as clay, and the lowest (46%) occurred in organic-rich clay. Clay and organic-rich clay, respectively, also exhibited the lowest and highest concentrations of both illite and kaolinite. The high smectite content is attributable to the low energy of the clay deposits, while the low concentrations of smectite in both organic-rich and peat material are due to instability of smectite in low pH environments.

  9. Clay composition and swelling potential estimation of soils using depth of absorption bands in the SWIR (1100-2500 nm) spectral domain

    NASA Astrophysics Data System (ADS)

    Dufréchou, Grégory; Granjean, Gilles; Bourguignon, Anne

    2014-05-01

    Swelling soils contain clay minerals that change volume with water content and cause extensive and expensive damage on infrastructures. Presence of clay minerals is traditionally a good estimator of soils swelling and shrinking behavior. Montmorillonite (i.e. smectite group), illite, kaolinite are the most common minerals in soils and are usually associated to high, moderate, and low swelling potential when they are present in significant amount. Characterization of swelling potential and identification of clay minerals of soils using conventional analysis are slow, expensive, and does not permit integrated measurements. SWIR (1100-2500 nm) spectral domain are characterized by significant spectral absorption bands related to clay content that can be used to recognize main clay minerals. Hyperspectral laboratory using an ASD Fieldspec Pro spectrometer provides thus a rapid and less expensive field surface sensing that permits to measure soil spectral properties. This study presents a new laboratory reflectance spectroscopy method that used depth of clay diagnostic absorption bands (1400 nm, 1900 nm, and 2200 nm) to compare natural soils to synthetic montmorillonite-illite-kaolinite mixtures. We observe in mixtures that illite, montmorillonite, and kaolinite content respectively strongly influence the depth of absorption bands at 1400 nm (D1400), 1900 nm (D1900), and 2200 nm (D2200). To attenuate or removed effects of abundance and grain size, depth of absorption bands ratios were thus used to performed (i) 3D (using D1900/D2200, D1400/D1900, and D2200/D1400 as axis), and (ii) 2D (using D1400/D1900 and D1900/D2200 as axis) diagrams of synthetic mixtures. In this case we supposed that the overall reduction or growth of depth absorption bands should be similarly affected by the abundance and grain size of materials in soil. In 3D and 2D diagrams, the mixtures define a triangular shape formed by two clay minerals as external envelop and the three clay minerals mixtures are located inside of the triangular shape. Clay composition of natural soils were estimated using 3D and 2D diagrams used as standard template from: (i) the average clay composition of the three closer mixtures when soil samples were plotted inside the triangular distribution of mixtures; and (ii) the closer mixture when the soil sample were plotted outside of the triangular distribution of mixtures. Comparison with X-ray diffraction analysis show reliable prediction of montmorillonite content that were used to estimate the swelling potential of soils. This method allows a simple, fast, and low cost method that classes soils into four swelling classes based on comparison with Methylene Blue test, and could be used as complementary or alternative method to traditional geotechnical analysis.

  10. Coating of silica sand with aluminosilicate clay.

    PubMed

    Jerez, Jorge; Flury, Markus; Shang, Jianying; Deng, Youjun

    2006-02-01

    The objective of this work was to coat aluminosilicate clays on an inert silica support, and to characterize the properties and stability of the clay-silica coating. Two polymers, polyacrylamide (PAM) and polyvinyl alcohol (PVA), were used to bind kaolinite, illite, and smectite onto silica grains. The clay-polymer composites were studied by X-ray diffraction, FTIR, and electrophoretic mobility. Clay coatings on silica grains were characterized by mass coverage, scanning electron microscopy, specific surface area, and pH stability. Silica sand was successfully coated with clays by using the two polymers, but with PVA, the clay coating had a greater mass coverage and was more stable against pH variations. Less polymer was needed for the clay coating using PVA as compared to using PAM. Clay-polymer complexes and pure clay minerals had similar cation exchange capacities and electrophoretic mobilities, indicating that overall surface charge of the clays was little affected by the polymers. Some decrease in hydrophilicity was observed for illite and smectite when clays where coated with the polymers. The methodology reported here allows the generation of a clay-based porous matrix, with hydraulic properties that can be varied by adjusting the grain size of the inert silica support. PMID:16085082

  11. The colloidal chemistry of ceramic clays

    NASA Technical Reports Server (NTRS)

    Phelps, G. W.

    1984-01-01

    The colloidal chemistry and mineralogy of two argil minerals were studied. Deposits of kaolin and of ceramic clays in the United States and England are discussed for the probable mechanism of formation. The structural modifications of the bed, original material associated with the clays and the proper use of flocculants are discussed.

  12. Clay mineralogy of Lower Cretaceous deep-sea fan sediments, western North Atlantic basin

    SciTech Connect

    Holmes, M.A.

    1986-05-01

    The Lower Cretaceous of the eastern North American continent was a time of extensive deltaic progradation. The effects of deltaic deposition on sedimentation in the western North Atlantic were unknown until May 1982, when, at Deep Sea Drilling Project Site 603 off Cape Hatteras, over 260 m of micaceous, muddy turbidites were recovered that correlate with deltaic progradation on eastern North America. The results of clay mineral studies from onshore and offshore equivalents indicate that during the Cretaceous, some sorting of clay minerals by transport processes occurred. Kaolinite tends to accumulate in continental environments, illite in transitional to marine environments, and smectite in deep sea sediments as pelagic clay. In the sediments from the western North Atlantic, illite tended to be more abundant in thick bedded sandy muds, whereas kaolinite tended to be more abundant in thin bedded muddy sands. Although the occurrence of illite and kaolinite in pelagic sediments indicates a general increased terrigenous influence, the results of this study indicate that these two clays behave independently in these sediments. The presence of large amounts of kaolinite at certain levels in these sediments corresponds to phases of maximum deep-sea fan development, and so indicates a more direct input of continental material, with less sorting of sediments by continental and shelf processes (pericontinental fractionation) prior to redeposition.

  13. Clay energetics in chemical evolution

    NASA Technical Reports Server (NTRS)

    Coyne, L. M.

    1986-01-01

    Clays have been implicated in the origin of terrestrial life since the 1950's. Originally they were considered agents which aid in selecting, concentrating and promoting oligomerization of the organic monomeric substituents of cellular life forms. However, more recently, it has been suggested that minerals, with particular emphasis on clays, may have played a yet more fundamental role. It has been suggested that clays are prototypic life forms in themselves and that they served as a template which directed the self-assembly of cellular life. If the clay-life theory is to have other than conceptual credibility, clays must be shown by experiment to execute the operations of cellular life, not only individually, but also in a sufficiently concerted manner as to produce some semblance of the functional attributes of living cells. Current studies are focussed on the ability of clays to absorb, store and transfer energy under plausible prebiotic conditions and to use this energy to drive chemistry of prebiotic relevance. Conclusions of the work are applicable to the role of clays either as substrates for organic chemistry, or in fueling their own life-mimetic processes.

  14. Clay at Nili Fossae

    NASA Technical Reports Server (NTRS)

    2006-01-01

    This image of the Nili Fossae region of Mars was compiled from separate images taken by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) and the High-Resolution Imaging Science Experiment (HiRISE), two instruments on NASA's Mars Reconnaissance Orbiter. The images were taken at 0730 UTC (2:30 a.m. EDT) on Oct. 4, 2006, near 20.4 degrees north latitude, 78.5 degrees east longitude. CRISM's image was taken in 544 colors covering 0.36 to 3.92 micrometers, and shows features as small as 18 meters (60 feet) across. HiRISE's image was taken in three colors, but its much higher resolution shows features as small as 30 centimeters (1 foot) across.

    CRISM's sister instrument on the Mars Express spacecraft, OMEGA, discovered that some of the most ancient regions of Mars are rich in clay minerals, formed when water altered the planet's volcanic rocks. From the OMEGA data it was unclear whether the clays formed at the surface during Mars' earliest history of if they formed at depth and were later exposed by impact craters or erosion of the overlying rocks. Clays are an indicator of wet, benign environments possibly suitable for biological processes, making Nili Fossae and comparable regions important targets for both CRISM and HiRISE.

    In this visualization of the combined data from the two instruments, the CRISM data were used to calculate the strengths of spectral absorption bands due to minerals present in the scene. The two major minerals detected by the instrument are olivine, a mineral characteristic of primitive igneous rocks, and clay. Areas rich in olivine are shown in red, and minerals rich in clay are shown in green. The derived colors were then overlayed on the HiRISE image.

    The area where the CRISM and HiRISE data overlap is shown at the upper left, and is about 5 kilometers (3 miles) across. The three boxes outlined in blue are enlarged to show how the different minerals in the scene match up with different landforms. In the image at the upper right, the small mesa -- a flat-topped hill -- at the center of the image is a remnant of an overlying rock layer that was eroded away. The greenish clay areas at the base of the hill were exposed by erosion of the overlying rock. The images at the upper right and lower left both show that the reddish-toned olivine occurs as sand dunes on top of the greenish clay deposits. The image at the lower right shows details of the clay-rich rock, including that they are extensively fractured into small, polygonal blocks just a few meters in size. Taken together, the CRISM and HiRISE data show that the clay-rich rocks are the oldest at the site, that they are exposed where overlying rock has been eroded away, and that the olivine is not part of the clay-rich rock. Rather it occurs in sand dunes blowing across the clay.

    Many more images of Nili Fossae and other clay-rich areas will be taken over the next two years. They will be used to try to understand the earliest climate of Mars that is recorded in the planet's rocks.

    The Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) is one of six science instruments on NASA's Mars Reconnaissance Orbiter. Led by The Johns Hopkins University Applied Physics Laboratory, the CRISM team includes expertise from universities, government agencies and small businesses in the United States and abroad.

    CRISM's mission: Find the spectral fingerprints of aqueous and hydrothermal deposits and map the geology, composition and stratigraphy of surface features. The instrument will also watch the seasonal variations in Martian dust and ice aerosols, and water content in surface materials o leading to new understanding of the climate.

    NASA's Jet Propulsion Laboratory, a division of the Califonia Institute of Technology, Pasadena, manages the Mars Reconnaissance Orbiter for the NASA Science Mission Directorate, Washington. Lockheed Martin Space Systems, Denver, is the prime contractor and built the spacecraft.

  15. Effect of electrolytes on the microstructure and yielding of aqueous dispersions of colloidal clay.

    PubMed

    Ali, Samim; Bandyopadhyay, Ranjini

    2016-01-14

    Na-montmorillonite is a natural clay mineral and is available in abundance in nature. The aqueous dispersions of charged and anisotropic platelets of this mineral exhibit non-ergodic kinetically arrested states ranging from soft glassy phases dominated by interparticle repulsions to colloidal gels stabilized by salt induced attractive interactions. When the salt concentration in the dispersing medium is varied systematically, viscoelasticity and yield stress of the dispersion show non-monotonic behavior at a critical salt concentration, thus signifying a morphological change in the dispersion microstructures. We directly visualize the microscopic structures of these kinetically arrested phases using cryogenic scanning electron microscopy. We observe the existence of honeycomb-like network morphologies for a wide range of salt concentrations. The transition of the gel morphology, dominated by overlapping coin (OC) and house of cards (HoC) associations of clay particles at low salt concentrations to a new network structure dominated by face-face coagulation of platelets, is observed across the critical salt concentration. We further assess the stability of these gels under gravity using electroacoustics. This study, performed for concentrated clay dispersions for a wide concentration range of externally added salt, is useful in our understanding of many geophysical phenomena that involve the salt induced aggregation of natural clay minerals. PMID:26477340

  16. Clay mineral provinces in tidal mud flats at Germany's North Sea coast with illite K-Ar ages potentially modified by biodegradation

    NASA Astrophysics Data System (ADS)

    Brockamp, Olaf; Clauer, Norbert

    2012-07-01

    Mineralogical studies, chemical analyses and K-Ar dating were carried out on clay fractions from tidal mud flats along the Lower Saxony coast and its bays to identify material sources and sedimentary processes at this dynamic interface between air, land and sea. From the coast into the bays, sediments are enriched in fine-grained smectite relative to the coarser grained illite, chlorite and kaolinite, due to the weakening of the tidal current energy in the bays. In addition, the study area can be divided into two provinces on the basis of the illite K/Rb ratios and Mg contents. To the west [Schiermonnikoog, Dollart, Ley Bay up to Norderney island], longshore currents carry suspensions from the Belgian and Dutch coasts; to the east [from Langeoog island, Jade Bay to the Helgoland mud area] suspensions from the Elbe and Weser rivers are mixed with submarine reworked glacial sediments, whereas the portion of longshore current suspensions from the west decreases, becoming negligible in the Helgoland mud area off the Elbe and Weser estuaries. The illite K-Ar data vary considerably and fail as source indicators due to differential settling and mixing of the clay material and probably to Ar loss from illite by biodegradation during digestive processes. Only further offshore, outside the zone of dynamic sediment dispersion, do the K-Ar data fit provenance patterns.

  17. Clay for Little Fingers.

    ERIC Educational Resources Information Center

    Koster, Joan Bouza

    1999-01-01

    Discusses the renewed interest in clay as a modeling compound in early childhood programs; describes the nature of clay and presents a working vocabulary. Suggests methods of working with clay, including introducing clay to children, discovering its uses, clean up, firing clay, and finishing baked clay. Includes activity suggestions and…

  18. Fire clay

    USGS Publications Warehouse

    Virta, R.L.

    2004-01-01

    Seven companies mined fire clay in four states during 2003. From 1984 to 1992, production declined to 383 kt (422,000 st) from a high of 1.04 Mt (1.14 million st) as markets for clay-based refractories declined. Since 1992, production levels have been erratic, ranging from 383 kt (422,000 st) in 1992 and 2001 to 583 kt (642,000 st) in 1995. Production in 2003, based on preliminary data, was estimated to be around 450 kt (496,000 st) with a value of about $10.5 million. This was about the same as in 2002. Missouri remained the leading producer state, followed by South Carolina, Ohio and California.

  19. Clay sized fraction and powdered whole-rock X-ray analyses from alluvial basin deposits in central and southern New Mexico

    USGS Publications Warehouse

    Anderholm, S.K.

    1985-01-01

    As part of the study of the water quality and geochemistry of Southwest Alluvial Basins (SWAB) in parts of Colorado, New Mexico, and Texas, which is a Regional Aquifer-System Analysis (RASA) program, whole rock x-ray analysis and clay-size fraction mineralogy (x-ray) analysis of selected samples from alluvial basin deposits were done to investigate the types of minerals and clay types present in the aquifers. This was done to determine the plausible minerals and clay types in the aquifers that may be reacting with groundwater and affecting the water quality. The purpose of this report is only to present the whole rock x-ray and clay-fraction mineralogy data. Nineteen surface samples or samples from outcrop of Tertiary and Quaternary alluvial basin deposits in the central and southern Rio Grande rift were collected and analyzed. The analysis of the samples consisted of grain size analysis, and clay-size fraction mineralogy and semiquantitative analysis of the relative abundance of different clay mineral groups present. (USGS)

  20. Effects of clay minerals and organic matter in formulated sediments on the bioavailability of sediment-associated uranium to the freshwater midge, Chironomus dilutus.

    PubMed

    Crawford, Sarah E; Liber, Karsten

    2015-11-01

    It is well established that bioavailability influences metal toxicity in aquatic ecosystems. However, the factors and mechanisms that influence uranium (U) bioavailability and toxicity in sediment have not been thoroughly evaluated, despite evidence that suggests different sediment components can influence the sorption and interaction of some metals. Given that dissolved U is generally accepted as being the primary bioavailable fraction of U, it is hypothesized that adsorption and interaction of U with different sediment components will influence the bioavailability of U in sediment. We investigated the effects of key sediment physicochemical properties on the bioavailability of U to a model freshwater benthic invertebrate, Chironomus dilutus. Several 10-day spiked sediment bioaccumulation experiments were performed, exposing C. dilutus larvae to a variety of formulated sediments spiked with different concentrations of U (5, 50 and/or 200 mg U/kg d.w.). Mean accumulation of U in C. dilutus larvae decreased significantly from 1195 to 10 mg U/kg d.w. as kaolin clay content increased from 0% to 60% in sediment spiked with 50 mg U/kg d.w. Similarly, higher organic matter content also resulted in a significant reduction of U bioaccumulation in C. dilutus larvae, indicating a reduction in U bioavailability. Concentrations of U in both the overlying water and sediment pore water displayed a strong positive relationship to U bioaccumulation in C. dilutus larvae (r(2) = 0.77, p<0.001 and r(2) = 0.57, p < 0.001, respectively) for all experiments, while total U concentrations in the sediment had a poor relationship to U bioaccumulation (r(2) = 0.10, p = 0.028). Results from this research confirm that sediment clay and organic matter content play a significant role in altering U bioavailability, which is important in informing risk assessments of U contaminated sites and in the development of site-specific sediment quality guidelines for U. PMID:26205073

  1. Detailed mineral and chemical relations in two uranium-vanadium ores

    USGS Publications Warehouse

    Garrels, Robert M.; Larsen, E. S., III; Pommer, A.M.; Coleman, R.G.

    1956-01-01

    Channel samples from two mines on the Colorado Plateau have been studied in detail both mineralogically and chemically. A channel sample from the Mineral Joe No. 1 mine, Montrose County, Colo., extends from unmineralized rock on one side, through a zone of variable mineralization, into only weakly mineralized rock. The unmineralized rock is a fairly clean quartz sand cemented with gypsum and contains only minor amounts of clay minerals. One boundary between unmineralized and mineralized rock is quite sharo and is nearly at right angles to the bedding. Vanadium clay minerals, chiefly mixed layered mica-montmorillonite and chlorite-monmorillonite, are abundant throughout the mineralized zone. Except in the dark "eye" of the channel sample, the vanadium clay minerals are accompanied by hewettite, carnotite, tyuyamunite, and probably unidentified vanadates. In the dark "eye," paramontroseite, pyrite, and marcasite are abundant, and bordered on each side by a zone containing abundant corvusite. No recognizable uranium minerals were seen in the paramontroseite zone although uranium is abundant there. Coaly material is recognizable throughout all of the channel but is most abundant in and near the dark "eye." Detailed chemical studies show a general increase in Fe, Al, U, and V, and a decrease in SO4 toward the "eye" of the channel. Reducing capacity studies indicate that V(IV) and Fe(II) are present in the clay mineral throughout the channel, but only in and near the "eye" are other V(IV) minerals present (paramontroseite and corvusite). The uranium is sexivalent, although its state of combination is conjectural where it is associated with paramontroseite. Where the ore boundary is sharp, the boundary of introduced trace elements is equally sharp. Textural and chemical relations leave no doubt that the "eye: is a partially oxidized remnant of a former lower-valence ore, and the remainder of the channel is a much more fully oxidized remnant. A channel sample from the Virgin No. 3 mine, Montrose County, Colo., extends from weakly mineralized sandstone on both sides through a strongly mineralized central zone. The weakly mineralized zone is a poorly sorted sandstone with common detrital clay partings; chlorite and mixed layer mica-montmorrillonite are abundant interstitial to the quartz grains. No distinct vanadium or uranium minerals are recognizable, although the clay minerals are vanadium bearing. Euherdral pyrite grains and selenian galena are present but rare. The strongly mineralized rock is separated from the weakly mineralized rock by a narrow transition zone which only apporiximates the bedding planes. It contains abundant vanadium-bearing clay minerals (predominantly chlorite) interstitial to the quartz grains, and apparently replacing them. Paramontroseite is common and is intergrown with the clay minerals. Pyrite and marcasite are present, chiefly in or near the abundant blebs and fragments of carbonaceous material. Selenian galena is rarely present, and generally in or near carbonaceous material. Coffinite is the only uranium mineral idenitified; it is extremely fine grained and was identified only in X-ray diffraction patterns of heavy separates. Distribution of trace elements is not clear; some are consistently high in the strongly mineralized rocks, and some are consistently low. The trace element composition of the unmineralized rock is not known. Chemical studies show a very abrupt rise in the total U, V, and Fe from the weakly mineralized to strongly mineralized rock. Reducing-capacity studies indicate that most of the vanadium is present as V(IV), but some is present as V(V); that iron is present as both Fe(II) and Fe(III), the latter believed to have been present in the primary clays of the unmineralized rock; and that come of the uranium is present as U(VI) in addition to the U(IV) in the coffinite. All evidence points to weak oxidation of an ore once having a somewhat lower valence state. The channel samples from both the Mineral Joe No. 1 mine and the Virgin No. 3 mine are believe to have been essentially identical in mineralogy prior to oxidation by weathering: vanadium was present as V(III) in montroseite and V(IV) in the vanadium clays; uranium was present largely as U(IV) in coffinite and/or uraninite. The Mineral Joe No. 1 mine channel sample is now more fully oxidized. Vanadium clays are unquestionably formed abundantly during the primary mineralization, and they persist with a minimum of alteration during much of the weathering. They suggest that the vanadium is carried as V(IV) in the ore-forming fluids; it seems likely too that the uranium is carried as a U(VI) ion.

  2. Searching for reciclability of modified clays for an environmental application

    NASA Astrophysics Data System (ADS)

    Del Hoyo Martínez, Carmen; Solange Lozano García, Marina; Sánchez Escribano, Vicente; Antequera, Jorge

    2014-05-01

    Thanks to the development of the science and the technology of the nourishment in the last 50 years, there have revealed itself several new substances that can fulfill beneficial functions in the food, and these substances, named food additives, are today within reach of all. The food additives recover a very important role in the complex nourishing supply. The additives fulfill several useful functions in the food, which often we give for sat. Nevertheless the widespread use of food additives in the food production also influences the public health. The food industries, which are very important for the economy, spill residues proved from its activity that they have to be controlled to evaluate the environmental impact and to offer the necessary information about the quantitative evaluation of the chemical risk of the use of food additives for the public health. The clay materials have led to numerous applications in the field of public health (del Hoyo, 2007; Volzone, 2007) having been demonstrated its effectiveness as adsorbents of all contaminants. Some biodegradable materials are used for for adsorption of chemical contaminants: lignins (Valderrabano et al., 2008) and also clays and clay minerals, whose colloidal properties, ease of generating structural changes, abundance in nature, and low cost make them very suitable for this kind of applications. Among the strategies used at present to preserve the quality of the water and this way to diminish the environmental risk that supposes the chemical pollution, stands out the use of adsorbents of under cost, already they are natural or modified, to immobilize these compounds and to avoid the pollution of the water with the consequent reduction of environmental and economic costs. We have studied the adsorption of several contaminants related to the food industry by natural or modified clays, searching their interaction mechanisms and the possible recycling of these materials for environmental purposes and prevention of the health. We have used the FT-IR spectroscopy and DTA/TG studies to confirm the reciclability of these materials and the possible application in the industry to prevent the contamination. References -del Hoyo, C. (2007). Applied Clay Science. 36, 103-121.Layered Double Hydroxides and human health: An overview. -Valderrábano, M., Rodríguez-Cruz, S., del Hoyo, C., Sánchez-Martín, M.J. (2006). 4th International Workshop "Bioavalailability of pollutants and soil remediation". 1, 5-6. Physicochemical study of the adsorption of pesticides by lignins. -Volzone, C. (2007). Applied Clay Science. 36, 191-196. Retention of pollutant gases: Comparison between clay minerals and their modified products.

  3. Sorption of Cm(III) and Eu(III) onto clay minerals under saline conditions: Batch adsorption, laser-fluorescence spectroscopy and modeling

    NASA Astrophysics Data System (ADS)

    Schnurr, Andreas; Marsac, Rémi; Rabung, Thomas; Lützenkirchen, Johannes; Geckeis, Horst

    2015-02-01

    The present work reports experimental data for trivalent metal cation (Cm/Eu) sorption onto illite (Illite du Puy) and montmorillonite (Na-SWy-2) in NaCl solutions up to 4.37 molal (m) in the absence of carbonate. Batch sorption experiments were carried out for a given ionic strength at fixed metal concentration (mEu = 2 × 10-7 m, labeled with 152Eu for γ-counting) and at a constant solid to liquid ratio (S:L = 2 g/L) for 3 < pHm < 12 (pHm = -log mH+). The amount of clay sorbed Eu approaches almost 100% (with log KD > 5) for pHm > 8, irrespective of the NaCl concentration. Variations in Eu uptake are minor at elevated NaCl concentrations. Time-resolved laser fluorescence spectroscopy (TRLFS) studies on Cm sorption covering a wide range of NaCl concentrations reveal nearly identical fluorescence emission spectra after peak deconvolution, i.e. no significant variation of Cm surface speciation with salinity. Beyond the three surface complexes already found in previous studies an additional inner-sphere surface species with a fluorescence peak maximum at higher wavelength (λ ∼ 610 nm) could be resolved. This new surface species appears in the high pH range and is assumed to correspond to a clay/curium/silicate complex as already postulated in the literature for kaolinite. The 2 site protolysis non-electrostatic surface complexation and cation exchange sorption model (2SPNE SC/CE) was applied to describe Eu sorption data by involving the Pitzer and SIT (specific ion interaction) formalism in the calculation of the activities of dissolved aqueous species. Good agreement of model and experiment is achieved for sorption data at pHm < 6 without the need of adjusting surface complexation constants. For pHm > 6 in case of illite and pHm > 8 in case of montmorillonite calculated sorption data systematically fall below experimental data with increasing ionic strength. Under those conditions sorption is almost quantitative and deviations must be discussed considering uncertainties of measured Eu concentrations in the range of analytical detection limits.

  4. Reversible surface-sorption-induced electron-transfer oxidation of Fe(II) at reactive sites on a synthetic clay mineral

    NASA Astrophysics Data System (ADS)

    Géhin, A.; Grenèche, J.-M.; Tournassat, C.; Brendlé, J.; Rancourt, D. G.; Charlet, L.

    2007-02-01

    The sorption of 57Fe(II) onto an Fe-free, mineralogically pure and Ca-saturated synthetic montmorillonite sample (structural formula: Ca 0.15(Al 1.4Mg 0.6)(Si 4)O 10(OH,F) 2), was studied as a function of pH under strictly anoxic conditions (N 2 glove box atmosphere, O 2 content <1 ppm), using wet chemistry and cryogenic ( T = 77 K) 57Fe Mössbauer spectrometry. No Fe(III) was detected in solution at any pH. However, in pH conditions where Fe(II) is removed from solution, a significant amount of surface-bound Fe(III) was produced, which increased with pH from 0% to 3% of total Fe in a pre-sorption edge region (i.e. at pH < 7.5 where about 15% of total Fe is sorbed) to 7% of total Fe when all Fe is sorbed. At low pH, where the pre-sorption edge plateau occurs (2 < pH < 7.5), the total sorbed-Fe amount remained constant but, within this sorbed-Fe pool, the Fe(III)/Fe(II) ratio increased with pH, from 0.14 at pH 2 up to 0.74 at pH 7. The pre-sorption edge plateau is interpreted as cation exchange on interlayer surfaces together with a sorption phenomenon occurring on highly reactive (i.e. high affinity) surface sites. As pH increases and protons are removed from the clay edge surface, we propose that more and more of these highly reactive sites acquire a steric configuration that stabilizes Fe(III) relative to Fe(II), thereby inducing a Fe to clay particle electron transfer. A sorption model based on cation exchange combined with surface complexation and electron transfers reproduces both wet chemical as well as the Mössbauer spectrometric results. The mechanism is fully reversible: sorbed-Fe is reduced as pH decreases (Mössbauer solid-state analyses) and all Fe returned to solution is returned as Fe(II) (solution analyses). This would not be the case if the observed oxidations were due to contaminant oxidizing agents in solution. The present work shows that alternating pH may induce surface redox phenomena in the absence of an electron acceptor in solution other than H 2O.

  5. Genotoxic potential of montmorillonite clay mineral and alteration in the expression of genes involved in toxicity mechanisms in the human hepatoma cell line HepG2.

    PubMed

    Maisanaba, Sara; Hercog, Klara; Filipic, Metka; Jos, Ángeles; Zegura, Bojana

    2016-03-01

    Montmorillonite, also known as Cloisite(®)Na(+) (CNa(+)), is a natural clay with a wide range of well-documented and novel applications, such as pharmaceutical products or food packaging. Although considered a low toxic product, the expected increased exposure to CNa(+) arises concern on the potential consequences on human and environmental health especially as its genotoxicity has scarcely been investigated so far. Thus, we investigated, for the first time, the influence of non-cytotoxic concentrations of CNa(+) (15.65, 31.25 and 62.5 μg/mL) on genomic instability of human hepatoma cell line (HepG2) by determining the formation of micronuclei (MNi), nucleoplasmic bridges (NPBs) and nuclear buds (NBUDs) with the Cytokinesis block micronucleus cytome assay. Further on we studied the influence of CNa(+) on the expression of several genes involved in toxicity mechanisms using the real-time quantitative PCR. The results showed that CNa(+) increased the number of MNi, while the numbers of NBUDs and NPBs were not affected. In addition it deregulated genes in all the groups studied, mainly after longer time of exposure. These findings provide the evidence that CNa(+) is potentially genotoxic. Therefore further studies that will elucidate the molecular mechanisms involved in toxic activity of CNa(+) are needed for hazard identification and human safety assessment. PMID:26599662

  6. Magnetic composites from minerals: study of the iron phases in clay and diatomite using Mössbauer spectroscopy, magnetic measurements and XRD

    NASA Astrophysics Data System (ADS)

    Cabrera, M.; Maciel, J. C.; Quispe-Marcatoma, J.; Pandey, B.; Neri, D. F. M.; Soria, F.; Baggio-Saitovitch, E.; de Carvalho, L. B.

    2014-01-01

    Magnetic particles as matrix for enzyme immobilization have been used and due to the enzymatic derivative can be easily removed from the reaction mixture by a magnetic field. This work presents a study about the synthesis and characterization of iron phases into magnetic montmorillonite clay (mMMT) and magnetic diatomaceous earth (mDE) by 57Fe Mössbauer spectroscopy (MS), magnetic measurements and X-ray diffraction (XRD). Also these magnetic materials were assessed as matrices for the immobilization of invertase via covalent binding. Mössbauer spectra of the magnetic composites performed at 4.2 K showed a mixture of magnetite and maghemite about equal proportion in the mMMT, and a pure magnetite phase in the sample mDE. These results were verified using XRD. The residual specific activity of the immobilized invertase on mMMT and mDE were 83 % and 92.5 %, respectively. Thus, both magnetic composites showed to be promising matrices for covalent immobilization of invertase.

  7. Size-based speciation of iron in clay mineral particles by gravitational field-flow fractionation with electrothermal atomic absorption spectrometry

    NASA Astrophysics Data System (ADS)

    Chantiwas, Rattikan; Beckett, Ronald; Grudpan, Kate

    2005-01-01

    Gravitational field-flow fractionation (FFF) coupled to UV and ETAAS detectors has been tested for micron-size particles in the range of 5-20 μm using three Fe-rich clay samples. The iron content estimated after aqua regia extraction was about 20-40 mg kg -1. The ETAAS analysis was performed both off-line from collected fractions and in an online continuous sampling mode using a specially designed flow through vial placed in the autosampler of the ETAAS. Comparison of the direct injection method with total analysis after aqua regia digestion shows that slurry injection of the dilute samples in the gravitational field-flow fractionation (GrFFF) effluent is quite efficient in these samples. In the majority of cases, more than 90% recovery was obtained for the slurry injection method. Fe mass-based particle size distributions and Fe concentration versus particle diameter plots can be generated using certain assumptions. This provides detailed information on size-based speciation of particulate samples. Generally, the Fe concentrations in the particles decreased slightly with an increase in particle size as is often found for soil and sediment samples.

  8. Diagenesis and fluid flow in the San Juan Basin, New Mexico - regional zonation in the mineralogy and stable isotope composition of clay minerals in sandstone.

    USGS Publications Warehouse

    Whitney, G.; Northrop, H.R.

    1987-01-01

    The Westwater Canyon Member of the Upper Jurassic Morrison Formation is a relatively homogeneous, hydrologically continuous 100-m-thick sequence of massive fluvial sandstone, bounded above and below by relatively heterogeneous, hydrologically discontinuous units and has served as a primary conduit for fluids within this stratigraphic interval. Patterns of mineral-fluid reactions suggest a basinwide hydrologic regime in which warm, evolved fluids migrated up-dip from the center of the basin under the influence of a regional hydraulic head. -from Authors

  9. Graywacke matrix minerals: hydrothermal reactions with columbia river sediments.

    PubMed

    Hawkins, J W; Whetten, J T

    1969-11-14

    Experiments with sands chemically similar to graywackes produced "matrix" minerals at 250 degrees C and a water pressure of 1 kilobar. Starting materials were moderately well sorted sands containing abundant volcanic rock fragments and no detectable clay minerals. The results support the concept that graywacke matrix may form diagenetically by hydration and recrystallization of unstable clasts. Matrix need not be a recrystallized detrial fine fraction. Texture, therefore, is not a reliable criterion for sandstone classification. For graywackes, chemical composition may be more significant. PMID:17815746

  10. The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California

    SciTech Connect

    Maher, K.; Steefel, C. I.; White, A.F.; Stonestrom, D.A.

    2009-02-25

    In order to explore the reasons for the apparent discrepancy between laboratory and field weathering rates and to determine the extent to which weathering rates are controlled by the approach to thermodynamic equilibrium, secondary mineral precipitation and flow rates, a multicomponent reactive transport model (CrunchFlow) was used to interpret soil profile development and mineral precipitation and dissolution rates at the 226 ka marine terrace chronosequence near Santa Cruz, CA. Aqueous compositions, fluid chemistry, transport, and mineral abundances are well characterized (White et al., 2008, GCA) and were used to constrain the reaction rates for the weathering and precipitating minerals in the reactive transport modeling. When primary mineral weathering rates are calculated with either of two experimentally determined rate constants, the nonlinear, parallel rate law formulation of Hellmann and Tisser and [2006] or the aluminum inhibition model proposed by Oelkers et al. [1994], modeling results are consistent with field-scale observations when independently constrained clay precipitation rates are accounted for. Experimental and field rates, therefore, can be reconciled at the Santa Cruz site. Observed maximum clay abundances in the argillic horizons occur at the depth and time where the reaction fronts of the primary minerals overlap. The modeling indicates that the argillic horizon at Santa Cruz can be explained almost entirely by weathering of primary minerals and in situ clay precipitation accompanied by undersaturation of kaolinite at the top of the profile. The rate constant for kaolinite precipitation was also determined based on model simulations of mineral abundances and dissolved Al, SiO{sub 2}(aq) and pH in pore waters. Changes in the rate of kaolinite precipitation or the flow rate do not affect the gradient of the primary mineral weathering profiles, but instead control the rate of propagation of the primary mineral weathering fronts and thus total mass removed from the weathering profile. Our analysis suggests that secondary clay precipitation is as important as aqueous transport in governing the amount of dissolution that occurs within a profile because clay minerals exert a strong control over the reaction affinity of the dissolving primary minerals. The modeling also indicates that the weathering advance rate and the total mass of mineral dissolved is controlled by the thermodynamic saturation of the primary dissolving phases plagioclase and K-feldspar, as is evident from the difference in propagation rates of the reaction fronts for the two minerals despite their very similar kinetic rate laws.

  11. Characterizing regional soil mineral composition using spectroscopyand geostatistics

    USGS Publications Warehouse

    Mulder, V.L.; de Bruin, S.; Weyermann, J.; Kokaly, Raymond F.; Schaepman, M.E.

    2013-01-01

    This work aims at improving the mapping of major mineral variability at regional scale using scale-dependent spatial variability observed in remote sensing data. Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) data and statistical methods were combined with laboratory-based mineral characterization of field samples to create maps of the distributions of clay, mica and carbonate minerals and their abundances. The Material Identification and Characterization Algorithm (MICA) was used to identify the spectrally-dominant minerals in field samples; these results were combined with ASTER data using multinomial logistic regression to map mineral distributions. X-ray diffraction (XRD)was used to quantify mineral composition in field samples. XRD results were combined with ASTER data using multiple linear regression to map mineral abundances. We testedwhether smoothing of the ASTER data to match the scale of variability of the target sample would improve model correlations. Smoothing was donewith Fixed Rank Kriging (FRK) to represent the mediumand long-range spatial variability in the ASTER data. Stronger correlations resulted using the smoothed data compared to results obtained with the original data. Highest model accuracies came from using both medium and long-range scaled ASTER data as input to the statistical models. High correlation coefficients were obtained for the abundances of calcite and mica (R2 = 0.71 and 0.70, respectively). Moderately-high correlation coefficients were found for smectite and kaolinite (R2 = 0.57 and 0.45, respectively). Maps of mineral distributions, obtained by relating ASTER data to MICA analysis of field samples, were found to characterize major soil mineral variability (overall accuracies for mica, smectite and kaolinite were 76%, 89% and 86% respectively). The results of this study suggest that the distributions of minerals and their abundances derived using FRK-smoothed ASTER data more closely match the spatial variability of soil and environmental properties at regional scale.

  12. Thermo Gravimetric and Differential Thermal Analysis of Clay of Western Rajasthan (india)

    NASA Astrophysics Data System (ADS)

    Shekhawat, M. S.

    The paper presents the study of thermo gravimetric and differential thermal analysis of blended clay. Western part of Rajasthan (India) is rich resource of Ball clays and it is mainly used by porcelain, sanitary ware, and tile industry. The quality and grade of clay available in the region vary from one deposit to other. To upgrade the fired colour and strength properties, different variety of clays may be blended together. The paper compares the results of thermal analysis one of blended clay B2 with reference clay of Ukraine which is imported by industries owners. The result revealed that the blended clay is having mineral kaolinite while the Ukrainian clay is Halloysite.

  13. CLAY AND CLAY-SUPPORTED REAGENTS IN ORGANIC SYNTHESES

    EPA Science Inventory

    CLAY AND CLAY-SUPPORTED REAGENTS HAVE BEEN USED EXTENSIVELY FOR SYNTHETIC ORGANIC TRANSFORMATIONS. THIS OVERVIEW DESCRIBES THE SALIENT STRUCTURAL PROPERTIES OF VARIOUS CLAY MATERIALS AND EXTENDS THE DISCUSSION TO PILLARED CLAYS AND REAGENTS SUPPORTED ON CLAY MATERIALS. A VARIET...

  14. Formation of hydrocarbons from acid-Clay suspensions by gamma irradiation

    NASA Astrophysics Data System (ADS)

    Cruz-Castañeda, J.; Negron-Mendoza, A.; Ramos-Bernal, S.

    2013-07-01

    The adsorption of certain organic compounds by clays gives rise to the transformation of the adsorbate through the action of the clays. This phenomenon can be enhanced using ionizing radiation. In this context, these kinds of reactions play an important role in many natural and industrial processes. For example, in oil and gas exploration, the source and trap of petroleum hydrocarbons is frequently clay-rich rocks. Clay-water-based muds are also seen as environmentally friendly alternatives to toxic oil-based fluids. The principal processes that occur in sediments are usually held to be of bacterial action and thermal transformation, which may include thermally induced catalytic alteration of the organic debris. On the other hand, radioactive materials are widely distributed throughout Earth. They were more abundant in the past, but are present in petroleum reservoirs. Their presence induced radioactive bombardment, which may have altered these sediments. This important subject has not been extensively studied. The aim of this work is to study the behavior of fatty acids—like behenic acid—and dicarboxylic acids—like fumaric acid—as model compounds, which are adsorbed in a clay mineral (Na-montmorillonite) and exposed to gamma radiation. The results show that the radiation-induced decomposition of the clay-acid system goes along a definitive path (oxidation), rather than following several modes of simultaneous decomposition, as happens in radiolysis without clay or by heating the system. The main radiolytic products for fatty acids are their corresponding hydrocarbons, with one C-atom less than the original acid.

  15. Formation of hydrocarbons from acid-Clay suspensions by gamma irradiation

    SciTech Connect

    Cruz-Castaneda, J.; Negron-Mendoza, A.; Ramos-Bernal, S.

    2013-07-03

    The adsorption of certain organic compounds by clays gives rise to the transformation of the adsorbate through the action of the clays. This phenomenon can be enhanced using ionizing radiation. In this context, these kinds of reactions play an important role in many natural and industrial processes. For example, in oil and gas exploration, the source and trap of petroleum hydrocarbons is frequently clay-rich rocks. Clay-water-based muds are also seen as environmentally friendly alternatives to toxic oil-based fluids. The principal processes that occur in sediments are usually held to be of bacterial action and thermal transformation, which may include thermally induced catalytic alteration of the organic debris. On the other hand, radioactive materials are widely distributed throughout Earth. They were more abundant in the past, but are present in petroleum reservoirs. Their presence induced radioactive bombardment, which may have altered these sediments. This important subject has not been extensively studied. The aim of this work is to study the behavior of fatty acids-like behenic acid-and dicarboxylic acids-like fumaric acid-as model compounds, which are adsorbed in a clay mineral (Na-montmorillonite) and exposed to gamma radiation. The results show that the radiation-induced decomposition of the clay-acid system goes along a definitive path (oxidation), rather than following several modes of simultaneous decomposition, as happens in radiolysis without clay or by heating the system. The main radiolytic products for fatty acids are their corresponding hydrocarbons, with one C-atom less than the original acid.

  16. Imprinted Clay Coil Vessels

    ERIC Educational Resources Information Center

    Lohr, Tresa Rae

    2006-01-01

    The author teaches clay vessel construction in the fifth grade, and it is amazing what can be accomplished in one forty-five minute period when the expectations are clarified in the initial lesson. The author introduces clay coil vessels with a discussion of the sources of clay and how clay relates to fifth-grade science curriculum concepts such…

  17. Griffith Saponite as an Analog for Clay Minerals at Yellowknife Bay in Gale Crater, Mars: A Marker for Low-temperature Hydrothermal Processes

    NASA Technical Reports Server (NTRS)

    Morris, R.V.; Treiman, A. H.; Agresti, D. G.; Graff, T. G.; Achilles, C. N.; Rampe, E. B.; Bristow, T. F.; Ming, D. W.; Blake, D. F.; Vaniman, D. T.; Bish, D. L.; Chipera, S. J.; Morrison, S. M.; Downs, R. T.

    2014-01-01

    The CheMin X-ray diffraction (XRD) instrument onboard the Mars Science Laboratory rover Curiosity in Gale Crater, Mars, discovered smectite in drill fines of the Sheepbed mudstone at Yellowknife Bay (YNB). The mudstone has a basaltic composition, and the XRD powder diffraction pattern shows smectite 02l diffraction bands peaking at 4.59 A for targets John Klein and Cumberland, consistent with tri-octahedral smectites (saponite). From thermal analysis, the saponite abundance is 20 wt. %. Among terrestrial analogues we have studied, ferrian saponite from Griffith Park (Los Angeles, CA) gives the best match to the position of the 02l diffraction band of YNB saponites. Here we describe iron-rich saponites from a terrestrial perspective, with a focus on Griffith saponite, and discuss their implications for the mineralogy of Sheepbed saponite and its formation pathways. Iron-rich saponite: Iron-rich saponite on the Earth is recognized as a low-temperature (<100 C), authigenic alteration product of basalt [e.g., 4-16]. In the discussion that follows, we reference the position of the 02l band because it is a measure of the unit cell 'b' dimension of the octahedral layer and thus the cations (including Fe redox state) in the octahedral layer. Ordinarily, the 06l band near 1.5 A is used to determine the 'b' dimension of smectite, but this band is not accessible with MSL CheMin instrument. For reference, a ferrosaponite (i.e., Fe2+ saponite) studied by [15] has a 02l spacing of 4.72 A and Fe3+/?Fe = 0.27 [15]. Samples of terrestrial ferrosaponite, however, are reported to oxidize on the timescale of days when removed from their natural environment and not protected from oxidation. The Griffith saponite is Mg-rich ferrian saponite, and sample AMNH 89172 has an 02l spacing of 4.59 A (same as the Sheepbed saponites) and Fe3+/?Fe = 0.64 [3]. This similarity suggests that Sheepbed saponites are ferrian (incompletely oxidized ferrosaponite). More oxidized Griffith saponites (Fe3+/?Fe > 0.90) have somewhat smaller 02l d-spacings and also show Mossbauer evidence for an XRD amorphous Fe-bearing phase (e.g., ferrihydrite, hisingerite, superparamagnetic ferric oxides, etc.). The Griffith saponite occurs as vesicle fills, as replacements of olivine, and as replacements of mesostasis (basaltic glass). Similar occurrence modes are reported elsewhere. Hisingerite has been proposed by [13] as the alteration product of ferrian saponite whose precursor by oxidation was ferrosaponite.

  18. Common clay and shale

    USGS Publications Warehouse

    Virta, R.L.

    2011-01-01

    The article discusses the latest developments in the global common clay and shale industry, particularly in the U.S. It claims that common clay and shale is mainly used in the manufacture of heavy clay products like brick, flue tile and sewer pipe. The main producing states in the U.S. include North Carolina, New York and Oklahoma. Among the firms that manufacture clay and shale-based products are Mid America Brick & Structural Clay Products LLC and Boral USA.

  19. Abundances of platinum group elements in native sulfur condensates from the Niuatahi-Motutahi submarine volcano, Tonga rear arc: Implications for PGE mineralization in porphyry deposits

    NASA Astrophysics Data System (ADS)

    Park, Jung-Woo; Campbell, Ian H.; Kim, Jonguk

    2016-02-01

    Some porphyry Cu-Au deposits, which are enriched in Pd, are potentially an economic source of Pd. Magmatic volatile phases are thought to transport the platinum group elements (PGEs) from the porphyry source magma to the point of deposition. However, the compatibilities of the PGEs in magmatic volatile phases are poorly constrained. We report PGE and Re contents in native sulfur condensates and associated altered dacites from the Niuatahi-Motutahi submarine volcano, Tonga rear arc, in order to determine the compatibility of PGEs and Re in magmatic volatile phases, and their mobility during secondary hydrothermal alteration. The native sulfur we analyzed is the condensate of a magmatic volatile phase exsolved from the Niuatahi-Motutahi magma. The PGEs are moderately enriched in the sulfur condensates in comparison to the associated fresh dacite, with enrichment factors of 11-285, whereas Au, Cu and Re are strongly enriched with enrichment factors of ∼20,000, ∼5000 and ∼800 respectively. Although the PGEs are moderately compatible into magmatic volatile phases, their compatibility is significantly lower than that of Au, Cu and Re. Furthermore, the compatibility of PGEs decrease in the order: Ru > Pt > Ir > Pd. This trend is also observed in condensates and sublimates from other localities. PGE mineralization in porphyry Cu-Au deposits is characterized by substantially higher Pd/Pt (∼7-60) and Pd/Ir (∼100-10,500) than typical orthomagmatic sulfide deposits (e.g. Pd/Pt ∼0.6 and Pd/Ir ∼20 for the Bushveld). It has previously been suggested that the high mobility of Pd, relative to the other PGEs, may account for the preferential enrichment of Pd in porphyry Cu-Au deposits. However, the low compatibility of Pd in the volatile phase relative to the other PGEs, shown in this study, invalidates this explanation. We suggest that the PGE geochemistry of Pd-rich Cu-Au deposits is principally derived from the PGE characteristics of the magma from which the ore-forming fluid exsolved. Pd-rich porphyry Cu-Au deposits are associated with highly oxidized magmas. Prior to sulfide saturation Pd, Au and Cu behave as incompatible elements and concentrate in the melt with fractional crystallization, whereas Pt is depleted by early crystallization of a Pt-rich alloy and the other PGEs by the co-crystallization of the Pt-rich alloy and Cr spinel. As a consequence the Pd/Pt and Pd/Ir in the evolving melt and the magmatic volatile phases that exsolve from that melt, increase with increased fractionation. The high Pd content and high Pd/Pt (∼7-60) of Cu-Au porphyry ores therefore require the parent magma to have undergone extensive sulfide-undersaturated fractional crystallization prior to volatile exsolution. Our study also showed that the altered dacites contain PGE abundances that are similar to those of fresh dacites although Pt and Rh are slightly enriched in the altered dacites, which indicates low mobility of PGEs during secondary hydrothermal alteration.

  20. A granulometry and secondary mineral fingerprint of chemical weathering in periglacial landscapes and its application to blockfield origins

    NASA Astrophysics Data System (ADS)

    Goodfellow, Bradley W.

    2012-12-01

    A review of published literature was undertaken to determine if there was a fingerprint of chemical weathering in regoliths subjected to periglacial conditions during their formation. If present, this fingerprint would be applied to the question of when blockfields in periglacial landscapes were initiated. These blocky diamicts are usually considered to represent remnants of regoliths that were chemically weathered under a warm, Neogene climate and therefore indicate surfaces that have undergone only a few metres to a few 10s of metres of erosion during the Quaternary. Based on a comparison of clay and silt abundances and secondary mineral assemblages from blockfields, other regoliths in periglacial settings, and regoliths from non-periglacial settings, a fingerprint of chemical weathering in periglacial landscapes was identified. A mobile regolith origin under, at least seasonal, periglacial conditions is indicated where clay(%) ≤ 0.5*silt(%) + 8 across a sample batch. This contrasts with a mobile regolith origin under non-periglacial conditions, which is indicated where clay(%) ≥ 0.5*silt(%) - 6 across a sample batch with clay(%) ≥ 0.5*silt(%) + 8 in at least one sample. A range of secondary minerals, which frequently includes interstratified minerals and indicates high local variability in leaching conditions, is also commonly present in regoliths exposed to periglacial conditions during their formation. Clay/silt ratios display a threshold response to temperature, related to the freezing point of water, but there is little response to precipitation or regolith residence time. Lithology controls clay and silt abundances, which increase from felsic, through intermediate, to mafic compositions, but does not control clay/silt ratios. Use of a sedigraph or Coulter Counter to determine regolith granulometry systematically indicates lower clay abundances and intra-site variability than use of a pipette or hydrometer. In contrast to clay/silt ratios, secondary mineral assemblages vary according to regolith residence time, temperature, and/or precipitation. A microsystems model is invoked as a conceptual framework in which to interpret the concurrent formation of the observed secondary mineral ranges. According to the fingerprint of chemical weathering in periglacial landscapes, there is generally no evidence of blockfield origins under warm Neogene climates. Nearly all blockfields appear to be a product of Quaternary physical and chemical weathering. A more dominant role for periglacial processes in further bevelling elevated, low relief, non-glacial surface remnants in otherwise glacially eroded landscapes is therefore indicated.

  1. Maps showing interpretation, using R-mode factor analysis, of trace-element abundances in heavy-mineral concentrate samples, Delta 1° x 2° Quadrangle, Utah

    USGS Publications Warehouse

    Zimbelman, David R.

    1994-01-01

    A set of heavy-mineral concentrate data for the Delta 1° x 2° quadrangle, Utah Conterminous U.S. Mineral Assessment Program (CUSMAP) project was compiled from results of analyses of samples collected during the National Uranium Resource Evaluation Program (SURE), as well as results obtained from samples collected more recently by the USGS. Data results, sampling methods, and analytical methods are provided in Abrogast and others, 1993; 1990; 1988a; 1988b). A similar report, discussing results obtained from stream-sediment samples, is presented in Zimbelman (1993a). The Delta 1° x 2° quadrangle, Utah (figure 1) contains a variety of hydrothermal mineral deposit types, including porphyry-, vein-, replacement-, and Carlin-type deposits. These deposit types have been worked for commodities including gold, silver, beryllium, uranium, lead, zinc, copper, manganese, and cadmium (Lindsey, 1977; Morris and Mogensen, 1978; Zimbelman and others, 1990; Zimbelman and others, 1988). Heavy-mineral concentrate and stream-sediment samples derived from these hydrothermally altered rocks typically contain many geochemical anomalies (for example, see Zimbelman 1993b, c, d). Element associations characterizing lithology and hydrothermal mineral deposits can be distinguished using R-mode factor analysis. This tool often is useful in reconnaissance-scale surveys where sample anomalies are often weak. and single-element distributions may not help to delineate targets. R-mode factors analysis can help identify geologic trends and areas most likely to contain the mineral deposits. R-mode factor analysis was performed on a data set of results of analyses for 19 elements in 643 samples and produced a six-factor model. These six factors represent the geochemical contributions to the data set provided by lithologic and mineralization processes, The distribution of samples that contain high scores for mineralization-related factors is widespread in the Delta quadrangle. These sample sites are though to relate to both known prospect and mineralization areas, as well as define new areas that are geochemically favorable to contain altered or mineralized rocks.

  2. Ion-exchange reactions on clay minerals coupled with advection/dispersion processes. Application to Na+/Ca2+ exchange on vermiculite: Reactive-transport modeling, batch and stirred flow-through reactor experiments

    NASA Astrophysics Data System (ADS)

    Tertre, E.; Hubert, F.; Bruzac, S.; Pacreau, M.; Ferrage, E.; Prêt, D.

    2013-07-01

    The present study aims at testing the validity of using an Na+/Ca2+ ion-exchange model, derived from batch data to interpret experimental Ca2+-for-Na+ exchange breakthrough curves obtained on vermiculite (a common swelling clay mineral in surface environments). The ion-exchange model was constructed considering the multi-site nature of the vermiculite surface as well as the exchange of all aqueous species (Mg2+ derived from the dissolution of the solid and H+). The proposed ion-exchange model was then coupled with a transport model, and the predicted breakthrough curves were compared with the experimental ones obtained using a well stirred flow-through reactor. For a given solute residence time in the reactor (typically 50 min), our thermodynamic model based on instantaneous equilibrium was found to accurately reproduce several of the experimental breakthrough curves, depending on the Na+ and Ca2+ concentrations of the influents pumped through the reactor. However the model failed to reproduce experimental breakthrough curves obtained at high flow rates and low chemical gradient between the exchanger phase and the solution. An alternative model based on a hybrid equilibrium/kinetic approach was thus used and allowed predicting experimental data. Based on these results, we show that a simple parameter can be used to differentiate between thermodynamic and kinetic control of the exchange reaction with water flow. The results of this study are relevant for natural systems where two aquatic environments having contrasted chemistries interact. Indeed, the question regarding the attainment of a full equilibrium in such a system during the contact time of the aqueous phase with the particle/colloid remains most often open. In this context, we show that when a river (a flow of fresh water) encounters marine colloids, a systematic full equilibrium can be assumed (i.e., the absence of kinetic effects) when the residence time of the solute in 1 m3 of the system is ⩾6200 h.

  3. Phosphates in some missouri refractory clays

    USGS Publications Warehouse

    Hall, R.B.; Foord, E.E.; Keller, D.J.; Keller, W.D.

    1997-01-01

    This paper describes in detail phosphate minerals occurring in refractory clays of Missouri and their effect on the refractory degree of the clays. The minerals identified include carbonate-fluorapatite (francolite), crandallite, goyazite, wavellite, variscite and strengite. It is emphasized that these phosphates occur only in local isolated concentrations, and not generally in Missouri refractory clays. The Missouri fireclay region comprises 2 districts, northern and southern, separated by the Missouri River In this region, clay constitutes a major part of the Lower Pennsylvanian Cheltenham Formation. The original Cheltenham mud was an argillic residue derived from leaching and dissolution of pre-Pennsylvanian carbonates. The mud accumulated on a karstic erosion surface truncating the pre-Cheltenham rocks. Fireclays of the northern district consist mainly of poorly ordered kaolinite, with variable but minor amounts of illite, chlorite and fine-grained detrital quartz. Clays of the southern district were subjected to extreme leaching that produced well-ordered kaolinite flint clays. Local desilication formed pockets of diaspora, or more commonly, kaolinite, with oolite-like nubs or burls of diaspore ("burley" clay). The phosphate-bearing materials have been studied by X-ray diffraction (XRD), scanning electron microscopy-energy dispersive spectral analysis (SEM-EDS) and chemical analysis. Calcian goyazite was identified in a sample of diaspore, and francolite in a sample of flint clay. A veinlet of wavellite occurs in flint clay at one locality, and a veinlet of variscite-strengite at another locality. The Missouri flint-clay-hosted francolite could not have formed in the same manner as marine francolite The evidence suggests that the Cheltenham francolite precipitated from ion complexes in pore water nearly simultaneously with crystallization of kaolinite flint clay from an alumina-silica gel. Calcian goyazite is an early diagenetic addition to its diaspore host. The wavellite and variscite-strengite veinlets are secondary, precipitated from ion complexes in ground water percolating along cracks in the flint clay. The flint clay host of the variscite-strengite veinlet contains strontian crandallite. All of the phosphates contain significant amounts of strontium. The source of P, Ca and Sr was the marine carbonates. Dissolution of these carbonates produced the argillic residue that became the primordial Cheltenham paludal mud, which ultimately altered to fireclay. Preliminary firing tests show that the presence of phosphates lowers fusion temperature. However, it is not clear whether poor refractoriness is due to the presence of phosphates, per se, or to Ca, Sr and other alkaline elements present in the phosphates.

  4. Coronal Abundances

    NASA Astrophysics Data System (ADS)

    Fludra, A.; Saba, J. L. R.; Henoux, J.-C.; Murphy, R. J.; Reames, D. V.; Lemen, J. R.; Strong, K. T.; Sylwester, J.; Widing, K. G.

    Flare X-Ray Measurements from BCS Calcium Abundance Fe/H and Fe/Ca Abundance Relative Abundances of Ar. Ca. and Fe in Flares Factors Affecting Abundance Determinations from X-Ray Spectra FCS Abundances FCS Active-Region Abundances Abundance Variability in Active Regions Impact of Resonance Scattering Assessment of FCS Active-Region Abundance Results FCS Flare Abundance Studies Coronal CI/S and Ar/S Measurements Dem Studies of Flare Abuncances Determination of Solar Abundances by Solar Flare γ-Ray Spectrometry γ-Ray Spectral Analysis γ-Ray Results Solar Energetic Particles Major Proton Events CIR Events from Coronal Holes Impulsive Flare Events Theory of Abundance Fractionation Gravitational Settling Pressure Gradient and Stationary Diffusion Ion-Neutral Separation Due to Currents Ion-Neutral Separation Due to Electromagnetic Forces Discussion Summary

  5. ADSORPTION OF BACTERIOPHAGES ON CLAY MINERALS

    EPA Science Inventory

    Theability to predict the fate of microorganisms in soil is dependent on an understanding of the process of their sorption on soil and subsurface materials. Presently, we have focused on studying the thermodynamics of sorption of bacteriophages (T-2, MS-2, and

  6. Prolonged triboluminescence in clays and other minerals

    NASA Technical Reports Server (NTRS)

    Lahav, N.; Coyne, L. M.; Lawless, J. G.

    1982-01-01

    The decay curves of various triboluminescent-excited materials were obtained, including well-crystallized and poorly crystallized kaolin, bentonite, quartz, sodium chloride, and chalk calcite. A qualitative increase in triboluminescence was observed for kaolin dipped in water or tryptophan solution compared to dry kaolin, and for frozen kaolin and montmorillonite pastes. Theoretical explanations for the tryptophan effect are discussed.

  7. Natural Radioactivity of Boron Added Clay Samples

    NASA Astrophysics Data System (ADS)

    Akkurt, I.; ćanakciı, H.; Mavi, B.; Günoǧlu, K.

    2011-12-01

    Clay, consisting fine-grained minerals, is an interesting materials and can be used in a variety of diferent fields especially in dermatology application. Using clay such a field it is important to measure its natural radioacitivty. Thus the purpose of this study is to measure 226Ra, 232Th and 40K concentration in clay samples enriched with boron. Three different types of clay samples were prepared where boron is used in different rate. The measurements have been determined using a gamma-ray spectrometry consists of a 3″×3″ NaI(Tl) detector. From the measured activity the radium equivalent activities (Raeq), external hazard index (Hex), absorbed dose rate in air (D) and annual effective dose (AED) have also been obtained.

  8. Natural Radioactivity of Boron Added Clay Samples

    SciTech Connect

    Akkurt, I.; Guenoglu, K.; Canakcii, H.; Mavi, B.

    2011-12-26

    Clay, consisting fine-grained minerals, is an interesting materials and can be used in a variety of different fields especially in dermatology application. Using clay such a field it is important to measure its natural radioactivity. Thus the purpose of this study is to measure {sup 226}Ra, {sup 232}Th and {sup 40}K concentration in clay samples enriched with boron. Three different types of clay samples were prepared where boron is used in different rate. The measurements have been determined using a gamma-ray spectrometry consists of a 3''x3'' NaI(Tl) detector. From the measured activity the radium equivalent activities (Ra{sub eq}), external hazard index (H{sub ex}), absorbed dose rate in air (D) and annual effective dose (AED) have also been obtained.