Understanding Potassium Isotope Fractionation During Authigenic Clay Formation in Pore-fluid Systems: Implications for the δ41K of Seawater

NASA Astrophysics Data System (ADS)

Santiago Ramos, D. P.; Higgins, J. A.

2015-12-01

Improvements in analytical precision on the latest generation multi-collector inductively coupled plasma mass spectrometers (MC-ICP-MS) have revealed a ~2‰ range in the ratios of stable potassium isotopes (41K/39K) in terrestrial materials (Morgan et al., in prep). Preliminary measurements of δ41K values indicate that seawater and silicate rocks are isotopically distinct reservoirs, with seawater having a δ41K value that is ~0.5‰ heavier than the silicate average (-0.5‰; Morgan et al., in prep). The heavy δ41K character of seawater might be related to 1) an isotopically enriched input flux (rivers and high-temperature hydrothermal reactions); or 2) a 41K-depleted sink associated with authigenic clay formation during low-temperature alteration of volcanic rocks. Here we present measurements of the δ41K values of pore-fluids from ODP site 1052 in order to constrain potassium isotope fractionation during secondary clay formation. We find that δ41K values and K concentrations both decline systematically with depth. Results from 1-D diffusion-advection-reaction modeling of potassium concentrations and isotopic compositions indicate that fractionation of K isotopes during diffusion (Bourg et al., 2010) can explain all of the change in δ41K values of the pore-fluid with depth. Although the size of the K sink at site 1052 is a trivial fraction of the global K sink in clay minerals, our results suggest that diffusive fractionation of K isotopes in shallow pore-fluids may be, in part, responsible for the elevated δ41K value of seawater.

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.

Geology and Refractory Clay Deposits of the Haldeman and Wrigley Quadrangles, Kentucky

USGS Publications Warehouse

Patterson, Sam H.; Hosterman, John W.; Huddle, John Warfield

1962-01-01

The Haldeman and Wrigley 7th-minute quadrangles are near the western edge of the eastern Kentucky coal field and cover an area of approximately 117 square miles in parts of Carter, Rowan, Elliott, and Morgan Counties, Ky. The rocks exposed in the two quadrangles are of Early and Late Mississippian and Early and Middle Pennsylvanian age. The Mississippian rocks are composed of the thick Brodhead formation, which consists of siltstone and shale, and eleven thin marine limestone and shale formations, having an aggregate thickness of about 150 feet. The Lee and Breathitt formations, of Pennsylvanian age, consist of sandstone, siltstone, and shale; they also contain thin beds of coal and several beds of underclay, including the economically important Olive Hill clay bed of Crider, 1913. Pennsylvanian rocks include beds of both continental and marine origin. The eleven thin Mississippian formations and the upper-most part of the thick Brodhead formation are truncated by a prominent unconformity on which rocks of Pennsylvanian age rest. The rocks occupy a region of gentle dips between the Cincinnati arch and the Appalachian Mountains. Refractory clay deposits are in the Olive Hill clay bed, which occurs in the lower part of the Lee formation. The Olive Hill clay bed is discontinuous and consists of a series of irregularly shaped lenses. The bed is approximately two-thirds semifiint clay and one-third flint clay, and it contains minor amounts of plastic clay. Some of the flint clay is nearly pure kaolinite, but the semi flint and plastic clay consists of mixtures of kaolinite, illite, and mixed-layer clay minerals. The structure of the kaolinite ranges from highly crystalline to very poorly crystalline 'fireclay' type. The degree of crystallinity of the kaolinite and the hardness of the clay vary inversely with the amount of illite and mixed-layer clay minerals present. The nearly pure kaolinite is believed to have formed by the removal of alkalies and some silica fram mixtures of kaolinite, illite, and mixed-layer clays by leaching in swamps to the deposition of the beds overlying the clay. The refractory properties of the clay vary directly with the purity of the kaolinite, and refractoriness decreases as the proportions of illite and mixed-layer clays increase. Certain nonclay minerals, chiefly siderite, pyrite, and iron oxide-bearing minerals, also act as fiuxes, reducing the refractory properties of the clay. The entire resources of clay in the Olive Hill clay bed are roughly and tentatively estimated to include 105,000,000 tons in the Haldeman quadrangle and 175,000,000 tons in the Wrigley quadrangle. Much of this clay is of poor quality and the amount that is better than the minimum requirements for use in refractories is probably about 30,000,000 tons. Only a fraction of this tonnage is suitable for superheat-duty products. Limestone is the only nonmetallic mineral resource other than refractory clay that has been developed in the two quadrangles, but 1arge amounts of shale suitable for use in making lightweight aggregate and structural clay products may also be present. Most of the limestone, which is quarried. in both quadrangles, is used for road-metal, concrete aggregate, and agriculture stone, but some of the limestone is of the quality that would be suitable for other uses. Virtually all the Mississippian Beech Creek limestone of Malott, 1919 which is as much as 18 feet thick, consists of high-calcium limestone. Shale beds that appear most favoralble for making lightweight aggregate are in the shale facies of the Lee formation of Pennsylvanian age. Shale that is probably suitable for structural clay products is present in the shale flacles of the Lee formation and in the Muldraugh formation of Mississippian age. Several dry holes have been drilled in search for oil and gas within the area of the two quadrangles. Though no commercial production was ever attained, one well furnished a supply of gas f

Microbially-accelerated consolidation of oil sands tailings. Pathway II: solid phase biogeochemistry.

PubMed

Siddique, Tariq; Kuznetsov, Petr; Kuznetsova, Alsu; Li, Carmen; Young, Rozlyn; Arocena, Joselito M; Foght, Julia M

2014-01-01

Consolidation of clay particles in aqueous tailings suspensions is a major obstacle to effective management of oil sands tailings ponds in northern Alberta, Canada. We have observed that microorganisms indigenous to the tailings ponds accelerate consolidation of mature fine tailings (MFT) during active metabolism by using two biogeochemical pathways. In Pathway I, microbes alter porewater chemistry to indirectly increase consolidation of MFT. Here, we describe Pathway II comprising significant, direct and complementary biogeochemical reactions with MFT mineral surfaces. An anaerobic microbial community comprising Bacteria (predominantly Clostridiales, Synergistaceae, and Desulfobulbaceae) and Archaea (Methanolinea/Methanoregula and Methanosaeta) transformed Fe(III) minerals in MFT to amorphous Fe(II) minerals during methanogenic metabolism of an added organic substrate. Synchrotron analyses suggested that ferrihydrite (5Fe2O3. 9H2O) and goethite (α-FeOOH) were the dominant Fe(III) minerals in MFT. The formation of amorphous iron sulfide (FeS) and possibly green rust entrapped and masked electronegative clay surfaces in amended MFT. Both Pathways I and II reduced the surface charge potential (repulsive forces) of the clay particles in MFT, which aided aggregation of clays and formation of networks of pores, as visualized using cryo-scanning electron microscopy (SEM). These reactions facilitated the egress of porewater from MFT and increased consolidation of tailings solids. These results have large-scale implications for management and reclamation of oil sands tailings ponds, a burgeoning environmental issue for the public and government regulators.

Microbially-accelerated consolidation of oil sands tailings. Pathway II: solid phase biogeochemistry

PubMed Central

Siddique, Tariq; Kuznetsov, Petr; Kuznetsova, Alsu; Li, Carmen; Young, Rozlyn; Arocena, Joselito M.; Foght, Julia M.

2014-01-01

Consolidation of clay particles in aqueous tailings suspensions is a major obstacle to effective management of oil sands tailings ponds in northern Alberta, Canada. We have observed that microorganisms indigenous to the tailings ponds accelerate consolidation of mature fine tailings (MFT) during active metabolism by using two biogeochemical pathways. In Pathway I, microbes alter porewater chemistry to indirectly increase consolidation of MFT. Here, we describe Pathway II comprising significant, direct and complementary biogeochemical reactions with MFT mineral surfaces. An anaerobic microbial community comprising Bacteria (predominantly Clostridiales, Synergistaceae, and Desulfobulbaceae) and Archaea (Methanolinea/Methanoregula and Methanosaeta) transformed FeIII minerals in MFT to amorphous FeII minerals during methanogenic metabolism of an added organic substrate. Synchrotron analyses suggested that ferrihydrite (5Fe2O3. 9H2O) and goethite (α-FeOOH) were the dominant FeIII minerals in MFT. The formation of amorphous iron sulfide (FeS) and possibly green rust entrapped and masked electronegative clay surfaces in amended MFT. Both Pathways I and II reduced the surface charge potential (repulsive forces) of the clay particles in MFT, which aided aggregation of clays and formation of networks of pores, as visualized using cryo-scanning electron microscopy (SEM). These reactions facilitated the egress of porewater from MFT and increased consolidation of tailings solids. These results have large-scale implications for management and reclamation of oil sands tailings ponds, a burgeoning environmental issue for the public and government regulators. PMID:24711806

Deep sea authigenic clays as a sink for seawater Mg through the Cenozoic

NASA Astrophysics Data System (ADS)

Dunlea, A. G.; Murray, R. W.; Ramos, D. S.; Higgins, J. A.

2016-12-01

The most enigmatic sink of many elements in the global ocean is the formation of authigenic aluminosilicates. Pelagic clays cover 40% of the seafloor and "reverse weathering" type reactions within this lithology have the potential to be a large sink of seawater Mg and affect carbon cycling in the ocean. We use pelagic clays from Integrated Ocean Drilling Program Expedition 329 Site U1366 in the South Pacific Gyre to track authigenic aluminosilicates with two complementary methods: (1) Mg isotopic analyses, and (2) bulk sediment geochemistry with provenance modeling. Mg isotopic analyses of the bulk, unleached clay samples reveal isotopic values significantly heavier than average continental crust (δ26Mg = -0.1 to -0.3%o) indicating significant authigenic uptake. The bulk sediment geochemistry (i.e., major, trace, rare earth element concentrations) and multivariate statistical models of provenance determine the mass fraction of six different sediment sources that mixed to create the sediments: Fe/Mn-oxyhydroxides, apatite, excess Si, dust, and two altered volcanic ashes. A significant correlation between the mass fraction of one of the specific altered ash end-member and the δ26Mg signature allows us to characterize and track the abundance of the authigenic aluminosilicate component downcore. Trends in the provenance models suggest that the elements that compose the authigenic aluminosilicates may originate from volcanic ash, biogenic Si, and/or hydrothermal plume deposits. We examine variations in the spatial and temporal contributions of each of these sources and assess how these variations may have affected the amount of Mg authigenically consumed by deep sea authigenic clays through the Cenozoic. If the authigenic aluminosilicates are created by "reverse weathering" reactions, their formation also has important implications for carbon cycling in the global ocean.

Semianalytical solutions for transport in aquifer and fractured clay matrix system

NASA Astrophysics Data System (ADS)

Huang, Junqi; Goltz, Mark N.

2015-09-01

A three-dimensional mathematical model that describes transport of contaminant in a horizontal aquifer with simultaneous diffusion into a fractured clay formation is proposed. A group of semianalytical solutions is derived based on specific initial and boundary conditions as well as various source functions. The analytical model solutions are evaluated by numerical Laplace inverse transformation and analytical Fourier inverse transformation. The model solutions can be used to study the fate and transport in a three-dimensional spatial domain in which a nonaqueous phase liquid exists as a pool atop a fractured low-permeability clay layer. The nonaqueous phase liquid gradually dissolves into the groundwater flowing past the pool, while simultaneously diffusing into the fractured clay formation below the aquifer. Mass transfer of the contaminant into the clay formation is demonstrated to be significantly enhanced by the existence of the fractures, even though the volume of fractures is relatively small compared to the volume of the clay matrix. The model solution is a useful tool in assessing contaminant attenuation processes in a confined aquifer underlain by a fractured clay formation.

Chemistry of the Marlboro Clay in Virginia and Implications for the Paleocene-Eocene Thermal Maximum

NASA Astrophysics Data System (ADS)

Zimmer, M.; Cai, Y.; Corley, A.; Liang, J. A.; Powars, D.; Goldstein, S. L.; Kent, D. V.; Broecker, W. S.

2017-12-01

The Paleocene-Eocene Thermal Maximum (PETM) was a global hyperthermal ( 5ºC warming) event marked by a rapid carbon isotope excursion (CIE) of >1‰ in the marine carbonate record (e.g. Zeebe et al. Nature Geoscience 2009). Possible explanations for the CIE include intrusion of a sill complex into organic carbonate (Aarnes et al. J. Geol. Soc. 2015), dissolution of methane hydrates (Thomas et al. Geology 2002), and a comet impact event (Schaller et al. Science 2016). Here we present new data across the PETM from the VirginiaDEQ-USGS Surprise Hill (SH) core, Northumberland Co., VA. We analyzed the Marlboro Clay, a thick, kaolinite-rich clay unit that marks the initiation of the PETM in the mid-Atlantic Coastal Plain of North America, as well as units above and below it. Bulk sediment records a δ13C excursion of approximately -5‰ across the CIE, while benthic foraminifera (Cibicidoides spp.) record a synchronous excursion of approximately -4.5‰. These results are consistent with other records from the New Jersey Coastal Plain (Makarova et al. Paleoceanography 2017). The excursion coincides with an increase in magnetic susceptibility, a decrease in bulk CaCO3 content, and an 2.5‰ decrease of δ18O in both the bulk sediment and benthic foraminifera of the SH core. Pb isotope analyses of the <63 μm fraction sediments indicate a unique provenance make-up for the Marlboro Clay. The results of the study thus indicate that PETM Marlboro Clay was not generated simply by intensified weathering of the same source area as the underlying Aquia Formation and overlying Nanjemoy Formation. Any hypothesis that aims to explain the mechanism that triggered the PETM must also account for the observed distinct provenance make-up of the Marlboro Clay.

Clay-catalyzed reactions of coagulant polymers during water chlorination

USGS Publications Warehouse

Lee, J.-F.; Liao, P.-M.; Lee, C.-K.; Chao, H.-P.; Peng, C.-L.; Chiou, C.T.

2004-01-01

The influence of suspended clay/solid particles on organic-coagulant reactions during water chlorination was investigated by analyses of total product formation potential (TPFP) and disinfection by-product (DBP) distribution as a function of exchanged clay cation, coagulant organic polymer, and reaction time. Montmorillonite clays appeared to act as a catalytic center where the reaction between adsorbed polymer and disinfectant (chlorine) was mediated closely by the exchanged clay cation. The transition-metal cations in clays catalyzed more effectively than other cations the reactions between a coagulant polymer and chlorine, forming a large number of volatile DBPs. The relative catalytic effects of clays/solids followed the order Ti-Mont > Fe-Mont > Cu-Mont > Mn-Mont > Ca-Mont > Na-Mont > quartz > talc. The effects of coagulant polymers on TPFP follow the order nonionic polymer > anionic polymer > cationic polymer. The catalytic role of the clay cation was further confirmed by the observed inhibition in DBP formation when strong chelating agents (o-phenanthroline and ethylenediamine) were added to the clay suspension. Moreover, in the presence of clays, total DBPs increased appreciably when either the reaction time or the amount of the added clay or coagulant polymer increased. For volatile DBPs, the formation of halogenated methanes was usually time-dependent, with chloroform and dichloromethane showing the greatest dependence. ?? 2003 Elsevier Inc. All rights reserved.

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.

[Interaction of clay minerals with microorganisms: a review of experimental data].

PubMed

Naĭmark, E B; Eroshchev-Shak, V A; Chizhikova, N P; Kompantseva, E I

2009-01-01

A review of publications containing results of experiments on the interaction of microorganisms with clay minerals is presented. Bacteria are shown to be involved in all processes related to the transformation of clay minerals: formation of clays from metamorphic and sedimentary rocks, formation of clays from solutions, reversible transitions of different types of clay minerals, and consolidation of clay minerals into sedimentary rocks. Integration of these results allows to conclude that bacteria reproduced all possible abiotic reactions associated with the clay minerals, these reactions proceed much faster with the bacteria being involved. Thus, bacteria act as a living catalyst in the geochemical cycle of clay minerals. The ecological role of bacteria can be considered as a repetition of a chemical process of the abiotic world, but with the use of organic catalytic innovation.

The origin and implications of clay minerals from Yellowknife Bay, Gale crater, Mars†

PubMed Central

Bristow, Thomas F.; Bish, David L.; Vaniman, David T.; Morris, Richard V.; Blake, David F.; Grotzinger, John P.; Rampe, Elizabeth B.; Crisp, Joy A.; Achilles, Cherie N.; Ming, Doug W.; Ehlmann, Bethany L.; King, Penelope L.; Bridges, John C.; Eigenbrode, Jennifer L.; Sumner, Dawn Y.; Chipera, Steve J.; Moorokian, John Michael; Treiman, Allan H.; Morrison, Shaunna M.; Downs, Robert T.; Farmer, Jack D.; Marais, David Des; Sarrazin, Philippe; Floyd, Melissa M.; Mischna, Michael A.; McAdam, Amy C.

2016-01-01

The Mars Science Laboratory (MSL) rover Curiosity has documented a section of fluvio-lacustrine strata at Yellowknife Bay (YKB), an embayment on the floor of Gale crater, approximately 500 m east of the Bradbury landing site. X-ray diffraction (XRD) data and evolved gas analysis (EGA) data from the CheMin and SAM instruments show that two powdered mudstone samples (named John Klein and Cumberland) drilled from the Sheepbed member of this succession contain up to ~20 wt% clay minerals. A trioctahedral smectite, likely a ferrian saponite, is the only clay mineral phase detected in these samples. Smectites of the two samples exhibit different 001 spacing under the low partial pressures of H2O inside the CheMin instrument (relative humidity <1%). Smectite interlayers in John Klein collapsed sometime between clay mineral formation and the time of analysis to a basal spacing of 10 Å, but largely remain open in the Cumberland sample with a basal spacing of ~13.2 Å. Partial intercalation of Cumberland smectites by metal-hydroxyl groups, a common process in certain pedogenic and lacustrine settings on Earth, is our favored explanation for these differences. The relatively low abundances of olivine and enriched levels of magnetite in the Sheepbed mudstone, when compared with regional basalt compositions derived from orbital data, suggest that clay minerals formed with magnetite in situ via aqueous alteration of olivine. Mass-balance calculations are permissive of such a reaction. Moreover, the Sheepbed mudstone mineral assemblage is consistent with minimal inputs of detrital clay minerals from the crater walls and rim. Early diagenetic fabrics suggest clay mineral formation prior to lithification. Thermodynamic modeling indicates that the production of authigenic magnetite and saponite at surficial temperatures requires a moderate supply of oxidants, allowing circum-neutral pH. The kinetics of olivine alteration suggest the presence of fluids for thousands to hundreds of thousands of years. Mineralogical evidence of the persistence of benign aqueous conditions at YKB for extended periods indicates a potentially habitable environment where life could establish itself. Mediated oxidation of Fe2+ in olivine to Fe3+ in magnetite, and perhaps in smectites provided a potential energy source for organisms. PMID:28798492

The origin and implications of clay minerals from Yellowknife Bay, Gale crater, Mars.

PubMed

Bristow, Thomas F; Bish, David L; Vaniman, David T; Morris, Richard V; Blake, David F; Grotzinger, John P; Rampe, Elizabeth B; Crisp, Joy A; Achilles, Cherie N; Ming, Doug W; Ehlmann, Bethany L; King, Penelope L; Bridges, John C; Eigenbrode, Jennifer L; Sumner, Dawn Y; Chipera, Steve J; Moorokian, John Michael; Treiman, Allan H; Morrison, Shaunna M; Downs, Robert T; Farmer, Jack D; Marais, David Des; Sarrazin, Philippe; Floyd, Melissa M; Mischna, Michael A; McAdam, Amy C

2015-04-01

The Mars Science Laboratory (MSL) rover Curiosity has documented a section of fluvio-lacustrine strata at Yellowknife Bay (YKB), an embayment on the floor of Gale crater, approximately 500 m east of the Bradbury landing site. X-ray diffraction (XRD) data and evolved gas analysis (EGA) data from the CheMin and SAM instruments show that two powdered mudstone samples (named John Klein and Cumberland) drilled from the Sheepbed member of this succession contain up to ~20 wt% clay minerals. A trioctahedral smectite, likely a ferrian saponite, is the only clay mineral phase detected in these samples. Smectites of the two samples exhibit different 001 spacing under the low partial pressures of H 2 O inside the CheMin instrument (relative humidity <1%). Smectite interlayers in John Klein collapsed sometime between clay mineral formation and the time of analysis to a basal spacing of 10 Å, but largely remain open in the Cumberland sample with a basal spacing of ~13.2 Å. Partial intercalation of Cumberland smectites by metal-hydroxyl groups, a common process in certain pedogenic and lacustrine settings on Earth, is our favored explanation for these differences. The relatively low abundances of olivine and enriched levels of magnetite in the Sheepbed mudstone, when compared with regional basalt compositions derived from orbital data, suggest that clay minerals formed with magnetite in situ via aqueous alteration of olivine. Mass-balance calculations are permissive of such a reaction. Moreover, the Sheepbed mudstone mineral assemblage is consistent with minimal inputs of detrital clay minerals from the crater walls and rim. Early diagenetic fabrics suggest clay mineral formation prior to lithification. Thermodynamic modeling indicates that the production of authigenic magnetite and saponite at surficial temperatures requires a moderate supply of oxidants, allowing circum-neutral pH. The kinetics of olivine alteration suggest the presence of fluids for thousands to hundreds of thousands of years. Mineralogical evidence of the persistence of benign aqueous conditions at YKB for extended periods indicates a potentially habitable environment where life could establish itself. Mediated oxidation of Fe 2+ in olivine to Fe 3+ in magnetite, and perhaps in smectites provided a potential energy source for organisms.

Fe isotope composition of the Quaternary Red Clay in Southeast China and its paleo-environmental implications

NASA Astrophysics Data System (ADS)

Hu, Xue-Feng; Xue, Yong

2015-04-01

Fe has four stable isotopes, 54Fe (5.84%), 56Fe (91.76%), 57Fe (2.12%) and 58Fe (0.28%). The occurrence of Fe isotopic fractionation during the weathering and pedogenic processes might have some significant paleo-environmental implications. The Quaternary Red Clay (QRC), widely distributed to the south of the Yangtze River, is regarded as a potential archive to record the paleoclimatic changes in subtropical China since the Middle Pleistocene. The composition of Fe isotopes in a profile of the QRC in Langxi County, Anhui Province, Southeast China, was analyzed by the MC-ICP-MS method in this study. The results were as follows: (1) δ56Fe of the Yellow-brown Earth (YBE), the uppermost layer of the profile, only slightly fluctuates between 0.10‰ ~ 0.12‰. That of the Uniform Red Clay (URC) was stable and 0.03‰ in content. That of the Reticulate Red Clay (RRC) in the lower part of the profile, however, was instable and fluctuates between -0.06‰ ~ 0.05‰. (2) The reticulate (net-like) pattern of the RRC was formed by the partial leaching of Fe in the red clay possibly due to long-term frequent fluctuations of groundwater table. The white veins of the RRC were deficiency in both total Fe (Fet) and free Fe (Fed), but the red ones were not. A significant difference of δ56Fe between the white and red veins of the RRC was found. δ56Fe of the white veins, 0.35‰ on average, was significantly higher than that of the red veins, -0.09‰ on average. This suggests that lighter Fe isotopes were preferentially removed during the formation of the reticulate pattern. (3) The content of free Fe oxides in soil is evaluated by the CBD-extracted method. δ56Fe of the CBD-extracted fraction of the red clay samples, -0.083‰ on average, is significantly lower than that of the residual fraction, 0.361‰ on average, suggesting that lighter Fe isotopes were preferentially released from primary minerals to form Fe oxides in the red clay. (4) δ56Fe of the entire profile was negatively significantly correlated with Fet and Fed contents (r2=0.3009 and 0.5105, respectively), which also suggests that Fe in the QRC becomes heavier after the preferential leaching of lighter Fe during the intensive weathering and reticulating processes. In short, the Fe isotopes were only weakly fractionated in the red clay formation under an aerobic condition. When the RRC was formed, however, a large amount of lighter Fe isotopes were preferentially removed under an anaerobic condition and heavier Fe were relatively accumulated in the residues. Therefore, heavier Fe in the red clay may imply a warm and humid climate and luxuriant vegetation during the Middle Pleistocene. The Fe isotope composition of soils or paleosols is a promising factor to interpret pedogenic processes and indicate paleo-environmental changes.

Effect of Electric Field on Gas Hydrate Nucleation Kinetics: Evidence for the Enhanced Kinetics of Hydrate Nucleation by Negatively Charged Clay Surfaces.

PubMed

Park, Taehyung; Kwon, Tae-Hyuk

2018-03-06

Natural gas hydrates are found widely in oceanic clay-rich sediments, where clay-water interactions have a profound effect on the formation behavior of gas hydrates. However, it remains unclear why and how natural gas hydrates are formed in clay-rich sediments in spite of factors that limit gas hydrate formation, such as small pore size and high salinity. Herein, we show that polarized water molecules on clay surfaces clearly promote gas hydrate nucleation kinetics. When water molecules were polarized with an electric field of 10 4 V/m, gas hydrate nucleation occurred significantly faster with an induction time reduced by 5.8 times. Further, the presence of strongly polarized water layers at the water-gas interface hindered gas uptake and thus hydrate formation, when the electric field was applied prior to gas dissolution. Our findings expand our understanding of the formation habits of naturally occurring gas hydrates in clay-rich sedimentary deposits and provide insights into gas production from natural hydrate deposits.

The influence of shale depositional fabric on the kinetics of hydrocarbon generation through control of mineral surface contact area on clay catalysis

NASA Astrophysics Data System (ADS)

Rahman, Habibur M.; Kennedy, Martin; Löhr, Stefan; Dewhurst, David N.; Sherwood, Neil; Yang, Shengyu; Horsfield, Brian

2018-01-01

Accurately assessing the temperature and hence the depth and timing of hydrocarbon generation is a critical step in the characterization of a petroleum system. Clay catalysis is a potentially significant modifier of hydrocarbon generation temperature, but experimental studies of clay catalysis show inconsistent or contradictory results. This study tests the hypothesis that source rock fabric itself is an influence on clay mineral catalysis as it controls the extent to which organic matter and clay minerals are physically associated. Two endmember clay-organic fabrics distinguish the source rocks studied: (1) a particulate fabric where organic matter is present as discrete, >5 μm particles and (2) a nanocomposite fabric in which amorphous organic matter is associated with clay mineral surfaces at sub-micron scale. High-resolution electron imaging and bulk geochemical characterisation confirm that samples of the Miocene Monterey Formation (California) are representative of the nanocomposite source rock endmember, whereas samples from the Permian Stuart Range Formation (South Australia) represent the particulate source rock endmember. Kinetic experiments are performed on paired whole rock and kerogen isolate samples from these two formations using open system, non-isothermal pyrolysis at three different heating rates (0.7, 2 and 5 K/min) to determine the effects of the different shale fabrics on hydrocarbon generation kinetics. Extrapolation to a modelled geological heating rate shows a 20 °C reduction in the onset temperature of hydrocarbon generation in Monterey Formation whole rock samples relative to paired kerogen isolates. This result is consistent with the Monterey Formations's nanocomposite fabric where clay catalysis can proceed because reactive clay minerals are intimately associated with organic matter. By contrast, there is no significant difference in the modelled hydrocarbon generation temperature of paired whole rock and kerogen isolates from the Stuart Range Formation. This is consistent with its particulate fabric, where relatively large, discrete organic particles have limited contact with the mineral matrix and the clay minerals are mainly diagenetic and physically segregated within pores. While heating rate may have a control on mineral matrix effects, this result shows that the extent to which organic matter and clay minerals are physically associated could have a significant effect on the timing of hydrocarbon generation, and is a function of the depositional environment and detrital vs diagenetic origin of clay minerals in source rocks.

Investigation of quartz diagenesis in mudstones of the Spraberry and Wolfcamp Formations

NASA Astrophysics Data System (ADS)

Eakin, A.; Reece, J. S.

2016-12-01

Here we present preliminary core analysis of the diagenetic variability existing within a siliceous mudstone facies of the Permian Spraberry and Wolfcamp Formations in the Midland Basin, Texas. Within this mudstone facies, the carbonate content varies from absent in several Wolfcamp Formation samples to >40 wt. % in the Spraberry Formation. A normalized ratio of quartz to clay content with carbonate removed reveals a systematic decrease in quartz content with increasing clay content. This relationship is typical of rocks with variable amounts of detrital quartz content. However, in this siliceous mudstone facies, the abundance of detrital quartz silt grains does not vary widely. Additionally, for the same clay content, the Wolfcamp Formation shows a higher concentration of quartz than the Spraberry Formation. Scanning electron microscopy (SEM) reveals the presence of microcrystalline quartz cement that likely accounts for the increased quartz content in the Wolfcamp Formation. This research tests the hypothesis that the increased quartz cement in the Wolfcamp Formation may occur at the expense of the carbonate cement present in the overlying Spraberry Formation. Furthermore, the deviation in quartz content for the same clay concentration only occurs once the ratio of quartz to clay content increases beyond 1.2. This ratio may represent a threshold of detrital quartz in the clay matrix required to have enough porosity and nucleation surface area for authigenic quartz growth. The presence of matrix cement may impact the mechanical properties to favor fracturing and cataclasis over more ductile deformation. This would enhance development of secondary porosity, while also increasing permeability through the connection of primary pores. Acquiring a fundamental understanding of diagenesis in the Spraberry and Wolfcamp Formations will aid in better prediction of mechanical behavior during drilling and optimized resource recovery.

Enhancement of peptide bond formation by polyribonucleotides on clay surfaces in fluctuating environments

NASA Technical Reports Server (NTRS)

White, D. H.; Erickson, J. C.

1981-01-01

The selective effects of polyribonucleotides on the formation of glycine peptide bonds in glycine on clay surfaces are investigated as a model for a template mechanism for the effects of polynucleotides on peptide bond formation. Free oligoglycine yields were determined for the cycling reaction of glycine in the presence and absence of clay and polyribonucleotides or polydeoxyribonucleotides. The polyribonucleotides are observed to lead to increases of up to fourfold increases in oligoglycine formed, with greater enhancements for poly-G nucleotides than for poly-A, poly-U and poly-C, indicating a codonic bias. Polydeoxyribonucleotides are found to provide no enhancement in peptide formation rates, and yields were also greatly reduced in the absence of clay. A mechanism for peptide synthesis is proposed which involves the activation of glycine on the clay surface, followed by the formation of esters between glycine and the 2-prime OH groups of the polyribonucleotide and peptide bonds between adjacent amino acyl esters. It is pointed out that if this mechanism is correct, it may provide a basis for a direct template translation process, which would produce a singlet genetic code.

Assessing the role of clay authigenesis in the seawater potassium cycle: A paired K and Mg isotope study of deep-sea pore fluids

NASA Astrophysics Data System (ADS)

Santiago Ramos, D. P.; Higgins, J. A.

2017-12-01

In situ formation of clays (clay authigenesis) in marine sediments and altered oceanic crust is an important sink of a number of seawater cations. In particular, clay authigenesis is a major, and yet unconstrained, flux in the global seawater potassium cycle. Potassium is the fourth most abundant cation in the ocean, which constitutes an isotopically enriched K reservoir (δ41K 0‰) compared to the solid Earth (δ41K -0.5‰). Understanding what processes control this isotopic offset is the main goal of this study. Here we use a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) to measure the K and Mg isotope ratios (41K/39K and 26Mg/24Mg) of deep-sea pore fluids in order to assess the effects of clay formation in the K isotope composition of seawater. Mg isotopes are used as an independent proxy for clay formation, since marine authigenic clays are isotopically distinct from their detrital counterpart, an abundant component of marine sediments. Our study sites (ODP/IODP 1052, U1378, U1395, U1403) vary in location, lithology, age and sedimentation rates; however, pore-fluids from all sites show decreasing K concentrations with depth, suggesting potassium uptake into the sediments. We find that although K concentration trends are similar across all sites, measured δ41K values vary significantly. Results from 1-D diffusion-advection-reaction models suggest that these differences in isotopic profiles arise from a complex interplay between sedimentation rate and K isotopic fractionation during clay formation, aqueous K diffusion and ion exchange reactions. Further, model simulations yield fractionation factors between 0.9980 and 1.0000 for clay formation in deep-sea sediments. Despite the minor contribution of these deep-sea pore-fluids as sinks of seawater K, the processes responsible for K isotope fractionation in our study sites (clay formation and aqueous K diffusion) are also observed at shallow marine systems (major K sinks) and are thus likely responsible for setting the K isotopic composition of seawater.

Soil stabilization by a prokaryotic desert crust - Implications for Precambrian land biota

NASA Technical Reports Server (NTRS)

Campbell, S. E.

1979-01-01

The ecology of the cyanophyte-dominated stromatolitic mat forming the ground cover over desert areas of Utah and Colorado is investigated and implications for the formation of mature Precambrian soils are discussed. The activation of the growth of the two species of filamentous cyanophyte identified and the mobility of their multiple trichromes upon wetting are observed, accompanied by the production and deposition of a sheath capable of accreting and stabilizing sand and clay particles. The formation of calcium carbonate precipitates upon the repeated wetting and drying of desert crust is noted, and it is suggested that the desert crust community may appear in fossil calcrete deposits as lithified microscopic tubes and cellular remains of algal trichromes. The invasion of dry land by both marine and freshwater algae on the model of the desert crust is proposed to be responsible for the accumulation, stabilization and biogenic modification of mature Precambrian soils.

Hf-Nd isotopic variability in mineral dust from Chinese and Mongolian deserts: implications for sources and dispersal

PubMed Central

Zhao, Wancang; Sun, Youbin; Balsam, William; Lu, Huayu; Liu, Lianwen; Chen, Jun; Ji, Junfeng

2014-01-01

Mineral dust provenances are closely related to the orogenic processes which may have distinct Hf-Nd isotopic signatures. Here we report the clay-sized (<2 μm) Hf-Nd isotope data from Asian dust sources to better constrain the source and transport dynamics of dust deposition in the North Pacific. Our results show that there is a more positive radiogenic Hf isotopic composition with clay-sized fractions than the corresponding bulk sample and a decoupling of the Hf-Nd couplets in the clay formation during the weathering process. The clay-sized Hf-Nd isotopic compositions of the desert samples from the Sino-Korean-Tarim Craton (SKTC) are different from those of the Gobi and deserts from the Central Asian Orogeny Belt (CAOB) due to varying tectonic and weathering controls. The Hf-Nd isotopic compositions of dust in the North Pacific central province (NPC) match closely with those from the Taklimakan, Badain Jaran and adjacent Tengger deserts, implying that the NPC dust was mainly transported from these potential sources by the westerly jet. Our study indicates that dusts from the CAOB Gobi deserts either didn't arrive in NPC or were quantitatively insignificant, but they were likely transported to the North Pacific margin province (NPM) by East Asian winter monsoon. PMID:25060781

Hf-Nd isotopic variability in mineral dust from Chinese and Mongolian deserts: implications for sources and dispersal.

PubMed

Zhao, Wancang; Sun, Youbin; Balsam, William; Lu, Huayu; Liu, Lianwen; Chen, Jun; Ji, Junfeng

2014-07-25

Mineral dust provenances are closely related to the orogenic processes which may have distinct Hf-Nd isotopic signatures. Here we report the clay-sized (<2 μm) Hf-Nd isotope data from Asian dust sources to better constrain the source and transport dynamics of dust deposition in the North Pacific. Our results show that there is a more positive radiogenic Hf isotopic composition with clay-sized fractions than the corresponding bulk sample and a decoupling of the Hf-Nd couplets in the clay formation during the weathering process. The clay-sized Hf-Nd isotopic compositions of the desert samples from the Sino-Korean-Tarim Craton (SKTC) are different from those of the Gobi and deserts from the Central Asian Orogeny Belt (CAOB) due to varying tectonic and weathering controls. The Hf-Nd isotopic compositions of dust in the North Pacific central province (NPC) match closely with those from the Taklimakan, Badain Jaran and adjacent Tengger deserts, implying that the NPC dust was mainly transported from these potential sources by the westerly jet. Our study indicates that dusts from the CAOB Gobi deserts either didn't arrive in NPC or were quantitatively insignificant, but they were likely transported to the North Pacific margin province (NPM) by East Asian winter monsoon.

Clay catalysis of oligonucleotide formation: kinetics of the reaction of the 5'-phosphorimidazolides of nucleotides with the non-basic heterocycles uracil and hypoxanthine

NASA Technical Reports Server (NTRS)

Kawamura, K.; Ferris, J. P.

1999-01-01

The montmorillonite clay catalyzed condensation of activated monocleotides to oligomers of RNA is a possible first step in the formation of the proposed RNA world. The rate constants for the condensation of the phosphorimidazolide of adenosine were measured previously and these studies have been extended to the phosphorimidazolides of inosine and uridine in the present work to determine of substitution of neutral heterocycles for the basic adenine ring changes the reaction rate or regioselectivity. The oligomerization reactions of the 5'-phosphoromidazolides of uridine (ImpU) and inosine (ImpI) on montmorillonite yield oligo(U)s and oligo(I)s as long as heptamers. The rate constants for oligonucleotide formation were determined by measuring the rates of formation of the oligomers by HPLC. Both the apparent rate constants in the reaction mixture and the rate constants on the clay surface were calculated using the partition coefficients of the oligomers between the aqueous and clay phases. The rate constants for trimer formation are much greater than those dimer synthesis but there was little difference in the rate constants for the formation of trimers and higher oligomers. The overall rates of oligomerization of the phosphorimidazolides of purine and pyrimidine nucleosides in the presence of montmorillonite clay are the same suggesting that RNA formed on the primitive Earth could have contained a variety of heterocyclic bases. The rate constants for oligomerization of pyrimidine nucleotides on the clay surface are significantly higher than those of purine nucleotides since the pyrimidine nucleotides bind less strongly to the clay than do the purine nucleotides. The differences in the binding is probably due to Van der Waals interactions between the purine bases and the clay surface. Differences in the basicity of the heterocyclic ring in the nucleotide have little effect on the oligomerization process.

Adsorption of Dissolved Gases (CH4, CO2, H2, Noble Gases) by Water-Saturated Smectite Clay Minerals

NASA Astrophysics Data System (ADS)

Bourg, I. C.; Gadikota, G.; Dazas, B.

2016-12-01

Adsorption of dissolved gases by water-saturated clay minerals plays important roles in a range of fields. For example, gas adsorption in on clay minerals may significantly impact the formation of CH4 hydrates in fine-grained sediments, the behavior of CH4 in shale, CO2 leakage across caprocks of geologic CO2 sequestration sites, H2 leakage across engineered clay barriers of high-level radioactive waste repositories, and noble gas geochemistry reconstructions of hydrocarbon migration in the subsurface. Despite its importance, the adsorption of gases on clay minerals remains poorly understood. For example, some studies have suggested that clay surfaces promote the formation of CH4 hydrates, whereas others indicate that clay surfaces inhibit the formation of CH4 hydrates. Here, we present molecular dynamics (MD) simulations of the adsorption of a range of gases (CH4, CO2, H2, noble gases) on clay mineral surfaces. Our results indicate that the affinity of dissolved gases for clay mineral surfaces has a non-monotone dependence on the hydrated radius of the gas molecules. This non-monotone dependence arises from a combination of two effects: the polar nature of certain gas molecules (in particular, CO2) and the templating of interfacial water structure by the clay basal surface, which results in the presence of interfacial water "cages" of optimal size for intermediate-size gas molecules (such as Ne or Ar).

Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CO2: Implications for Caprock Integrity

NASA Astrophysics Data System (ADS)

Loring, J. S.; Chen, J.; Thompson, C.; Schaef, T.; Miller, Q. R.; Martin, P. F.; Ilton, E. S.; Qafoku, O.; Felmy, A. R.; Rosso, K. M.

2012-12-01

The effectiveness of geologic sequestration as an enterprise for CO2 storage depends partly on the reactivity of supercritical CO2 (scCO2) with caprock minerals. Injection of scCO2 will displace formation water, and the pore space adjacent to overlying caprocks could eventually be dominated by dry to water-saturated scCO2. Caprock formations have high concentrations of clay minerals, including expandable montmorillonites. Water-bearing scCO2 is highly reactive and capable of hydrating or dehydrating clays, possibly leading to porosity and permeability changes that directly impact caprock performance. Dehydration will cause montmorillonite clay minerals in caprocks to contract, thereby decreasing solid volume and possibly increasing caprock permeability and porosity. On the other hand, water intercalation will cause these clays to expand, thereby increasing solid volume and possibly leading to self-sealing of caprock fractures. Pacific Northwest National Laboratory's Carbon Sequestration Initiative is developing capabilities for studying wet scCO2-mineral reactions in situ. Here, we introduce novel in situ infrared (IR) spectroscopic instrumentation that enables quantitative titrations of reactant minerals with water in scCO2. Results are presented for the infrared spectroscopic titrations of Na-, Ca-, and Mg-saturated Wyoming betonites with water over concentrations ranging from zero to scCO2 saturated. These experiments were carried out at 50°C and 90 bar. Transmission IR spectroscopy was used to measure concentrations of water dissolved in the scCO2 or intercalated into the clays. The titration curves evaluated from the transmission-IR data are compared between the three types of clays to assess the effects of the cation on water partitioning. Single-reflection attenuated total reflection (ATR) IR spectroscopy was used to collect the spectrum of the clays as they hydrate at every total water concentration during the titration. Clay hydration is evidenced by increases in absorbance of the OH stretching and HOH bending modes of the intercalated waters. The ATR-IR data also indicate that CO2 is intercalated in the clay. The asymmetric stretching band of the CO2 molecules that are intercalated in the clay is narrower than that stretching band of bulk scCO2, which indicates that the spectral contribution from rotational fine structure is minimal and the intercalated CO2 is rotationally constrained. A chemometrics analysis of the complete set of ATR-IR spectra spanning the range of total water concentrations covered in the titration finds that there are at least two types of intercalated waters, two types of intercalated CO2 molecules, and the concentrations of these intercalated waters and CO2 molecules are correlated. These quantitative data, when coupled with in situ XRD results that predict interlayer spacing and clay volume, demonstrate that water and CO2 intercalation processes in expandable montmorillonite clays could lead to porosity and permeability changes that directly impact caprock performance.

Pentachlorophenol radical cations generated on Fe(III)-montmorillonite initiate octachlorodibenzo-p-dioxin formation in clays: DFT and FTIR studies

PubMed Central

Gu, Cheng; Liu, Cun; Johnston, Cliff T.; Teppen, Brian J.; Li, Hui; Boyd, Stephen A.

2011-01-01

Octachlorodibenzodioxin (OCDD) forms spontaneously from pentachlorophenol (PCP) on the surfaces of Fe(III)-saturated smectite clay (1). Here, we used in situ FTIR methods and quantum mechanical calculations to determine the mechanism by which this reaction is initiated. As the clay was dehydrated, vibrational spectra showed new peaks that grew and then reversibly disappeared as the clay rehydrated. First principle DFT calculations of hydrated Fe-PCP clusters reproduced these transient FTIR peaks when inner-sphere complexation and concomitant electron transfer produced Fe(II) and PCP radical cations. Thus, our experimental (FTIR) and theoretical (quantum mechanical) results mutually support the hypothesis that OCDD formation on Fe-smectite surfaces is initiated by the reversible formation of metastable PCP radical cations via single electron transfer from PCP to Fe(III). The negatively charged clay surface apparently selects for this reaction mechanism by stabilizing PCP radical cations. PMID:21254769

Beneath the scaly clay and clay breccia of Karangsambung area

NASA Astrophysics Data System (ADS)

Arisbaya, Ilham; Handayani, Lina

2018-02-01

Karangsambung area, Central Java-Indonesia, records tectonic evolution of the western part of Sundaland margin. The area is thought to have undergone a long tectonic evolution from palaeosubduction, collision with the continental fragments of Gondwana, to the formation of the recent subduction zone. An interesting phenomenon in this area is the presence of the Late Cretaceous ophiolitic blocks with an east northeast (ENE) trending-direction surrounded by the east trend of Eocene - Oligocene sedimentary melange formation. There was also an ENE trending Dakah volcanic rocks unit found in this area, with approximately equivalent age with the sedimentary mélange formation. There are two main interpretations regarding this volcanic unit, as an olistostrome and as an insitu shallow subduction magmatic product. Detailed mechanism of the emplacement of the Late Cretaceous ophiolite and the genesis of the volcanic rocks unit and their implications to the regional tectonic model is still open for discussion. Geophysical research in this key area may help to reveal the geometry, relationship among rocks units, and tectonic evolution. Unfortunately, geophysical studies in this area are still lacking. Previous geophysical work in Karangsambung still leaves uncertainty, especially in depth control and spatial resolution issue. Here we describe the results of previous works in Karangsambung as basic knowledge for the upcoming geophysical study.

Mineralogy and Geochemistry of the Main Glauconite Bed in the Middle Eocene of Texas: Paleoenvironmental Implications for the Verdine Facies

PubMed Central

Harding, Sherie C.; Nash, Barbara P.; Petersen, Erich U.; Ekdale, A. A.; Bradbury, Christopher D.; Dyar, M. Darby

2014-01-01

The Main Glauconite Bed (MGB) is a pelleted greensand located at Stone City Bluff on the south bank of the Brazos River in Burleson County, Texas. It was deposited during the Middle Eocene regional transgression on the Texas Gulf Coastal Plain. Stratigraphically it lies in the upper Stone City Member, Crockett Formation, Claiborne Group. Its mineralogy and geochemistry were examined in detail, and verdine facies minerals, predominantly odinite, were identified. Few glauconitic minerals were found in the green pelleted sediments of the MGB. Without detailed mineralogical work, glaucony facies minerals and verdine facies minerals are easily mistaken for one another. Their distinction has value in assessing paleoenvironments. In this study, several analytical techniques were employed to assess the mineralogy. X-ray diffraction of oriented and un-oriented clay samples indicated a clay mixture dominated by 7 and 14Å diffraction peaks. Unit cell calculations from XRD data for MGB pellets match the odinite-1M data base. Electron microprobe analyses (EMPA) from the average of 31 data points from clay pellets accompanied with Mössbauer analyses were used to calculate the structural formula which is that of odinite: Fe3+ 0.89 Mg0.45 Al0.67 Fe2+ 0.30 Ti0.01 Mn0.01) Σ = 2.33 (Si1.77 Al0.23) O5.00 (OH)4.00. QEMSCAN (Quantitative Evaluation of Minerals by Scanning Electron Microscopy) data provided mineral maps of quantitative proportions of the constituent clays. The verdine facies is a clay mineral facies associated with shallow marine shelf and lagoonal environments at tropical latitudes with iron influx from nearby runoff. Its depositional environment is well documented in modern nearshore locations. Recognition of verdine facies clays as the dominant constituent of the MGB clay pellets, rather than glaucony facies clays, allows for a more precise assessment of paleoenvironmental conditions. PMID:24503875

Abiogenic photochemical synthesis on surface of meteorites and other small space bodies

NASA Astrophysics Data System (ADS)

Simakov, Michael B.; Kuzicheva, Eugenia A.

The abiogenic photochemical synthesis of complex biochemical compounds on the surface of small bodies in our Solar system was examined. Hydrated minerals are found within a chondrite matrix of meteorites together with significant amounts of organic matter. Clays are likely to have formed when water was present on parent meteoritic bodies. In order to verify the existence of a relationship between abiogenic synthesis of nucleotides and inorganic components of the meteorites, we have investigated possible abiogenic reactions associated with different clay (montmorillonite, kaolinite) and a basaltic one (Tyatya's volcanic ash) under action of open space energy sources as a model of different exobiological environments on the surface of small space bodies. The abiogenic synthesis of natural adenine nucleotides from a mixture of adenosine and inorganic phosphate has been observed following irradiation with VUV light in the presence of different mineral samples. The yields of the products (5'AMP, 2'AMP, 3'AMP, 2'3'cAMP and 3'5'cAMP) depended on irradiation time and kinds of minerals used. The discovery that meteoritic organic compounds may be trapped and protected within a clay mineral matrix has implications for our understanding of prebiotic molecular evolution in the early Solar system. Clay minerals may also have concentrated organic compounds thereby promoting polymerization reactions. An adsorption/binding of nucleic acids components by clay crystals could change the electron distribution and/or the conformation of the molecules. The remnant water molecules in the clay sheets also could influence the course of the reaction. Clay immobilization of phosphate could play an important role in this reaction. Chondritic material could have been a common component of the inner Solar system shortly after its formation and the biologically useful products of clay mineral-organic matter interactions could have also widespread, and delivered to planetary surfaces through the accretion of carbonaceous asteroids.

An abiogenic photochemical synthesis on surface of meteorites and other small space bodies

NASA Astrophysics Data System (ADS)

Simakov, M.; Kuzicheva, E.

Abiogenic photochemical synthesis of complex biochemical compounds on the surface of small bodies in our Solar system was examined. The hydrated minerals are found within a chondrite matrix of meteorites together with significant amounts of organic matter. Clays are likely to have formed when water was presented on parent meteoritic bodies. In order to verify the existence of a relationship between abiogenic synthesis of nucleotides and inorganic components of the meteorites we have investigated possible abiogenic reactions at the presence of different clay minerals (montmorillonite, kaolinite) and basaltic sample (Tjatja's volcanic ash) under action of open space energy sources for modeling of different exobiological environments on the surface of small space bodies. The abiogenic synthesis of natural adenine nucleotides from mixture of adenosine plus inorganic phosphate has been observed under an irradiation with VUV radiation at the presence of different mineral samples. The yields of the products (5'AMP, 2'AMP, 3'AMP, 2'3'cAMP and 3'5'cAMP) were depended from irradiation time and kind of used minerals. The discovery that meteoritic organic compounds may be trapped and protected within a clay mineral matrix has implications for our understanding of prebiotic molecular evolution in the early Solar system. Clay minerals may have concentrated organic compounds thereby promoting polymerization reactions also. An adsorption/binding of nucleic acids components by clay crystals could change in the electron distribution and/or the conformation of the molecules. The remnant water molecules in the clay sheets also could influence on the course of the reaction. Besides, an immobilization of phosphate on clay also could play an important role in our reaction. Chondritic material would have been a common component of the inner Solar system shortly after its formation and the biologically useful products of clay mineral-organic matter interactions would have also widespread, and delivered to planetary surfaces through the accretion of carbonaceous asteroids.

Snowball gouge-aggregates formed in experimental fault gouges at seismic slip rates

NASA Astrophysics Data System (ADS)

Kim, J. H.; Ree, J. H.; Hirose, T.; Yang, K.; Kim, J. W.

2015-12-01

Clay-clast aggregates (CCA) have commonly been reported from experimental and natural fault gouges, but their formation process and mechanical meaning are not so clear. We call CCA snowball gouge aggregate (SGA) since its formation process is similar to that of snowball (see below) and CCA-like structure has been reported also from pure quartz and pure calcite gouges. Here, we discuss the formation process of SGA and its implication for faulting from experimental results of simulated gouges. We conducted high-velocity rotary shear experiments on Ca-bentonite gouges at a normal stress of 1 MPa, slip rate of 1.31 m/s, room temperature and room humidity conditions. Ca-bentonite gouge consists of montmorillonite (>95%) and other minor minerals including quartz and plagioclase. Upon displacement, the friction abruptly increases to the 1st peak (friction coefficient μ≈ 0.7) followed by slip weakening to reach a steady state (μ≈ 0.25~0.3). The simulated fault zone can be divided into slip-localization zone (SLZ) and low-slip-rate zone (LSZ) based on grain size. Spherical SGAs with their size ranging from 1 to 100 μm occur only in LSZ, and their proportion is more than 90%. Two types of SGA occur; SGA with and without a central clast. Both types of SGA show a concentric layering defined by the alternation of pore-rich (1-1.5 μm thick) and pore-poor layers (1.5-2 μm thick). Clay minerals locally exhibit a preferred orientation with their basal plane parallel to the layer boundary. We interpret that the pore-poor layers are clay-accumulated layers formed by rolling of SGA nuclei, and pore-rich layers correspond to the boundary between accumulated clay layers. Water produced from dehydration of clays due to frictional heating presumably acts as an adhesion agent of clay minerals during rolling of SGA. Since the number of layers within each SGA represents the number of rolling, the minimum displacement estimated from the number of layers and layer thickness of the largest SGA (with a diameter of 100 μm) is about 2.7 mm (slip rate≈ 170 μm/s) which is much less than the total displacement of 20 m, suggesting that most of the displacement occurred along the SLZ. Our results imply that SGA can be formed only in subseismic slip-rate zones and that minimum displacement and slip rate can be estimated from SGA.

Clay hydration/dehydration in dry to water-saturated supercritical CO2: Implications for caprock integrity

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

Loring, John S.; Schaef, Herbert T.; Thompson, Christopher J.

2013-01-01

Injection of supercritical CO2 (scCO2) for the geologic storage of carbon dioxide will displace formation water, and the pore space adjacent to overlying caprocks could eventually be dominated by dry to water-saturated scCO2. Wet scCO2 is highly reactive and capable of carbonating and hydrating certain minerals, whereas anhydrous scCO2 can dehydrate water-containing minerals. Because these geochemical processes affect solid volume and thus porosity and permeability, they have the potential to affect the long-term integrity of the caprock seal. In this study, we investigate the swelling and shrinkage of an expandable clay found in caprock formations, montmorillonite (Ca-STx-1), when exposed tomore » variable water-content scCO2 at 50 °C and 90 bar using a combination of in situ probes, including X-ray diffraction (XRD), in situ magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR), and in situ attenuated total reflection infrared spectroscopy (ATR-IR). We show that the extent of montmorillonite clay swelling/shrinkage is dependent not only on water hydration/dehydration, but also on CO2 intercalation reactions. Our results also suggest a competition between water and CO2 for interlayer residency where increasing concentrations of intercalated water lead to decreasing concentrations of intercalated CO2. Overall, this paper demonstrates the types of measurements required to develop fundamental knowledge that will enhance modeling efforts and reduce risks associated with subsurface storage of CO2.« less

Environmental Investigation and Risk Assessment. Phase 1 Report Tacony Warehouse, Philadelphia, Pennsylvania

DTIC Science & Technology

1993-08-24

Sayreville sand, the middle clay, the Old Bridge sand, and the upper clay. The Raritan is overlain in adjacent parts of New Jersey by the Magothy ...Formation, but the Magothy Formation has not been identified in the Philadelphia area. The sediments that overlie the Raritan are Pleistocene deposits...Qc,Pleistocene -.-- Unconjormity ... so Pensauken formation , Qp (Illinoian) Unconformitg . . . Magothy formation Kn 10 ... Uncontormity .... Upper

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.

Direct observation of heavy metal-mineral association from the Clark Fork River Superfund Complex: Implications for metal transport and bioavailability

USGS Publications Warehouse

Hochella, M.F.; Moore, J.N.; Putnis, C.V.; Putnis, A.; Kasama, T.; Eberl, D.D.

2005-01-01

Two sets of samples from riverbeds and adjacent floodplains, separated by 80 river kilometers, were collected from the Clark Fork River Superfund Complex, Montana, (the largest Superfund site in the United States), and studied primarily with transmission electron microscopy (TEM) with several supporting techniques to determine heavy metal-mineral association. Seven of the eight samples studied were strongly influenced by material that once resided in mining and smelting dumps and impoundments; this material was transported downstream sometime during the last century and a half from the Butte/Anaconda areas. The eighth sample was from a deeper floodplain level and dates to premining days. The TEM observations afford a direct look, down to the nanometer level, at secondary mineral formation as a result of the breakdown of sulfides and silicates in the acid environment of this massive mine-drainage system. In the shallow, oxic floodplain sediments, heavy metals of concern in this system (As, Cu, Pb, and Zn) are taken up by the formation of sulfates (particularly Pb in jarosite), as well as hydrous metal oxides (As, Cu, Pb, and Zn in and on ferrihydrite, and a possibly new vernadite-like mineral). The oxides are long-lived in these systems, as they were also found in the anoxic riverbeds. Metals are also taken up by the formation of sulfides in sulfate-reducing environments as observed in the formation of nanoclusters of chalcopyrite and sphalerite. In all samples, clays make up between 5 and 20% of the sediment and carry significant amounts of Cu and Zn. The hydrous oxides, secondary sulfides, and clays provide several routes for metal transport downstream over long distances. Besides the potential bioavailability of heavy metals exchanged on and off the hydrous metal oxides and clays, nanometer-sized sulfides may also be highly reactive in the presence of biologic systems. Copyright ?? 2005 Elsevier Ltd.

Processes affecting soil and groundwater contamination by DNAPL in low-permeability media

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

McWhorter, D.B.

1996-08-01

This paper is one of a set of focus papers intended to document the current knowledge relevant to the contamination and remediation of soils and ground water by dense, nonaqueous phase liquids (DNAPL). The emphasis is on low permeability media such as fractured clay and till and unconsolidated, stratified formations. Basic concepts pertaining to immiscible-fluid mixtures are described and used to discuss such aspects as DNAPL transport, dissolved-phase transport, and equilibrium mass distributions. Several implications for remediation are presented. 27 refs., 8 figs., 4 tabs.

Aqueous mineralogy and stratigraphy at and around the proposed Mawrth Vallis MSL Landing Site: New insights into the aqueous history of the region

USGS Publications Warehouse

Dobrea, Eldar Z. Noe; Michalski, Joseph; Swayze, Gregg

2011-01-01

In this work, we have confirmed the mineralogical stratigraphy previously inferred by other authors, but also demonstrate the presence of additional minerals, including a possible acid-leaching product near the top of the sequence, an Mh-OH bearing phyllosilicate at the to of the sequence, and potentially a Ca-sulfate at the bottom of the phyllosilicate sequence. The latter has important implications regarding the relative timing of sulfate vs clay formation on Mars.

The Suitable Geological Formations for Spent Fuel Disposal in Romania

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

Marunteanu, C.; Ionita, G.; Durdun, I.

2007-07-01

Using the experience in the field of advanced countries and formerly Romanian program data, ANDRAD, the agency responsible for the disposal of radioactive wastes, started the program for spent fuel disposal in deep geological formations with a documentary analysis at the national scale. The potential geological formations properly characterized elsewhere in the world: salt, clay, volcanic tuff, granite and crystalline rocks,. are all present in Romania. Using general or specific selection criteria, we presently consider the following two areas for candidate geological formations: 1. Clay formations in two areas in the western part of Romania: (1) The Pannonian basin Socodormore » - Zarand, where the clay formation is 3000 m thick, with many bentonitic strata and undisturbed structure, and (2) The Eocene Red Clay on the Somes River, extending 1200 m below the surface. They both need a large investigation program in order to establish and select the required homogeneous, dry and undisturbed zones at a suitable depth. 2. Old platform green schist formations, low metamorphosed, quartz and feldspar rich rocks, in the Central Dobrogea structural unit, not far from Cernavoda NPP (30 km average distance), 3000 m thick and including many homogeneous, fine granular, undisturbed, up to 300 m thick layers. (authors)« less

Ball clay and bentonite deposits of the central and western Gulf of Mexico Coastal Plain, United States

USGS Publications Warehouse

Hosterman, John W.

1984-01-01

The Gulf of Mexico Coastal Plain produces approximately 85 percent of the ball clay used in the United States. The best commercial-grade clay deposits are composed of poorly crystalline kaolinite and small amounts of Md illite and (or) smectite. Sand and silt and iron oxide minerals are virtually absent, but quartz is present in the clay-size fraction. The best grade ball clays are found as lenses limited to the Wilcox Group (Paleocene and lower Eocene) and Claiborne Group (middle Eocene). Reserves of ball clay are sufficient for the present, but because of the lenticular nature of the clay bodies, close-spaced drilling, detailed sampling, mineralogic analyses, and ceramic testing are needed to prove future reserves.Approximately 11 percent of the total bentonite produced in the United States comes from the Gulf Coast region. The commercial-grade bentonites are composed primarily of smectite with little or no Md illite and kaolinite. The nonclay impurities are quartz, feldspar, muscovite, biotite, calcite, dolomite, gypsum, and heulandite. Commercial bentonites occur in the Upper Cretaceous formations in Alabama and Mississippi, in Paleocene formations in Mississippi and Tennessee, and in Eocene and Miocene formations in Texas. The demand for low-swelling bentonite of the Gulf Coastal Plain has not increased along with the demand for swelling bentonite; therefore the reserves are adequate.

Clays in prebiological chemistry

NASA Technical Reports Server (NTRS)

Rao, M.; Oro, J.; Odom, D. G.

1980-01-01

The ways in which clays have been utilized in studies of prebiological chemistry are reviewed, and an assessment is given of the possible role of clays in prebiological systems. The adsorption of organic molecules on clays has been demonstrated, as has the synthesis of bioorganic monomers in the presence of clays. For instance, amino acids, purines and pyrimidines have been obtained from carbon monoxide and nitric acid in the presence of clays at relatively high temperatures (250-325 C). The oligomerization of biochemical monomers, mediated by clays, has also been shown to result in the formation of polymer molecules basic to life. Clays have also been found to affect the condensation of mononucleotides to oligonucleotides.

Rates and time scales of clay-mineral formation by weathering in saprolitic regoliths of the southern Appalachians from geochemical mass balance

Treesearch

Jason R. Price; Michael A. Velbel; Lina C. Patino

2005-01-01

Rates of clay formation in three watersheds located at the Coweeta Hydrologic Laboratory, western North Carolina, have been determined from solute flux-based mass balance methods. A system of mass balance equations with enough equations and unknowns to allow calculation of secondary mineral formation rates as well as the more commonly determined primary-...

Trepostome and cystoporate bryozoans from the Lexington Limestone and the Clays Ferry Formation (Middle and Upper Ordovician) of Kentucky

USGS Publications Warehouse

Karklins, O.L.

1984-01-01

The Lexington Limestone and the Clays Ferry Formation of Kentucky contain an abundant and diversified fossil invertebrate fauna. This report is concerned with the trepostome and cystoporate bryozoans that constitute a major part of that fauna. The Lexington Limestone, largely a biofragmental fossiliferous limestone, rests disconformably on the Tyrone Limestone (Middle Ordovician). The Clays Ferry Formation consists of approximately equal amounts of biofragmentallimestone and shale, and it overlies conformably, or intertongues with, the upper part of the Lexington Limestone. The Clays Ferry Formation is overlain by the Garrard Siltstone (Upper Ordovician) in central Kentucky and intertongues with the Kope Formation (Upper Ordovician) in northern Kentucky. The MiddleUpper Ordovician boundary falls within the upper part of the Lexington Limestone and laterally equivalent strata of the Clays Ferry Formation. The Lexington Limestone has been divided into 12 members, consisting of calcarenites, calcisiltites, calcilutites, nodular limestones, and shales in various amounts, that intertongue complexly. Because of the great abundance of bryozoans this study is generally limited to bryozoans recovered from, in ascending order, the Grier Limestone Member, the Perryville Limestone Member, the Brannon Member, the Tanglewood Limestone Member, and the Millersburg Member of the Lexington Limestone and from the Clays Ferry Formation and its Point Pleasant Tongue. The trepostome and cystoporate bryozoans discussed are referred to 36 species belonging to 22 genera. The trepostome component includes 29 species belonging to 16 genera: Amplexopora, Atactoporella, Balticopora, Batostoma, Cyphotrypa, Dekayia, Eridotrypa, Hetero-_ trypa, Homotrypa, Homotrypella, Mesotrypa, Parvohallopora, Peronopora, Prasopora, Stigmatella, and Tarphophragma, a new genus. Five of the trepostome species are new: Balticopora arcuatilis, Cyphotrypa switzeriensis, Dekayia epetrima, Eridotrypa sadievillensis, and Homotrypa cressmani. The cystoporate bryozoans include 7 species belonging to 6 genera: Acanthoceramoporella, Ceramophylla, Ceramoporella, Constellaria, Crepipora, and Papillalunaria. One cystoporate species is new: Acanthoceramoporella valliensis. The trepostome and cystoporate fauna on the generic level is, with few exceptions, cosmopolitan. Five genera, Eridotrypa, Parvohallopora, Heterotrypa, Constellaria, and Peronopora, dominate the fauna, comprising about 77 percent of the thin-sectioned specimens. On the species level the fauna is endemic to the Ordovician of eastern North America and is biostratigraphically restricted to strata of late Blackriveran Stage (Middle Ordovician) to early Maysvillian Stage (middle Late Ordovician). In Kentucky the species of this fauna are restricted to strata between the base of the Lexington Limestone (Kirkfieldian Stage, Middle Ordovician) and the top of the Clays Ferry Formation and its lateral equivalent the Kope Formation (Edenian Stage, lower Upper Ordovician), with few species ranging into strata of early Maysvillian Stage (middle Late Ordovician) in adjacent areas of Indiana and Ohio. On the basis of the known geographic distribution of the various species, the fauna in Kentucky consists of an intermingling of immigrant and endemic species. The immigrant component (11 species) is generally limited to the lower half of the Lexington-Clays Ferry depositional sequence and permits the establishment of a degree of biostratigraphic equivalence with outcrop areas in Minnesota-Iowa and New York. On the species level the fauna in Kentucky is dominated by four: Constellaria teres, Heterotrypa foliacea, Parvohallopora nodulosa, and Eridotrypa mutabilis, in decreasing relative abundance. The first three species are restricted to the upper part of the Lexington Limestone and the Clays Ferry Formation. Eridotrypa mutabilis is restricted to the middle part of the Lexington Limestone and the lower half of the Clays Fer

Diffusive transport and reaction in clay rocks: A storage (nuclear waste, CO2, H2), energy (shale gas) and water quality issue

NASA Astrophysics Data System (ADS)

Charlet, Laurent; Alt-Epping, Peter; Wersin, Paul; Gilbert, Benjamin

2017-08-01

Clay rocks are low permeability sedimentary formations that provide records of Earth history, influence the quality of water resources, and that are increasingly used for the extraction or storage of energy resources and the sequestration of waste materials. Informed use of clay rock formations to achieve low-carbon or carbon-free energy goals requires the ability to predict the rates of diffusive transport processes for chemically diverse dissolved and gaseous species over periods up to thousands of years. We survey the composition, properties and uses of clay rock and summarize fundamental science challenges in developing confident conceptual and quantitative gas and solute transport models.

Effects of clay dispersion on aquifer storage and recovery in coastal aquifers

USGS Publications Warehouse

Konikow, Leonard F.; August, L.L.; Voss, C.I.

2001-01-01

Cyclic injection, storage, and withdrawal of freshwater in brackish aquifers is a form of aquifer storage and recovery (ASR) that can beneficially supplement water supplies in coastal areas. A 1970s field experiment in Norfolk, Virginia, showed that clay dispersion in the unconsolidated sedimentary aquifer occurred because of cation exchange on clay minerals as freshwater displaced brackish formation water. Migration of interstitial clay particles clogged pores, reduced permeability, and decreased recovery efficiency, but a calcium preflush was found to reduce clay dispersion and lead to a higher recovery efficiency. Column experiments were performed in this study to quantify the relations between permeability changes and clay mineralogy, clay content, and initial water salinity. The results of these experiments indicate that dispersion of montmorillonite clay is a primary contributor to formation damage. The reduction in permeability by clay dispersion may be expressed as a linear function of chloride content. Incorporating these simple functions into a radial, cross-sectional, variable-density, ground-water flow and transport model yielded a satisfactory simulation of the Norfolk field test - and represented an improvement over the model that ignored changes in permeability. This type of model offers a useful planning and design tool for ASR operations in coastal clastic aquifer systems.

Evaluation of the healing activity of therapeutic clay in rat skin wounds.

PubMed

Dário, Giordana Maciel; da Silva, Geovana Gomes; Gonçalves, Davi Ludvig; Silveira, Paulo; Junior, Adilson Teixeira; Angioletto, Elidio; Bernardin, Adriano Michael

2014-10-01

The use of clays for therapeutic practice is widespread in almost all regions of the world. In this study the physicochemical and microbiological healing characteristics of a clay from Ocara, Brazil, popularly used for therapeutic uses, were analyzed. The presence of Ca, Mg, Al, Fe, and Si was observed, which initially indicated that the clay had potential for therapeutic use. The average particle size of the clay (26.3 μm) can induce the microcirculation of the skin and the XRD analysis shows that the clay is formed by kaolinite and illite, a swelling clay. During the microbiological evaluation there was the need to sterilize the clay for later incorporation into the pharmaceutical formula. The accelerated stability test at 50°C for 3 months has showed that the pharmaceutical formula remained stable with a shelf life of two years. After the stability test the wound-healing capacity of the formulation in rats was evaluated. It was observed that the treatment made with the formulation containing the Ocara clay showed the best results since the formula allowed greater formation of collagen fibers and consequent regeneration of the deep dermis after seven days of treatment and reepithelialization and continuous formation of granulation tissue at the 14th day. Copyright © 2014 Elsevier B.V. All rights reserved.

Field trip guidebook on environmental impact of clays along the upper Texas coast

NASA Technical Reports Server (NTRS)

Garcia, Theron D.; Ming, Douglas W.; Tuck, Lisa Kay

1991-01-01

The field trip was prepared to provide an opportunity to see first hand some the environmental hazards associated with clays in the Houston, Texas area. Because of the very high clay content in area soils and underlying Beaumont Formation clay, Houston is a fitting location to host the Clay Mineral Society. Examinations were made of (1) expansive soils, (2) subsidence and surface faulting, and (3) a landfill located southeast of Houston at the Gulf Coast Waste Disposal Authority where clay is part of the liner material.

Mineralogical Characterization of the Miocene Olcese Formation, Southern San Joaquin Valley, California

NASA Astrophysics Data System (ADS)

Lopez, K. A.; Baron, D.; Guo, J.; Woolford, J. M.

2016-12-01

The early to middle Miocene Olcese Formation in the southern San Joaquin Valley of California consists of shallow marine shelf sands in its lower and upper parts, and non-marine, frequently pumiceous sands in its middle part, and varies in thickness up to 1800 ft. There is little known as to the origin, nature, quantity, and distribution of clay minerals throughout the formation. This study examined 95 sidewall core samples from three wells, as well as 388 cutting samples from four wells and 12 samples from 3 outcrops. Well samples were from depths between 1,800 and 4,000 ft. Qualitative and quantitative mineralogy including clay minerals of the sidewall samples and selected cutting samples was determined by powder X-ray diffraction (XRD). XRD analyses were supplemented by scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS) and petrographic microscopy of selected samples. The main minerals of bulk samples include composite clay, quartz, potassium feldspar/plagioclase, calcite, and clinoptilolite. Content of composite clay varies between 17% and 51%. The clay-size fraction is predominantly composed of smectite, illite, kaolinite and chlorite with smectite being the most abundant. Smectite and clinoptilolite may be the alteration products of deeper burial of volcanic materials. The formation permeability could be significantly lowered by these authigenic minerals.

Detection and cultivation of indigenous microorganisms in Mesozoic claystone core samples from the Opalinus Clay Formation (Mont Terri Rock Laboratory)

NASA Astrophysics Data System (ADS)

Mauclaire, L.; McKenzie, J. A.; Schwyn, B.; Bossart, P.

Although microorganisms have been isolated from various deep-subsurface environments, the persistence of microbial activity in claystones buried to great depths and on geological time scales has been poorly studied. The presence of in-situ microbial life in the Opalinus Clay Formation (Mesozoic claystone, 170 million years old) at the Mont Terri Rock Laboratory, Canton Jura, Switzerland was investigated. Opalinus Clay is a host rock candidate for a radioactive waste repository. Particle tracer tests demonstrated the uncontaminated nature of the cored samples, showing their suitability for microbiological investigations. To determine whether microorganisms are a consistent and characteristic component of the Opalinus Clay Formation, two approaches were used: (i) the cultivation of indigenous micoorganisms focusing mainly on the cultivation of sulfate-reducing bacteria, and (ii) the direct detection of molecular biomarkers of bacteria. The goal of the first set of experiments was to assess the presence of cultivable microorganisms within the Opalinus Clay Formation. After few months of incubation, the number of cell ranged from 0.1 to 2 × 10 3 cells ml -1 media. The microorganisms were actively growing as confirmed by the observation of dividing cells, and detection of traces of sulfide. To avoid cultivation bias, quantification of molecular biomarkers (phospholipid fatty acids) was used to assess the presence of autochthonous microorganisms. These molecules are good indicators of the presence of living cells. The Opalinus Clay contained on average 64 ng of PLFA g -1 dry claystone. The detected microbial community comprises mainly Gram-negative anaerobic bacteria as indicated by the ratio of iso/anteiso phospholipids (about 2) and the detection of large amount of β-hydroxy substituted fatty acids. The PLFA composition reveals the presence of specific functional groups of microorganisms in particular sulfate-reducing bacteria ( Desulfovibrio, Desulfobulbus, and Desulfobacter). This study demonstrates that microorganisms are a characteristic component of the unperturbed Opalinus Clay Formation.

Effect of confining pressure on diffusion coefficients in clay-rich, low-permeability sedimentary rocks.

PubMed

Xiang, Y; Al, T; Mazurek, M

2016-12-01

The effect of confining pressure (CP) on the diffusion of tritiated-water (HTO) and iodide (I - ) tracers through Ordovician rocks from the Michigan Basin, southwestern Ontario, Canada, and Opalinus Clay from Schlattingen, Switzerland was investigated in laboratory experiments. Four samples representing different formations and lithologies in the Michigan Basin were studied: Queenston Formation shale, Georgian Bay Formation shale, Cobourg Formation limestone and Cobourg Formation argillaceous limestone. Estimated in situ vertical stresses at the depths from which the samples were retrieved range from 12.0 to 17.4MPa (Michigan Basin) and from 21 to 23MPa (Opalinus Clay). Effective diffusion coefficients (D e ) were determined in through-diffusion experiments. With HTO tracer, applying CP resulted in decreases in D e of 12.5% for the Queenston Formation shale (CP max =12MPa), 30% for the Georgian Bay Formation shale (15MPa), 34% for the Cobourg Formation limestone (17.4MPa), 31% for the Cobourg Formation argillaceous limestone (17.4MPa) and 43-46% for the Opalinus Clay (15MPa). Decreases in D e were larger for the I - tracer: 13.8% for the Queenston shale, 42% for the Georgian Bay shale, 50% for the Cobourg Formation limestone, 55% for the Cobourg Formation argillaceous limestone and 63-68% for the Opalinus Clay. The tracer-specific nature of the response is attributed to an increasing influence of anion exclusion as the pore size decreases at higher CP. Results from the shales (including Opalinus Clay) indicate that the pressure effect on D e can be represented by a linear relationship between D e and ln(CP), which provides valuable predictive capability. The nonlinearity results in a relatively small change in D e at high CP, suggesting that it is not necessary to apply the exact in situ pressure conditions in order to obtain a good estimate of the in situ diffusion coefficient. Most importantly, the CP effect on shale is reversible (±12%) suggesting that, for argillaceous rocks, it is possible to obtain D e values that are representative of the in-situ condition by conducting measurements on re-pressurized samples that were obtained with standard drilling practices. This may not be the case for brittle rock samples as the results from limestone suggest that irreversible damage occurred during the pressure cycling. Copyright © 2016 Elsevier B.V. All rights reserved.

In situ synthesis, characterization, and catalytic performance of tungstophosphoric acid encapsulated into the framework of mesoporous silica pillared clay.

PubMed

Li, Baoshan; Liu, Zhenxing; Han, Chunying; Ma, Wei; Zhao, Songjie

2012-07-01

Mesoporous silica pillared clay (SPC) incorporated with tungstophosphoric acid (HPW) has been synthesized via in situ introducing P and W source in the acidic suspension of the clay interlayer template during the formation of the silica pillared clay. The samples were characterized by XRD, XRF, FT-IR, TG-DTA, N(2) adsorption-desorption, and SEM techniques. The results showed that the HPW formed by in situ method has been effectively introduced into the framework of mesoporous silica pillared clay and its Keggin structure remained perfectly after formation of the materials. In addition, samples with similar HPW loadings were also prepared by impregnation method using SPC as the support. HPW in the incorporated samples was better dispersed into the silica pillared clay than in the impregnated samples. The results of catalytic tests indicated that the encapsulated materials demonstrated better catalytic performance than the impregnated samples in oxidative desulfurization (ODS) of dibenzothiophene (DBT). Copyright © 2012 Elsevier Inc. All rights reserved.

Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CH4 and CH4/CO2 Mixtures: Implications for CO2-Enhanced Gas Production

NASA Astrophysics Data System (ADS)

Loring, J.

2015-12-01

Injection of CO2 into low permeability shale formations leads to additional gas recovery and reduces the flux of CO2 into the atmosphere, thus combining a strong economic incentive with a permanent storage option for CO2. Reduced formation transmissivity due to clay swelling is a concern in CO2-enhanced gas production. Clay minerals partly determine the physical (i.e. permeability, brittleness) and certain chemical properties (i.e. wetting ability, gas adsorption) of shales, and montmorillonites are of particular interest because they swell by the uptake of species in their interlayer. In this study, the hydration and expansion of Na-, Cs-, and NH4+-saturated montmorillonite (Na-, Cs-, and NH4-SWy-2) in high-pressure (90 bar) and moderate temperature (50 °C) methane, carbon dioxide, and CO2/CH4 mixtures (3 and 25 mole% CO2) were investigated using in situ IR spectroscopic titrations, in situ XRD, in situ MAS-NMR, and ab initio electronic structure calculations. The overarching goal was to better understand the hydration/expansion behavior of Na-SWy-2 in CO2/CH4 fluid mixtures by comparison to Cs-, and NH4+-saturated clays. Specific aims were to (1) determine if CH4 intercalates the clays, (2) probe the effects of increasing dissolved CO2 and H2O concentrations, and (3) understand the role of cation solvation by H2O and/or CO2. In pure CH4, no evidence of CH4 intercalation was detected by IR for any of the clays. Similarly, no measurable changes to the basal spacing were observed by XRD in the presence of pure CH4. However, when dry Cs- and NH4-SWy-2 were exposed to dry fluids containing CO2, IR showed maximum CO2 penetrated the interlayer, XRD indicated the clays expanded, and NMR showed evidence for cation solvation by CO2, in line with theoretical predictions. IR titration of these clays with water showed sorbed H2O concentrations decreased with increasing dissolved CO2, suggesting competition for interlayer residency by CO2 and H2O. For Na-SWy-2, on the other hand, CO2 intercalated the clay and was at a maximum only after a minimum sorbed H2O was achieved. Further increases in sorbed H2O led to displacement of intercalated CO2. These findings demonstrate that complicated H2O and CO2 intercalation processes could lead to permeability changes that directly impact methane transmissivity in shales.

Hydrogeologic characterization of the Modesto Area, San Joaquin Valley, California

USGS Publications Warehouse

Burow, Karen R.; Shelton, Jennifer L.; Hevesi, Joseph A.; Weissmann, Gary S.

2004-01-01

Hydrogeologic characterization was done to develop an understanding of the hydrogeologic setting near Modesto by maximizing the use of existing data and building on previous work in the region. A substantial amount of new lithologic and hydrologic data are available that allow a more complete and updated characterization of the aquifer system. In this report, geologic units are described, a database of well characteristics and lithology is developed and used to update the regional stratigraphy, a water budget is estimated for water year 2000, a three-dimensional spatial correlation map of aquifer texture is created, and recommendations for future data collection are summarized. The general physiography of the study area is reflected in the soils. The oldest soils, which have low permeability, exist in terrace deposits, in the interfan areas between the Stanislaus, Tuolumne, and Merced Rivers, at the distal end of the fans, and along the San Joaquin River floodplain. The youngest soils have high permeability and generally have been forming on the recently deposited alluvium along the major stream channels. Geologic materials exposed or penetrated by wells in the Modesto area range from pre-Cretaceous rocks to recent alluvium; however, water-bearing materials are mostly Late Tertiary and Quaternary in age. A database containing information from more than 3,500 drillers'logs was constructed to organize information on well characteristics and subsurface lithology in the study area. The database was used in conjunction with a limited number of geophysical logs and county soil maps to define the stratigraphic framework of the study area. Sequences of red paleosols were identified in the database and used as stratigraphic boundaries. Associated with these paleosols are very coarse grained incised valley-fill deposits. Some geophysical well logs and other sparse well information suggest the presence of one of these incised valley-fill deposits along and adjacent to the Tuolumne River east of Modesto, a feature that may have important implications for ground-water flow and transport in the region. Although extensive work has been done by earlier investigators to define the structure of the Modesto area aquifer system, this report has resulted in some modification to the lateral extent of the Corcoran Clay and the regional dip of the Mehrten Formation. Well logs in the database indicating the presence of the Corcoran Clay were used to revise the eastern extent of the Corcoran Clay, which lies approximately parallel to the axis of valley. The Mehrten Formation is distinguished in the well-log database by its characteristic black sands consisting of predominantly andesitic fragments. Black sands in wells listed in the database indicate that the formation may lie as shallow as 120 meters (400 feet) below land surface under Modesto, approximately 90 meters (300 feet) shallower than previously thought. The alluvial aquifer system in the Modesto area comprises an unconfined to semiconfined aquifer above and east of the Corcoran Clay confining unit and a confined aquifer beneath the Corcoran Clay. The unconfined aquifer is composed of alluvial sediments of the Modesto, Riverbank, and upper Turlock Lake formations. The unconfined aquifer east of the Corcoran Clay becomes semiconfined with depth due to the numerous discontinuous clay lenses and extensive paleosols throughout the aquifer thickness. The confined aquifer is composed primarily of alluvial sediments of the Turlock Lake and upper Mehrten Formations, extending from beneath the Corcoran Clay to the base of fresh water. Ground water in the unconfined to semiconfined aquifer flows to the west and southwest. The primary source of present-day recharge is percolating excess irrigation water. The primary ground-water discharge is extensive ground-water pumping in the unconfined to semiconfined aquifer, imposing a significant component of vertical flo

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.

Enhanced transcription and translation in clay hydrogel and implications for early life evolution

PubMed Central

Yang, Dayong; Peng, Songming; Hartman, Mark R.; Gupton-Campolongo, Tiffany; Rice, Edward J.; Chang, Anna Kathryn; Gu, Zi; Lu, G. Q. (Max); Luo, Dan

2013-01-01

In most contemporary life forms, the confinement of cell membranes provides localized concentration and protection for biomolecules, leading to efficient biochemical reactions. Similarly, confinement may have also played an important role for prebiotic compartmentalization in early life evolution when the cell membrane had not yet formed. It remains an open question how biochemical reactions developed without the confinement of cell membranes. Here we mimic the confinement function of cells by creating a hydrogel made from geological clay minerals, which provides an efficient confinement environment for biomolecules. We also show that nucleic acids were concentrated in the clay hydrogel and were protected against nuclease, and that transcription and translation reactions were consistently enhanced. Taken together, our results support the importance of localized concentration and protection of biomolecules in early life evolution, and also implicate a clay hydrogel environment for biochemical reactions during early life evolution. PMID:24196527

Installation Restoration Program. Phase 1. Record Search for the 106th Aerospace Rescue and Recovery Group, New York Air National Guard, Suffolk County Air National Guard Base, Westhampton Beach, New York.

DTIC Science & Technology

1987-07-01

Raritan Formation and the Magothy Formation. The Raritan Formation, which rests on the bedrock, is subdivided into the Lloyd Sand Member and the clay...member, which is the uppermost part. The Raritan Formation is below sea level. The Magothy Formation outcrops at only a few locations on Long Island...the Magothy , and the Lloyd Sand member of the Raritan Formation. These aquifers are made up of sand and gravel and small amounts of silt and clay

Paired measurements of K and Mg isotopes and clay authigenesis in marine sediments

NASA Astrophysics Data System (ADS)

Santiago Ramos, D. P.; Dunlea, A. G.; Higgins, J. A.

2016-12-01

Despite its importance as a major sink for seawater K and Mg, estimates of clay authigenesis in marine sediments remain poorly constrained. Previous work on Mg isotope fractionation during clay formation has revealed a preferential uptake of 26Mg, yielding authigenic clay products with potentially distinct δ26Mg compared to the detrital component. In a similar manner, we aim to quantify the K isotope fractionation during authigenic clay formation and to use paired δ26Mg and δ41K measurements as proxies for the identification and quantification of authigenic clays in shallow and deep marine sedimentary systems. To better understand the behavior of paired Mg and K isotopes during authigenic clay formation in marine sediments, we measured δ26Mg and δ41K values of pore-fluids and sediments from ODP/IODP sites 1052, U1395, U1403 and U1366. We find that while pore-fluid K concentrations at sites 1052, U1395 and U1403 all decline with depth, δ41K profiles differ significantly. These differences might be a result of a complex interplay between clay authigenesis, sedimentation rate, and fractionation of K isotopes during diffusion. Results from 1-D diffusion-advection-reaction models suggest that, in contrast to Mg, diffusion may play an important role in determining the overall K isotope fractionation during clay authigenesis in sites with low-sedimentation rates. Sites with high sedimentation rates may act as close systems where diffusion is negligible. In such cases, K uptake can be modeled as a Rayleigh distillation process and K isotope fractionation can be estimated. Measurements of δ26Mg and δ41K of pore-fluids from site U1395 and bulk sediments from U1366 suggest that paired measurements of these isotopic systems in siliciclastic marine sediments can provide new insights into rates of marine clay authigenesis, a globally important but understudied component of many geochemical cycles.

Frictional melting of clayey gouge during seismic fault slip: Experimental observation and implications

NASA Astrophysics Data System (ADS)

Han, Raehee; Hirose, Takehiro; Jeong, Gi Young; Ando, Jun-ichi; Mukoyoshi, Hideki

2014-08-01

Clayey gouges are common in fault slip zones at shallow depths. Thus, the fault zone processes and frictional behaviors of the gouges are critical to understanding seismic slip at these depths. We conducted rotary shear tests on clayey gouge (~41 wt % clay minerals) at a seismic slip rate of 1.3 m/s. Here we report that the gouge was melted at 5 MPa of normal stress and room humidity conditions. The initial local melting was followed by melt layer formation. Clay minerals (e.g., smectite and illite) and plagioclase were melted and quenched to glass with numerous vesicles. Both flash heating and bulk temperature increases appear to be responsible for the melting. This observation of clayey gouge melting is comparable to that of natural faults (e.g., Chelungpu fault, Taiwan). Due to heterogeneous fault zone properties (e.g., permeability), frictional melting may be one of the important processes in clayey slip zones at shallow depths.

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.

Clay-Alcohol-Water Dispersions: Anomalous Viscosity Changes Due to Network Formation of Clay Nanosheets Induced by Alcohol Clustering.

PubMed

Kimura, Yuji; Haraguchi, Kazutoshi

2017-05-16

Clay-alcohol-water ternary dispersions were compared with alcohol-water binary mixtures in terms of viscosity and optical absorbance. Aqueous clay dispersions to which lower alcohols (ethanol, 1-propanol, 2-propanol, and tert-butanol) were added exhibited significant viscosity anomalies (maxima) when the alcohol content was 30-55 wt %, as well as optical absorbance anomalies (maxima). The maximum viscosity (η max ) depended strongly on the clay content and varied between 300 and 8000 mPa·s, making it remarkably high compared with the viscosity anomalies (2 mPa·s) observed in alcohol-water binary mixtures. The alcohol content at η max decreased as the hydrophobicity of the alcohol increased. The ternary dispersions with viscosity anomalies exhibited thixotropic behaviors. The effects of other hydrophilic solvents (glycols) and other kinds of clays were also clarified. Based on these findings and the average particle size changes, the viscosity anomalies in the ternary dispersions were explained by alcohol-clustering-induced network formation of the clay nanosheets. It was estimated that 0.9, 1.7, and 2.5 H 2 O molecules per alcohol molecule were required to stabilize the ethanol, 2-propanol, and tert-butanol, respectively, in the clay-alcohol-water dispersions.

Kaolinite, illite and quartz dissolution in the karstification of Paleozoic sandstones of the Furnas Formation, Paraná Basin, Southern Brazil

NASA Astrophysics Data System (ADS)

Melo, Mário Sérgio de; Guimarães, Gilson Burigo; Chinelatto, Adilson Luiz; Giannini, Paulo César Fonseca; Pontes, Henrique Simão; Chinelatto, Adriana Scoton Antonio; Atencio, Daniel

2015-11-01

Karstification processes in sandstones of the Furnas Formation, Silurian to Devonian of the Paraná Basin, have been described since the mid-twentieth century. However, some geologists still doubt the idea of true karst in sandstones. Studies carried out in the Campos Gerais region, Paraná State, Southern Brazil, aimed at investigating the nature of erosion processes in Furnas Formation and the role of the dissolution in the development of their notorious erosive features and underground cavities. These studies have led to the recognition of dissolution macro to micro features ('furnas', caves, ponds, sinks, ruiniform relief on cliffs and rocky surfaces, grain corrosion, speleothems, mineral reprecipitation and incrustation). The analysis (scanning electron microscopy, energy dispersive spectrometry and x-ray diffractometry) of sandstones and their alterites has indicated significant dissolution of clay cement along with discrete quartz grain dissolution. This mesodiagenetic cement (kaolinite and illite) is dissolved and reprecipitated as clay minerals with poorly developed crystallinity along with other minerals, such as variscite and minerals of the alunite supergroup, suggesting organic participation in the processes of dissolution and incrustation. The mineral reprecipitation usually forms centimetric speleothems, found in cavities and sheltered rocky surfaces. The cement dissolution associated with other factors (fractures, wet weather, strong hydraulic gradient, antiquity of the landforms) leads to the rock arenisation, the underground erosion and the appearance of the karst features. Carbonate rocks in the basement may locally be increasing the karst forms in the overlying Furnas Formation. The recognition of the karst character of the Furnas Formation sandstones has important implications in the management of underground water resources (increasingly exploited in the region), in the use of the unique geological heritage and in the prevention of geo-environmental accidents resulting from underground erosion phenomena.

Clay alteration and gold deposition in the genesis and blue star deposits, Eureka County, Nevada

USGS Publications Warehouse

Drews-Armitage, S. P.; Romberger, S.B.; Whitney, C.G.

1996-01-01

The Genesis and Blue Star sedimentary rock-hosted gold deposits occur within the 40-mile-long Carlin trend and are located in Eureka County, Nevada. The deposits are hosted within the Devonian calcareous Popovich Formation, the siliciclastic Rodeo Creek unit and the siliciclastic Vinini Formation. The host rocks have undergone contact metamorphism, decalcification, silicification, argillization, and supergene oxidation. Detailed characterization of the alteration patterns, mineralogy, modes of occurrence, and associated geochemistry of clay minerals resulted in the following classifications: least altered rocks, found distal to the orebody, consisting of both metamorphosed and unmetamorphosed host rock that has not been completely decalcified; and altered rocks, found proximal to the orebody that have been decalcified. Altered rocks are classified further into the following groups based on clay mineral content: silicic, 1 to 10 percent clay; silicicargillic, 10 to 35 percent clay; and argillic, 35 to 80 percent clay. Clay species identified are 1M illite, 2M1 illite, kaolinite, halloysite, and dioctahedral smectite. An early hydrothermal event resulted in the precipitation of euhedral kaolinite and at least one generation of silica. This event occurred contemporaneously with decalcification which increased rock permeability and porosity. A second clay alteration event resulted in the precipitation of hydrothermal 1M illite which replaced hydrothermal kaolinite and is associated with gold deposition. Silver and silica deposition is also associated with this phase of hydrothermal alteration. Hydrothermal alteration was followed by supergene alteration which resulted in the formation of supergene kaolinite, halloysite, and smectite as well as the oxidation of iron-bearing minerals. Supergene clays are concentrated along faults, dike margins, and within rocks containing carbonate. Gold mineralization is not associated with supergene clay minerals within the Genesis and Blue Star deposits. Rocks classified as silicic-argillic in the Popovich Formation represent the most significant gold host. Silicicargillic rocks commonly exhibit bedding-parallel alteration zones. This pattern of alteration indicates that stratigraphy as well as northwest-trending structures played a significant role in the migration of gold-bearing fluids. Based on K-Ar age determinations of hydrothermal 1M illite associated with gold, the main event of mineralization in the Genesis and Blue Star deposits occurred between 93 and 100 Ma, during mid-Cretaceous time.

Mechanism of smectic arrangement of montmorillonite and bentonite clay platelets incorporated in gels of poly(acrylamide) induced by the interaction with cationic surfactants.

PubMed

Starodoubtsev, S G; Lavrentyeva, E K; Khokhlov, A R; Allegra, G; Famulari, A; Meille, S V

2006-01-03

Structure transitions, induced by the interaction with the cationic surfactant cetylpyridinium chloride in nanocomposite gels of poly(acrylamide) with incorporated suspensions of the two closely related layered clays bentonite and montmorillonite, were studied. Unexpectedly, different behaviors were revealed. X-ray diffraction measurements confirm that, due to the interaction with the surfactant, initially disordered bentonite platelets arrange into highly ordered structures incorporating alternating clay platelets and surfactant bilayers. The formation of these smectic structures also in the cross-linked polymer gels, upon addition of the surfactant, is explained by the existence of preformed, poorly ordered aggregates of the clay platelets in the suspensions before the gel formation. In the case of montmorillonite, smectic ordering of the disordered platelets in the presence of the surfactant is observed only after drying the suspensions and the clay-gel composites. Rheology studies of aqueous suspensions of the two clays, in the absence of both surfactant and gel, evidence a much higher viscosity for bentonite than for montmorillonite, suggesting smaller clay-aggregate size in the latter case. Qualitatively consistent results are obtained from optical micrographs.

Long-term non-isothermal reactive transport model of compacted bentonite, concrete and corrosion products in a HLW repository in clay

NASA Astrophysics Data System (ADS)

Mon, Alba; Samper, Javier; Montenegro, Luis; Naves, Acacia; Fernández, Jesús

2017-02-01

Radioactive waste disposal in deep geological repositories envisages engineered barriers such as carbon-steel canisters, compacted bentonite and concrete liners. The stability and performance of the bentonite barrier could be affected by the corrosion products at the canister-bentonite interface and the hyper-alkaline conditions caused by the degradation of concrete at the bentonite-concrete interface. Additionally, the host clay formation could also be affected by the hyper-alkaline plume at the concrete-clay interface. Here we present a non-isothermal multicomponent reactive transport model of the long-term (1 Ma) interactions of the compacted bentonite with the corrosion products of a carbon-steel canister and the concrete liner of the engineered barrier of a high-level radioactive waste repository in clay. Model results show that magnetite is the main corrosion product. Its precipitation reduces significantly the porosity of the bentonite near the canister. The degradation of the concrete liner leads to the precipitation of secondary minerals and the reduction of the porosity of the bentonite and the clay formation at their interfaces with the concrete liner. The reduction of the porosity becomes especially relevant at t = 104 years. The zones affected by pore clogging at the canister-bentonite and concrete-clay interfaces at 1 Ma are approximately equal to 1 and 3.3 cm thick, respectively. The hyper-alkaline front (pH > 8.5) spreads 2.5 cm into the clay formation after 1 Ma. Our simulation results share the key features of the models reported by others for engineered barrier systems at similar chemical conditions, including: 1) Pore clogging at the canister-bentonite and concrete-clay interfaces; 2) Narrow alteration zones; and 3) Limited smectite dissolution after 1 Ma.

Long-term non-isothermal reactive transport model of compacted bentonite, concrete and corrosion products in a HLW repository in clay.

PubMed

Mon, Alba; Samper, Javier; Montenegro, Luis; Naves, Acacia; Fernández, Jesús

2017-02-01

Radioactive waste disposal in deep geological repositories envisages engineered barriers such as carbon-steel canisters, compacted bentonite and concrete liners. The stability and performance of the bentonite barrier could be affected by the corrosion products at the canister-bentonite interface and the hyper-alkaline conditions caused by the degradation of concrete at the bentonite-concrete interface. Additionally, the host clay formation could also be affected by the hyper-alkaline plume at the concrete-clay interface. Here we present a non-isothermal multicomponent reactive transport model of the long-term (1Ma) interactions of the compacted bentonite with the corrosion products of a carbon-steel canister and the concrete liner of the engineered barrier of a high-level radioactive waste repository in clay. Model results show that magnetite is the main corrosion product. Its precipitation reduces significantly the porosity of the bentonite near the canister. The degradation of the concrete liner leads to the precipitation of secondary minerals and the reduction of the porosity of the bentonite and the clay formation at their interfaces with the concrete liner. The reduction of the porosity becomes especially relevant at t=10 4 years. The zones affected by pore clogging at the canister-bentonite and concrete-clay interfaces at 1Ma are approximately equal to 1 and 3.3cm thick, respectively. The hyper-alkaline front (pH>8.5) spreads 2.5cm into the clay formation after 1Ma. Our simulation results share the key features of the models reported by others for engineered barrier systems at similar chemical conditions, including: 1) Pore clogging at the canister-bentonite and concrete-clay interfaces; 2) Narrow alteration zones; and 3) Limited smectite dissolution after 1Ma. Copyright © 2016 Elsevier B.V. All rights reserved.

Application of Chromophoric Dissolved Organic Matter Absorbance and Excitation-Emission Matrix Fluorescence Spectra (EEMS) to Investigate Clay-Organic Matter Flocculation Processes in Riverine-Estuarine Systems

NASA Astrophysics Data System (ADS)

Smith, J. P.; Reed, A. H.; Boyd, T. J.

2016-12-01

Changes in hydrodynamic shear, variations in ionic strength (salinity), and to a lesser degree pH, along the salinity gradient influences clay-organic matter (OM) flocculation, disaggregation and particle size distributions with depth in natural river-estuarine waters. The scale and rate of aggregation and disaggregation of specific clay-OM flocs assemblages under different hydrodynamic and physiochemical conditions in estuaries or coastal river systems is an area of ongoing research. Chromophoric dissolved organic matter (CDOM) is the fraction of the DOM pool that absorbs and/or emits light at discrete wavelengths when excited. The CDOM absorbance and Excitation Emission Matrix (EEM) fluorescence spectra in natural waters can potentially be used to investigate clay-OM interactions and implications for formation kinetics, size, strength, and settling velocities of cohesive particulate aggregates (flocs and suspended sediments) as they respond to hydrodynamic shear under different physiochemical conditions. Size characteristics of particulate matter and sediment samples collected from the Misa River in Italy in 2014 were compared to the optical properties of the water column to identify potential OM components/constituents influencing flocculation processes in riverine-estuarine systems. The EEMs results were coupled with a parallel factor analysis (PARAFAC) model to associate previously identified EEMS regions of CDOM components to those found in the waters of this study and identify the main OM components/constituents influencing the multi-way variance of the EEMS data. Initial results from the Misa River and subsequent studies show a difference in dominant DOM types by salinity, clay-OM composition, and flow conditions that may be indicative of system specific particle flocculation and disaggregation under different hydrodynamic regimes. These results suggest that the CDOM absorbance and EEMS fluorescence spectra in natural waters can potentially be used to qualify the influence of OM on the flocculation and sedimentation of clay particulates in river-estuarine systems under different physiochemical and hydrodynamic conditions.

Influence of clay minerals on curcumin properties: Stability and singlet oxygen generation

NASA Astrophysics Data System (ADS)

Gonçalves, Joyce L. S.; Valandro, Silvano R.; Poli, Alessandra L.; Schmitt, Carla C.

2017-09-01

Curcumin (CUR) has showed promising photophysical properties regarding to biological and chemical sciences. However, the main barrier for those applications are their low solubility and stability in aqueous solution. The effects of two different clay minerals, the montmorillonite (SWy-2) and the Laponite RD (Lap) nanoclay, on the stabilization of Curcumin were investigated. Their effects were compared with two well-established environments (acidic and neutral aqueous media). CUR/clay hybrids were prepared using a simple and fast method, where CUR solution was added into clay suspensions, to obtain well dispersed hybrids in water. The degradation process of CUR and CUR/clays hybrids was investigated using UV-Vis spectroscopic. For both studied hybrids, the CUR degradation process was suppressed by the presence of the clay particles. Furthermore, the Lap showed a great stabilization effect than SWy-2. This behavior was due to the smaller particle size and higher exfoliation ability of Lap, providing a large surface for CUR adsorption compared to SWy-2. The degradation process of CUR solutions and CUR/clay hybrids was also studied in the presence of light. CUR photodegradation process was faster not only in the aqueous solution but also in the clay suspension compared to those studied in the dark. The presence of clay particles accelerated the photodegradation of CUR due to the products formation in the reactions between CUR and oxygen radicals. Our results showed that the singlet oxygen quantum yield (ΦΔ) of CUR were about 59% higher in the clay suspensions than CUR in aqueous solution. Therefore, the formation of CUR/clay hybrids, in particularly with Lap, suppressed the degradation in absence light of CUR and increased the singlet oxygen generation, which makes this hybrids of CUR/clay a promising material to enlarge the application of CUR in the biological sciences.

Theoretical investigation of the role of clay edges in prebiotic peptide bond formation. II - Structures and thermodynamics of the activated complex species

NASA Technical Reports Server (NTRS)

Collins, Jack R.; Loew, Gilda H.; Luke, Brian T.; White, David H.

1988-01-01

Molecular orbital calculations are used to study amino acid activation by anhydride formation in neutral phosphates and in tetrahedral silicate and aluminate sites on clay edges. The results agree with previous ab initio studies of Luke et al. (1984) on the reactant species. Relative heats of formation of the anhydrides indicate the extent of anhydride formation to be the greatest for Al and the least for phosphate, which is the same order as the stability of hydrolysis.

Bacterial interactions and transport in geological formation of alumino-silica clays.

PubMed

Vu, Kien; Yang, Guang; Wang, Boya; Tawfiq, Kamal; Chen, Gang

2015-01-01

Bacterial transport in the subsurface is controlled by their interactions with the surrounding environment, which are determined by the surface properties of the geological formation and bacterial surfaces. In this research, surface thermodynamic properties of Escherichia coli and the geological formation of alumino-silica clays were characterized based on contact angle measurements, which were utilized to quantify the distance-dependent interactions between E. coli and the geological formation according to the traditional and extended Derjaguin, Landau, Verwey and Overbeek (DLVO) theory. E. coli attachment to alumino-silica clays was evaluated in laboratory columns under saturated and steady-state flow conditions. E. coli deposition coefficient and desorption coefficient were simulated using convection-dispersion transport models against E. coli breakthrough curves, which were then linked to interactions between E. coli and the geological formation. It was discovered that E. coli deposition was controlled by the long-ranged electrostatic interaction and E. coli desorption was attributed to the short-ranged Lifshitz-van der Waals and Lewis acid-base interactions. E. coli transport in three layers of different alumino-silica clays was further examined and the breakthrough curve was simulated using E. coli deposition coefficient and desorption coefficient obtained from their individual column experiments. The well-fitted simulation confirmed that E. coli transport observations were interaction-dependent phenomena between E. coli and the geological formation. Published by Elsevier B.V.

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)

Boron Enrichment in Martian Clay

PubMed Central

Nagashima, Kazuhide; Freeland, Stephen J.

2013-01-01

We have detected a concentration of boron in martian clay far in excess of that in any previously reported extra-terrestrial object. This enrichment indicates that the chemistry necessary for the formation of ribose, a key component of RNA, could have existed on Mars since the formation of early clay deposits, contemporary to the emergence of life on Earth. Given the greater similarity of Earth and Mars early in their geological history, and the extensive disruption of Earth's earliest mineralogy by plate tectonics, we suggest that the conditions for prebiotic ribose synthesis may be better understood by further Mars exploration. PMID:23762242

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

2011-11-02

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.

Modeling Coupled Processes in Clay Formations for Radioactive Waste Disposal

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

Liu, Hui-Hai; Rutqvist, Jonny; Zheng, Liange

As a result of the termination of the Yucca Mountain Project, the United States Department of Energy (DOE) has started to explore various alternative avenues for the disposition of used nuclear fuel and nuclear waste. The overall scope of the investigation includes temporary storage, transportation issues, permanent disposal, various nuclear fuel types, processing alternatives, and resulting waste streams. Although geologic disposal is not the only alternative, it is still the leading candidate for permanent disposal. The realm of geologic disposal also offers a range of geologic environments that may be considered, among those clay shale formations. Figure 1-1 presents themore » distribution of clay/shale formations within the USA. Clay rock/shale has been considered as potential host rock for geological disposal of high-level nuclear waste throughout the world, because of its low permeability, low diffusion coefficient, high retention capacity for radionuclides, and capability to self-seal fractures induced by tunnel excavation. For example, Callovo-Oxfordian argillites at the Bure site, France (Fouche et al., 2004), Toarcian argillites at the Tournemire site, France (Patriarche et al., 2004), Opalinus clay at the Mont Terri site, Switzerland (Meier et al., 2000), and Boom clay at Mol site, Belgium (Barnichon et al., 2005) have all been under intensive scientific investigations (at both field and laboratory scales) for understanding a variety of rock properties and their relations with flow and transport processes associated with geological disposal of nuclear waste. Clay/shale formations may be generally classified as indurated and plastic clays (Tsang et al., 2005). The latter (including Boom clay) is a softer material without high cohesion; its deformation is dominantly plastic. For both clay rocks, coupled thermal, hydrological, mechanical and chemical (THMC) processes are expected to have a significant impact on the long-term safety of a clay repository. For example, the excavation-damaged zone (EDZ) near repository tunnels can modify local permeability (resulting from induced fractures), potentially leading to less confinement capability (Tsang et al., 2005). Because of clay's swelling and shrinkage behavior (depending on whether the clay is in imbibition or drainage processes), fracture properties in the EDZ are quite dynamic and evolve over time as hydromechanical conditions change. To understand and model the coupled processes and their impact on repository performance is critical for the defensible performance assessment of a clay repository. Within the Natural Barrier System (NBS) group of the Used Fuel Disposition (UFD) Campaign at DOE's Office of Nuclear Energy, LBNL's research activities have focused on understanding and modeling such coupled processes. LBNL provided a report in this April on literature survey of studies on coupled processes in clay repositories and identification of technical issues and knowledge gaps (Tsang et al., 2010). This report will document other LBNL research activities within the natural system work package, including the development of constitutive relationships for elastic deformation of clay rock (Section 2), a THM modeling study (Section 3) and a THC modeling study (Section 4). The purpose of the THM and THC modeling studies is to demonstrate the current modeling capabilities in dealing with coupled processes in a potential clay repository. In Section 5, we discuss potential future R&D work based on the identified knowledge gaps. The linkage between these activities and related FEPs is presented in Section 6.« less

Installation Restoration Program. Phase 1. Records Search Andrews AFB. Maryland

DTIC Science & Technology

1985-06-01

red to silvery-qrey, functions ma a conf ining bed. Formation. ~Va plastics thin lonses of pole gray silt. Ann"a Formation. ye (0-210 sand, qrsenieh...the Nanjemoy Formation (a clayey glauconi- tic sand, two to thirty feet thick) and the Marlboro Clay (a plastic clay with silt partings, two to... plastics , empty 55-gallon drums, waste lumber, tires, pipes, and hospital wastes such as unused needles and chemical reagents. In the past, Site D-4 was

Clay, Water, and Salt: Controls on the Permeability of Fine-Grained Sedimentary Rocks.

PubMed

Bourg, Ian C; Ajo-Franklin, Jonathan B

2017-09-19

The ability to predict the permeability of fine-grained soils, sediments, and sedimentary rocks is a fundamental challenge in the geosciences with potentially transformative implications in subsurface hydrology. In particular, fine-grained sedimentary rocks (shale, mudstone) constitute about two-thirds of the sedimentary rock mass and play important roles in three energy technologies: petroleum geology, geologic carbon sequestration, and radioactive waste management. The problem is a challenging one that requires understanding the properties of complex natural porous media on several length scales. One inherent length scale, referred to hereafter as the mesoscale, is associated with the assemblages of large grains of quartz, feldspar, and carbonates over distances of tens of micrometers. Its importance is highlighted by the existence of a threshold in the core scale mechanical properties and regional scale energy uses of shale formations at a clay content X clay ≈ 1/3, as predicted by an ideal packing model where a fine-grained clay matrix fills the gaps between the larger grains. A second important length scale, referred to hereafter as the nanoscale, is associated with the aggregation and swelling of clay particles (in particular, smectite clay minerals) over distances of tens of nanometers. Mesoscale phenomena that influence permeability are primarily mechanical and include, for example, the ability of contacts between large grains to prevent the compaction of the clay matrix. Nanoscale phenomena that influence permeability tend to be chemomechanical in nature, because they involve strong impacts of aqueous chemistry on clay swelling. The second length scale remains much less well characterized than the first, because of the inherent challenges associated with the study of strongly coupled nanoscale phenomena. Advanced models of the nanoscale properties of fine-grained media rely predominantly on the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, a mean field theory of colloidal interactions that accurately predicts clay swelling in a narrow range of conditions (low salinity, low compaction, Na + counterion). An important feature of clay swelling that is not predicted by these models is the coexistence, in most conditions of aqueous chemistry and dry bulk density, of two types of pores between parallel smectite particles: mesopores with a pore width of >3 nm that are controlled by long-range interactions (the osmotic swelling regime) and nanopores with a pore width <1 nm that are controlled by short-range interactions (the crystalline swelling regime). Nanogeochemical characterization and simulation techniques, including coarse-grained and all-atom molecular dynamics simulations, hold significant promise for the development of advanced constitutive relations that predict this coexistence and its dependence on aqueous chemistry.

A newly discovered K-bentonite zone in the Lower Devonian of the Appalachian Basin; Basal Esopus and Needmore Formations (Late Pragian-Emsian)

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

Ver Straeten, C.A.

1992-01-01

The K-bentonite-rich interval of the Esopus Formation (eastern New York and northeastern Pennsylvania) overlies the coeval Oriskany/Glenerie/Ridgely Formations and ranges from 1 to 6.3 m in thickness. Six to seventeen soapy-feeling, yellow, tan, green, or gray clay to claystone beds (0.001 to 0.5 m-thick) interbedded with thin siltstone and chert beds (0.02--1 m-thick) characterize outcrops in eastern New York. Heavy mineral separates from these layers yield abundant uncorraded euhedral zircons and apatites, indicating that these are K-bentonites. In eastern Pennsylvania, the westernmost outcrop of the Esopus Formation displays a 2.3 m-thick massive, soapy-feeling clay to claystone-dominated interval. The presence ofmore » both coarse, highly abraded and small, fragile, pristine-appearing zircons and apatites from a 20 cm sampled interval may indicate a complex amalgamation/reworking history to the relatively thick, clay-dominated strata. Similar clay/claystone-rich strata have been found in the lower 0.15 to 1 m of the Beaverdam Member (Needmore Formation) in central Pennsylvania. Interbedded clays and claystones with or without minor siltstone beds characterize some outcrops. Other localities are clay-dominated, with minor amounts of quartz sand present in strata immediately overlying the Ridgely Sandstone. These newly discovered K-bentonite-rich strata mark a transition from shelfal orthoquartzites and carbonates to basinal black/dark gray shales similar to the overlying Middle Devonian Tioga ash interval. Deposition of ash-rich strata, associated with increased volcanic activity, coincided with subsidence of the foreland basin/relative sea level rise. These events were concurrent with a flush of siliciclastic sediments into the basin and are indicative of the onset of an early tectophase of the Devonian Acadian Orogeny.« less

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

NASA Technical Reports Server (NTRS)

Orenberg, James; Handy, Jonathan

1992-01-01

The diffuse reflectance spectra of Hawaiian palagonite mixtures with an Fe-rich montmorillonite have prompted their present use as spectral analogs of the Martian surface. Like the Mars spectrum and unlike clays, the 2.2-micron reflectance spectrum absorption band is not present in the palagonite sample; neither is the 2.2-micron Al-OH clay lattice band seen in palagonite-montmorillonite mixtures, where the latter component remains below 15 wt pct. Fe-rich montmorillonite clay may therefore be present in Mars, in combination with palagonite, while remaining undetected in remotely sensed spectra.

Clay deposits of the Tierra Colorado district, southern Orange County, California

USGS Publications Warehouse

Daviess, Steven Norman; Bramlette, M.N.

1953-01-01

The clay of this district is being mined for fire brick by the Vitrofrax Corporation. Much of the clay contains 35 percent or more of alumina and between 1 and 2 percent of iron oxide. Production is largely from an underground mine as the best clay deposit known in the district occurs on the side of a steep hill with more than 100 feet of sandstone overlying most of it. The good clay deposits occur at the base of an Eocene sandstone formation, and overlie mottled clays with a high iron content that are residual deposits formed on an old weathered surface. Mapping indicates that the clay deposits are very lenticular, though all occur at the same stratigraphic position, and they grade laterally into sandy clay and quartz sand. Topographic relief and the dip of the strata preclude finding large areas where the clay strata have relatively little overburden.

K-T impact(s): Continental, oceanic or both

NASA Technical Reports Server (NTRS)

Sharpton, V. L.; Schuraytz, B. C.; Murali, A. V.; Ryder, G.; Burke, K.

1988-01-01

Although geochemical and mineralogical evidence indicate that a major accretionary event occurred at the K-T boundary, no impact crater of suitable size and age was recognized. The 35 km Manson Structure, Iowa, was suggested recently as a possibility and Ar-40/Ar-39 determinations indicate that its formation age is indistinguishable from that of the K-T boundary. In order to test a possible association between Manson and the K-T boundary clay, the geochemistry and mineralogy of the K-T boundary clays at the Scollard Canyon section, Alberta and the Starkville South section, Colorado are compared with three dominant lithologies affected by the Manson impact: Proterozoic red clastics, underlying late-state granites, and gneisses. The chemical and mineralogical makeup of the Scollard Canyon boundary clay and its clastic constituents are presented, commenting on the implications for impact models. An impact into crystalline material of continental affinity appears to be required to explain the mineralogy and chemistry of the Scollard Canyon (and other Western N. American K-T sections). The low REE abundances of some K-T boundary layers are unusual but perhaps attempts should be made to understand the contributions of individual crustal components (e.g., carbonates, arkoses) as well as the potential for alteration involving these and other elements during and after impact-induced vaporization, before mantle excavation is invoked. If further studies confirm the results of published studies of marine boundary clays that indicate an oceanic target, attention must be paid to the possibility that multiple impacts occurred at the K-T boundary - one or more on the continents and one or more in the ocean.

Constraints on silicates formation in the Si-Al-Fe system: Application to hard deposits in steam generators of PWR nuclear reactors

NASA Astrophysics Data System (ADS)

Berger, Gilles; Million-Picallion, Lisa; Lefevre, Grégory; Delaunay, Sophie

2015-04-01

Introduction: The hydrothermal crystallization of silicates phases in the Si-Al-Fe system may lead to industrial constraints that can be encountered in the nuclear industry in at least two contexts: the geological repository for nuclear wastes and the formation of hard sludges in the steam generator of the PWR nuclear plants. In the first situation, the chemical reactions between the Fe-canister and the surrounding clays have been extensively studied in laboratory [1-7] and pilot experiments [8]. These studies demonstrated that the high reactivity of metallic iron leads to the formation of Fe-silicates, berthierine like, in a wide range of temperature. By contrast, the formation of deposits in the steam generators of PWR plants, called hard sludges, is a newer and less studied issue which can affect the reactor performance. Experiments: We present here a preliminary set of experiments reproducing the formation of hard sludges under conditions representative of the steam generator of PWR power plant: 275°C, diluted solutions maintained at low potential by hydrazine addition and at alkaline pH by low concentrations of amines and ammoniac. Magnetite, a corrosion by-product of the secondary circuit, is the source of iron while aqueous Si and Al, the major impurities in this system, are supplied either as trace elements in the circulating solution or by addition of amorphous silica and alumina when considering confined zones. The fluid chemistry is monitored by sampling aliquots of the solution. Eh and pH are continuously measured by hydrothermal Cormet© electrodes implanted in a titanium hydrothermal reactor. The transformation, or not, of the solid fraction was examined post-mortem. These experiments evidenced the role of Al colloids as precursor of cements composed of kaolinite and boehmite, and the passivation of amorphous silica (becoming unreactive) likely by sorption of aqueous iron. But no Fe-bearing was formed by contrast to many published studies on the Fe-clay interactions in the nuclear waste storage, and by contrast with basic thermodynamic predictions. Conclusion: The Fe-clays and steam generators contexts imply relatively close aqueous environments: hydrothermal, reduced, diluted, neutral to slightly alkaline. The main difference is the status of iron: ferric/ferrous (magnetite) in the steam generators, metallic in the Fe-clay experiments. The concentration of aqueous iron when supplied by magnetite is low and does not allow its incorporation in secondary phases. By contrast, aqueous ferrous iron released by the corrosion of steel is not limited by the source, rather by the sink, and produces Fe-rich silicates. This example illustrates the discrepancy between complex mineral reactions and oversimplified predictions when sorption/passivation and nucleation/growth constraints are ignored. Reference: [1] Lanson et al. (2012) Amer. Min. 97, 864-871. [2] Lantenois et al. (2005) Clays & Clay Min. 53, 597-612. [3] Mosser-Ruck et al. (2010) Clays & Clay Min. 58, 280-291. [4] Perronnet et al. (2008) App. Clay Sci. 38, 187-202. [5] Osacky et al. (2010) App. Clay Sci. 50, 237-244. [6] Guillaume et al. (2003) Clay Min. 38, 281-302. [7] Rivard et al. (2013) Amer. Mineral. 98, 163-180. [8] Svensson and Hansen (2013) Clays & Clay Min. 61, 566-579.

Role of microbial processes in linking sandstone diagenesis with organic-rich clays

USGS Publications Warehouse

McMahon, P.B.; Chapelle, F.H.; Falls, W.F.; Bradley, P.M.

1992-01-01

Shows that the processes of microbial organic-acid production (via fermentation) in clays and microbial organic-acid consumption (via sulfate reduction) in sands effectively link organic-rich clays to sandstone diagenesis in the Black Creek Formation of South Carolina. Diagenetic processes have resulted in the formation of 10 volume percent calcite cement, 0.1 volume percent authigenic pyrite, and 1.5 volume percent secondary porosity in Black Creek sands. However, the distribution of these diagenetic processes is not uniform, resulting in net destruction of porosity in some parts of the sand and net porosity enchancement in other parts. -from Authors

Molecular Dynamics Simulation of the Crystal Nucleation and Growth Behavior of Methane Hydrate in the Presence of the Surface and Nanopores of Porous Sediment.

PubMed

Yan, Ke-Feng; Li, Xiao-Sen; Chen, Zhao-Yang; Xia, Zhi-Ming; Xu, Chun-Gang; Zhang, Zhiqiang

2016-08-09

The behavior of hydrate formation in porous sediment has been widely studied because of its importance in the investigation of reservoirs and in the drilling of natural gas hydrate. However, it is difficult to understand the hydrate nucleation and growth mechanism on the surface and in the nanopores of porous media by experimental and numerical simulation methods. In this work, molecular dynamics simulations of the nucleation and growth of CH4 hydrate in the presence of the surface and nanopores of clay are carried out. The molecular configurations and microstructure properties are analyzed for systems containing one H2O hydrate layer (System A), three H2O hydrate layers (System B), and six H2O hydrate layers (System C) in both clay and the bulk solution. It is found that hydrate formation is more complex in porous media than in the pure bulk solution and that there is cooperativity between hydrate growth and molecular diffusion in clay nanopores. The hydroxylated edge sites of the clay surface could serve as a source of CH4 molecules to facilitate hydrate nucleation. The diffusion velocity of molecules is influenced by the growth of the hydrate that forms a block in the throats of the clay nanopore. Comparing hydrate growth in different clay pore sizes reveals that the pore size plays an important role in hydrate growth and molecular diffusion in clay. This simulation study provides the microscopic mechanism of hydrate nucleation and growth in porous media, which can be favorable for the investigation of the formation of natural gas hydrate in sediments.

Dinosaurs, spherules, and the “magic” layer: A new K-T boundary clay site in Wyoming

NASA Astrophysics Data System (ADS)

Bohor, Bruce F.; Triplehorn, Don M.; Nichols, Douglas J.; Millard, Hugh T., Jr.

1987-10-01

A new Cretaceous-Tertiary (K-T) boundary clay site has been found along Dogie Creek in Wyoming in the drainage of Lance Creek—the type area of the Lance Formation of latest Cretaceous age. The boundary clay was discovered in the uppermost part of the Lance Formation, 4 7 cm beneath the lowest lignite in the Paleocene Fort Union Formation and approximately 1 m above a fragmented dinosaur bone. The boundary clay consists of a basal kaolinitic claystone layer as much as 3 cm thick containing hollow goyazite spherules, overlain by a 2 3 mm smectitic layer (the “magic” layer) containing both shock-metamorphosed minerals and an iridium anomaly of 21 ppb. A palynological break coincides with the base of the claystone layer; numerous Late Cretaceous palynomorph species terminate at this boundary. The paleontological significance of this new boundary site lies in its close association with the well-studied assemblage of dinosaurs and other vertebrates and flora within the type area of the Lance Formation. The spherules at the Dogie Creek site are extremely well preserved by virtue of their replacement by the mineral goyazite. This preservation should facilitate the resolution of the origin of the spherules and of their host layer.

Sensitive strata in Bootlegger Cove Formation

USGS Publications Warehouse

Olsen, Harold W.

1989-01-01

Sensitivity magnitudes are interpreted from remolded strength values in recent subsurface geologic, geotechnical, and geochemical data from the Bootlegger Cove Formation adjacent to the Turnagain Heights Landslide. The results show that strata composed of highly sensitive clays occur in both the middle and lower zones of the formation, and that between these strata the clays are generally of low-to-medium sensitivity. The most sensitive stratum is in the middle zone between two sand layers, and its sensitivity increases from both clay-sand interfaces to a maximum at the center of the stratum. The pore fluid chemistry of the highly sensitive materials differs from that in the materials of low to medium sensitivity only in their concentrations of organic carbon, chloride, bicarbonate, and sulfate. The total dissolved solids concentration is low, and the ratio of monovalent to divalent cations is very high throughout the middle and lower zones of the formation. Of the known causes of high and extremely high sensitivities, only organic and/or anionic dispersants are consistent with these findings.

Petrography and geochemistry of the Middle Miocene Gebel El Rusas sandstones, Eastern Desert, Egypt: Implications for provenance and tectonic setting

NASA Astrophysics Data System (ADS)

Zaid, Samir M.

2017-10-01

Petrography and bulk rock geochemistry of the Middle Miocene sandstones of the lower and upper members of Gebel El Rusas Formation along the Egyptian Red Sea Coastal plain, have been investigated to determine the provenance, tectonic setting, and weathering condition of this formation. The Lower Member is formed mainly of sandstones and conglomerates with clay interbeds. The Upper Member is more calcareous and formed mainly of sandstones and limestones with marls and clays intercalations. Petrographically, the Lower Member sandstones are mostly immature and classified as arkoses with an average framework composition of Q_{66}F_{29}R5, and the Upper Member sandstones are partly submature (more quartzose, less feldspathic) and classified as subarkoses with an average framework composition of Q_{80}F_{17}R3. The Gebel El Rusas sandstones are enriched in Sr, Ba, Zr and Rb and depleted in Co and U, as compared to UCC. The chemical index of alteration (CIA) values suggest moderate weathering conditions. The geochemistry results revealed that the Gebel El Rusas sandstones were derived from felsic-granitic source rocks and deposited in a passive margin of a synrift basin. The inferred tectonic setting for Middle Miocene Gebel El Rusas sandstones in the study area is consistent with the regional geology of the Eastern Desert of Egypt during Middle Miocene.

Cryosols Formation and classification in the semiarid Antarctica: the Weddel Sea sector of northern Seymour Island

NASA Astrophysics Data System (ADS)

Gjorup, Davi; Schaefer, Carlos; Francelino, Marcio

2015-04-01

The Seymour Island is located in the northern sector of the Weddell Sea zone, at the Antarctic Peninsular area, representing a transitional zone between Maritime and Continental Antarctica, with a subpolar, semiarid climate. The Seymour Island is predominantly composed by marine sedimentary rocks of Cretaceus to Eocene age. The aims of this work were to study the chemical, physical, mineralogical and morphological attributes of a selected, representative toposequence of soils at the northern sector of Seymour Island. Soil formation processes and taxonomical implications were discussed. Nine soil profiles were described, collected and analysed, following a toposequence according to different parent materials and landforms. Samples were subjected to textural analysis, routine chemical analysis, chemical extractions by ammonium oxalate and CBD, as well as X ray diffraction. Permafrost is continuous and widespread, generally at depths of less than 100 cm, so the Gelisols order (Soil Taxonomy), or Cryosols (WRB), are the dominant soils. Cryoturbation and organic matter accumulation were not observed. Soils were separated into two groups: acid-sulphate soils and alkaline soils, unaffected by sulphates. The first are the best developed in the study area, meaning a significant physico-chemical and mineralogical alteration. Low pH and high Al saturation and potential acidity are typical. This accounts for primary mineral dissolution, and its absence in the clay fraction. Secondary minerals are those related to sulphide oxidation: soluble and insoluble sulphates, low crystalline Fe-hydroxides and little crystalline Fe phases. The peculiar yellowish colour of these soils are attributed to the presence of Fe-oxides and Jarosite. The presence of 2:1 clays (smectite and illite) in the Clay fraction despite the acidity is due to low leaching. The alkaline soils, non affected by sulphates do not showed any marked weathering or transformation, with high pH, low potential acidity and zero Al saturation. The main process is cryoclastic and haloclastic weathering. Primary minerals are present even in the clay fraction, corroborating its low weathering degree and chemical alteration. The landform is determinant for the chemical status of theses soils, by favoring or reducing leaching. Sulphurization and halomorphism are the dominant soil-forming processes in Seymour Island.

Formation of mixed-layer structures in smectites intercalated with tryptone

NASA Astrophysics Data System (ADS)

Block, K. A.; Trusiak, A.; Steiner, J. C.; Katz, A.; Gottlieb, P.; Alimova, A.

2012-12-01

Stable clay-protein complexes are fundamental to studies of the critical zone, terrestrial ecosystems, pharmacology, and industrial applications such as bioremediation. Two sets of montmorillonite clays were purified and made homoionic for Na and Mg. Mg-montmorillonite and Na-montmorillonite were mixed with tryptone (casein digest) in a 9:1 and 18:1 clay:tryptone ratio, resulting in the formation of reversible intercalated structures. X-ray diffraction analysis of the protein-clay complexes produced profiles consisting of two peaks associated with the smectite 001 reflection and a related tryptone-packet peak similar to that produced by a mixed layer clay structure. Shifts in the 002, 003, and 004 diffraction maxima are attributed to disorder caused by the interaction with the protein. Line broadening in the smectite-tryptone XRD spectra is interpreted to be the result of interlayer absorption. Adsorption produces coherent crystalline packets of regularly interbedded tryptone and smectite platelets. SEM images reveal clay platelets with upwardly rolled edges that tend toward cylindrical structures with the production of occasional tubes in the smaller platelet size range as noted for organic compound-kaolinite intercalation reported by Fenoll Hach-Ali and Weiss (1969). Reference: Fenoll Hach-Ali, P.F., Weiss, A., 1969. Estudio de la reaccion de caolinita y N-metilform- amida. Quimica LXV, 769-790. Scanning electron micrograph of tryptone-intercalated clay platelets exhibiting rolled edge structure.

Timing and conditions of clay fault gouge formation on the Naxos detachment (Cyclades, Greece)

NASA Astrophysics Data System (ADS)

Mancktelow, N.; Zwingmann, H.; Mulch, A.

2016-10-01

Clay fault gouge from the Naxos detachment (locally up to 1.0-1.5 m thick) is reported and dated for the first time. K-Ar ages on eight clay size fractions from the detachment and a minor fault in the immediate footwall have a narrow range, from 10.3 to 9.0 Ma, with an average of 9.7 ± 0.5 Ma (±1σ). These results are in excellent accord with regional and local age constraints, independently demonstrating the reliability of the method. Hydrogen δD values fall in the range -89 to -95‰, indicating interaction with infiltrating meteoric water during gouge formation, which is consistent with deposition of freshwater sediments in the hanging wall at the same time. Clay mineralogy in the detachment gouge is predominantly mixed layer illite-smectite with subordinate 1 M illite and kaolinite but without higher-temperature 2 M1 illite/mica. Clay fault gouge predominantly formed over a limited time and temperature range, potentially acting as a weak lubricant promoting movement on the Naxos detachment, with correspondingly rapid exhumation and cooling of the underlying footwall.

Investigation on the Formation of Needle Frost. II,

DTIC Science & Technology

For example, clay forms mutual layers with the clay which had not yet frozen with ice. In the case of agar-agar, we obtained the same phenomenon from gelidium jelly as we do when making agar-agar. (Author)

Cost and Performance Report of Electrical Resistance Heating (ERH) for Source Treatment. Addendum

DTIC Science & Technology

2008-09-29

and clay. The Upper Cretaceous Severn, Matawan, and Magothy Formations underlie the Brightseat Formation. The groundwater table at the site is...Table 1, the aquifers include, in descending order, the Aquia, the Monmouth, the Magothy , the Upper and Lower Patapsco and the Patuxent. The... Magothy Magothy Aquifer Sand, light-gray to white, with interbedded thin layers of organic clay. _-300(1) Confining Unit _-360(1) Upper Patapsco

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.

Clay Mineralogy, Authigenic Smectite Concentration, and Fault Weakening of the San Gregorio Fault; Moss Beach, California

NASA Astrophysics Data System (ADS)

Mazzoni, S.; Moore, J.; Bish, D. L.

2002-12-01

The apparently weak nature of the San Andreas fault system poses a fundamental geophysical question. The San Gregorio fault at Moss Beach, CA is an active splay of the right-lateral San Andreas fault zone and has a total offset of about 150 km. At Moss Beach, the San Gregorio fault offsets Pliocene sedimentary rocks and consists of a clay-rich gouge zone, eastern sandstone block, and western mudstone block. In the presence of fluids, smectite clays can swell and become very weak to shearing. We studied a profile of samples across the fault zone and wall rocks to determine if there is a concentration of smectite in the gouge zone and propose a possible formation mechanism. Samples were analyzed using standard quantitative X-ray diffraction methods and software recently developed at Los Alamos National Lab. XRD results show a high smectite/illite (weak clay/strong clay) ratio in the gouge (S/I ratio=2-4), lower in the mudstone (S/I ratio=2), and very low in the sandstone (S/I ratio=1). The variability of smectite/illite ratio in the gouge zone may be evidence of preferential alteration where developed shear planes undergo progressive smectite enrichment. The amount of illite layers in illite/smectites is 5-30%, indicating little illitization; therefore, these fault rocks have not undergone significant diagenesis above 100 degrees C and illite present must be largely detrital. Bulk mineralogy shows significant anti-correlation of smectite with feldspar, especially in the gouge, suggesting authigenic smectite generation from feldspar. Under scanning-electron microscope inspection, smectites have fibrous, grain coating growth fabrics, also suggesting smectite authigenesis. If in situ production of smectite via chemical alteration is possible in active faults, it could have significant implications for self-generated weakening of faults above the smectite-to-illite transition (<150 degrees C, or 5-7km).

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Mineralogical characterization of Greda clays and monitoring of their phase transformations on thermal treatment

NASA Astrophysics Data System (ADS)

Panduro, E. Chavez; Cabrejos, J. Bravo

2010-01-01

The mineralogical characterization of two clay samples from the Central Andean Region of Peru, denominated White Greda and Red Greda, is reported. These clays contain the clay minerals mica and illite respectively. Both clays were treated thermally in an oxidising atmosphere under controlled conditions up to 1,100°C with the purpose of obtaining information about structural changes that may be useful for pottery manufacture. X-ray fluorescence was used for the elemental characterization of the samples and X-ray diffractometry was used to determine the collapse and formation of the mineral phases present in the samples caused by thermal treatment. At temperatures above 1,000°C it is observed the formation of spinel in the case of White Greda and of hematite, corundum and cristobalite in the case of Red Greda. Room temperature transmission Mössbauer spectroscopy allowed the monitoring of the variation of the hyperfine parameters with the thermal treatment temperature; In the case of the evolution of the quadruple splitting of the paramagnetic Fe3 + sites with temperature, in both clays, the analyses reproduced results such as the “camel back” curve shape, found by other workers (Wagner and Wagner, Hyperfine Interact 154:35-82, 2004; Wagner and Kyek, Hyperfine Interact 154:5-33, 2004).

Ground Truthing Orbital Clay Mineral Observations with the APXS Onboard Mars Exploration Rover Opportunity

NASA Technical Reports Server (NTRS)

Schroeder, C.; Gellert, R.; VanBommel, S.; Clark, B. C.; Ming, D. W.; Mittlefehldt, D. S.; Yen, A. S.

2016-01-01

NASA's Mars Exploration Rover Opportunity has been exploring approximately 22 km diameter Endeavour crater since 2011. Its rim segments predate the Hesperian-age Burns formation and expose Noachian-age material, which is associated with orbital Fe3+-Mg-rich clay mineral observations [1,2]. Moving to an orders of magnitude smaller instrumental field of view on the ground, the clay minerals were challenging to pinpoint on the basis of geochemical data because they appear to be the result of near-isochemical weathering of the local bedrock [3,4]. However, the APXS revealed a more complex mineral story as fracture fills and so-called red zones appear to contain more Al-rich clay minerals [5,6], which had not been observed from orbit. These observations are important to constrain clay mineral formation processes. More detail will be added as Opportunity is heading into her 10th extended mission, during which she will investigate Noachian bedrock that predates Endeavour crater, study sedimentary rocks inside Endeavour crater, and explore a fluid-carved gully. ESA's ExoMars rover will land on Noachian-age Oxia Planum where abundant Fe3+-Mg-rich clay minerals have been observed from orbit, but the story will undoubtedly become more complex once seen from the ground.

Thermal acidization and recovery process for recovering viscous petroleum

DOEpatents

Poston, Robert S.

1984-01-01

A thermal acidization and recovery process for increasing production of heavy viscous petroleum crude oil and synthetic fuels from subterranean hydrocarbon formations containing clay particles creating adverse permeability effects is described. The method comprises injecting a thermal vapor stream through a well bore penetrating such formations to clean the formation face of hydrocarbonaceous materials which restrict the flow of fluids into the petroleum-bearing formation. Vaporized hydrogen chloride is then injected simultaneously to react with calcium and magnesium salts in the formation surrounding the bore hole to form water soluble chloride salts. Vaporized hydrogen fluoride is then injected simultaneously with its thermal vapor to dissolve water-sensitive clay particles thus increasing permeability. Thereafter, the thermal vapors are injected until the formation is sufficiently heated to permit increased recovery rates of the petroleum.

Origin and diagenesis of clay minerals in relation to sandstone paragenesis: An example in eolian dune reservoirs and associated rocks, Permian upper part of the Minnelusa Formation, Powder River basin, Wyoming

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

Pollastro, R.M.; Schenk, C.J.

Eolian dune sandstones are the principal reservoir rocks in the Permian upper part of the Minnelusa Formation, Powder River basin, Wyoming. These sandstones formed as shorelines retreated and dunes migrated across siliciclastic sabkhas. Sandstones are mainly quartzarenites; on average, clay minerals constitute about 5 wt.% the whole rock. Although present in minor amounts, clay minerals play an important role in the diagenetic evolution of these sandstones. Allogenic clay minerals are present in shaly rock fragments and laminae. Early infiltration of clays into porous sabkha sands commonly form characteristic menisei or bridges between framework grains or, when more extensive, form coatingsmore » or rims on grain surfaces. Authigenic clays include nearly pure smectite, mixed-layer illite/smectite (I/S), and late diagenetic illite and corrensite; these clay minerals are present as pore-lining cements. In addition to the deposition and neoformation of clay minerals throughout sandstone paragenesis, the conversion of smectite to illite occurred as temperatures increased with progressive burial. A temperature of 103C is calculated at a present depth of 3,200 m using a geothermal gradient of 30C/km and a mean annual surface temperature of 7C. After correction for uplift and erosion (250 m), the maximum calculated temperature for the conversion of all random I/S to ordered I/S is 100C. This calculated temperature is in excellent agreement with temperatures of 100-110C implied from I/S geothermometry.« less

Aqueous clay suspensions stabilized by alginate fluid gels for coal spontaneous combustion prevention and control.

PubMed

Qin, Botao; Ma, Dong; Li, Fanglei; Li, Yong

2017-11-01

We have developed aqueous clay suspensions stabilized by alginate fluid gels (AFG) for coal spontaneous combustion prevention and control. Specially, this study aimed to characterize the effect of AFG on the microstructure, static and dynamic stability, and coal fire inhibition performances of the prepared AFG-stabilized clay suspensions. Compared with aqueous clay suspensions, the AFG-stabilized clay suspensions manifest high static and dynamic stability, which can be ascribed to the formation of a robust three-dimensional gel network by AFG. The coal acceleration oxidation experimental results show that the prepared AFG-stabilized clay suspensions can improve the coal thermal stability and effectively inhibit the coal spontaneous oxidation process by increasing crossing point temperature (CPT) and reducing CO emission. The prepared low-cost and nontoxic AFG-stabilized clay suspensions, exhibiting excellent coal fire extinguishing performances, indicate great application potentials in coal spontaneous combustion prevention and control.

An assessment of the erodibility of Holocene lithounits comprising streambanks in northeastern Kansas, USA

NASA Astrophysics Data System (ADS)

Layzell, Anthony L.; Mandel, Rolfe D.

2014-05-01

Streambanks are the primary source of sediment for watersheds in the Midwestern USA. In much of this region, deposits of fine-grained Holocene alluvium comprising streambanks have been assigned to a single lithostratigraphic unit, the DeForest Formation. This study examines the stratigraphic relationships and measures the erodibility of the different members of the DeForest Formation in three watersheds in northeastern Kansas. Distinct differences in erodibility, measured in terms of critical shear stress (τc) by a submerged jet-test device, were observed between the different members of the DeForest Formation. The most erodible member is the Camp Creek Member (average τc = 1.0 Pa) while the most resistant is the Gunder Member (average τc = 10.4 Pa). Variability in erodibility between and within the members of the DeForest Formation is attributed to the magnitude of post-depositional soil-forming processes, including the presence of buried soils, as well as the inherent natural variability in the different parent materials. A weak positive correlation was found between percent clay and τc. Resistance to erosion by fluid flow was found to be significantly greater where clay contents exceed 28%. Although the Camp Creek Member was found to be the most erodible, it always occurs, stratigraphically, as the uppermost member. Available bankfull stage indicators suggest that bankfull discharges rarely attain elevations sufficient to erode Camp Creek Member deposits. Therefore, other members of the DeForest Formation are able to exert some control on the rate of bank erosion by hydraulic flow. Furthermore, given the observed differences in lithology, soil development and erodibility, the susceptibility to mass wasting processes is also likely to vary between the different members. Therefore, lithostratigraphic and soil-stratigraphic relationships have important implications for streambank erodibility and are crucial for accurately determining areas prone to streambank erosion in alluvial settings.

Beryllium geochemistry in soils: Evaluation of 10Be/9Be ratios in authigenic minerals as a basis for age models

USGS Publications Warehouse

Barg, E.; Lal, D.; Pavich, M.J.; Caffee, M.W.; Southon, J.R.

1997-01-01

Soils contain a diverse and complex set of chemicals and minerals. Being an 'open system', both in the chemical and nuclear sense, soils have defied quantitative nuclear dating. However, based on the published studies of the cosmogenic atmospheric 10Be in soils, its relatively long half-life (1.5 Ma), and the fact that 10Be gets quickly incorporated in most soil minerals, this radionuclide appears to be potentially the most useful for soil dating. We therefore studied the natural variations in the specific activities of 10Be with respect to the isotope 9Be in mineral phases in eight profiles of diverse soils from temperate to tropical climatic regimes and evaluated the implications of the data for determining the time of formation of soil minerals, following an earlier suggestion [Lal et al., 1991. Development of cosmogenic nuclear methods for the study of soil erosion and formation rates. Current Sci. 61, 636-639.]. We find that the 10Be/9Be ratios in both bulk soils and in the authigenic mineral phases are confined within a narrower range than in 10Be concentrations. Also, the highest 10Be/9Be ratios in authigenic minerals are observed at the soil-rock interface as predicted by the model. We present model 10Be/9Be ages of the B-horizon and the corresponding soil formation rates for several soil profiles. The present study demonstrates that the 10Be/9Be ratios in the authigenic phases, e.g. clay and Fe-hydroxides, can indeed be used for obtaining useful model ages for soils younger than 10-15 Ma. However, the present work has to be pushed considerably further, to take into account more realistic age models in which, for instance, downward transport of 10Be and clays, and in-situ dissolution of clay minerals at depths, altering the 10Be/9Be ratios of the acidic solutions, are included. We show that in the case of younger soils (< 1 Ma) studied here, their 10Be inventories and 10Be/9Be ratios have been significantly disturbed possibly by mixing with transported soils. ?? 1997 Elsevier Science B.V.

EFFECT OF AQUEOUS PHASE PROPERTIES ON CLAY PARTICLE ZETA POTENTIAL AND ELECTRO-OSMOTIC PERMEABILITY: IMPLICATIONS FOR ELECTRO-KINETIC SOIL REMEDIATION PROCESSES

EPA Science Inventory

The influence of aqueous phase properties (pH, ionic strength and divalent metal ion concentration) on clay particle zeta potential and packed-bed electro-osmotic permeability was quantified. Although pH strongly altered the zeta potential of a Georgia kaolinite, it did not signi...

Learning about Fossil Formation by Classroom Simulation.

ERIC Educational Resources Information Center

Schlenker, Richard M.; Yoshida, Sarah J.

1991-01-01

Activities in which students build their own simulations of fossils, using seashells, chicken bones, toy dinosaurs, or leaves as models and plaster of paris, sand, mud, clay, or a mixture of gravel and clay as a matrix are presented. Curriculum extensions are included. (KR)

Transport of Organic Solutes in Clay Formations

EPA Science Inventory

The research is a pilot investigation for the SERDP (Strategic Environmental Research and Development Program, DoD) founded project, Impact of Clay-DNAPL Interactions on Transport and Storage of Chlorinated Solvents in Low Permeability Zones, from 2010-2012. The report tries to s...

Sub-glacial Origin of the Hot Springs Bay Valley hydrothermal System, Akutan, Alaska

NASA Astrophysics Data System (ADS)

Stelling, P. L.; Tobin, B.; Knapp, P.

2015-12-01

Exploration for geothermal energy in Hot Springs Bay Valley (HSBV) on Akutan Island, Alaska, has revealed a rich hydrothermal history, including what appears to be a stage of peak activity during a significant glacial period. Alteration mineralogy observed in 754 m of drill core recovered from the outflow zone is dominated by chlorite and includes minor smectite clays, a suite of zeolite species and several moderately high-temperature hydrothermal minerals (epidote/clinozoisite, prehnite, adularia and wairakite). The latter minerals each have minimum formation temperatures exceeding 200 oC, and fluid inclusion results in related calcite crystals indicate temperatures of formation to be as high as 275 oC, some 100 oC hotter than the modern boiling point with depth (BPD) curve at that depth (>62 m). In order to maintain liquid temperatures this high, the pressure during mineralization must have been substantially greater (~680 bar), a pressure change equivalent to erosion of ~280 m of rock (ρ=2.5 g/cm3). Although glacial erosion rates are too low (0.034 mm/yr; Bekele et al., 2003) for this amount of erosion to occur in a single glaciation, glacial melting and ablation are substantially more rapid (~100 mm/yr; Bekele et al., 2003; Person et al., 2012). Thus, a more probable scenario than pure erosion is that peak hydrothermal conditions occurred during a large glacial event, with the added pressure from the overlying ice allowing the high temperature minerals to form closer to the ground surface. Subsequent melting of the ice eroded upper tributary valleys and upper levels of the originally smectite-rich alteration assemblage, explaining the paucity of swelling clays in the region. We present mineralogical, fluid inclusion and geochronologic evidence to support these conclusions, and discuss the general implications of sub-glacial hydrothermal system formation and geothermal resource potential. References: Bekele, E., Rostron, B. and Person, M. (2003) Fluid pressure implications of erosional unloading, basin hydrodynamics and glaciation in the Alberta Basin, Western Canada. J. of Geochem. Exploration, 78-79, 143-7. Person, M., Bense, V., Cohen, D. and Banerjee, A, (2012). Models of ice-sheet hydrogeologic interactions: a review. Geofluids, 12, 58-78

Dioctahedral Phyllosilicates Versus Zeolites and Carbonates Versus Zeolites Competitions as Constraints to Understanding Early Mars Alteration Conditions

NASA Astrophysics Data System (ADS)

Viennet, Jean-Christophe; Bultel, Benjamin; Riu, Lucie; Werner, Stephanie C.

2017-11-01

Widespread occurrence of Fe,Mg-phyllosilicates has been observed on Noachian Martian terrains. Therefore, the study of Fe,Mg-phyllosilicate formation, in order to characterize early Martian environmental conditions, is of particular interest to the Martian community. Previous studies have shown that the investigation of Fe,Mg-smectite formation alone helps to describe early Mars environmental conditions, but there are still large uncertainties in terms of pH range, oxic/anoxic conditions, etc. Interestingly, carbonates and/or zeolites have also been observed on Noachian surfaces in association with the Fe,Mg-phyllosilicates. Consequently, the present study focuses on the dioctahedral/trioctahedral phyllosilicate/carbonate/zeolite formation as a function of various CO2 contents (100% N2, 10% CO2/90% N2, and 100% CO2), from a combined approach including closed system laboratory experiments for 3 weeks at 120°C and geochemical simulations. The experimental results show that as the CO2 content decreases, the amount of dioctahedral clay minerals decreases in favor of trioctahedral minerals. Carbonates and dioctahedral clay minerals are formed during the experiments with CO2. When Ca-zeolites are formed, no carbonates and dioctahedral minerals are observed. Geochemical simulation aided in establishing pH as a key parameter in determining mineral formation patterns. Indeed, under acidic conditions dioctahedral clay minerals and carbonate minerals are formed, while trioctahedral clay minerals are formed in basic conditions with a neutral pH value of 5.98 at 120°C. Zeolites are favored from pH ≳ 7.2. The results obtained shed new light on the importance of dioctahedral clay minerals versus zeolites and carbonates versus zeolites competitions to better define the aqueous alteration processes throughout early Mars history.

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.

Aquifers in the Sokoto basin, northwestern Nigeria, with a description of the general hydrogeology of the region

USGS Publications Warehouse

Anderson, H.R.; Ogilbee, William

1973-01-01

The Sokoto Basin of northwestern Nigeria lies in the sub-Saharan Sudan belt of west Africa in a zone of savannah-type vegetation. Rainfall, averaging about 30 inches annually in much of the basin, occurs chiefly in a wet season which lasts from May to October. A prolonged dry season extending from October to April is dominated by dusty harmattan winds from the northeast. April and May are the hottest months, when temperatures occasionally reach 105?F. Flow in streams of the Sokoto Basin is mostly overland runoff. Only in a few reaches, fed by ground-water discharge from the sedimentary rocks, are streams perennial. In the River Zamfara basin, ground-water discharge contributes almost 1 inch of the average 3.33 inches of total annual runoff. In the vicinity of Sokoto, the River Rima flows throughout the year sustained by spring discharge from perched ground water in limestone of the Kalambaina Formation. On the crystalline terrane where most of the streams rise, total annual runoff may exceed 5 inches, very little of which is ground-water discharge. The sedimentary rocks of the basin range in age from Cretaceous to Tertiary and are composed mostly of interbedded sand, clay, and some limestone; the beds dip gently toward the northwest. Alluvium of Quaternary age underlies the lowlands of the River Sokoto (now Sokoto) and its principal tributaries. These rocks contain three important artesian aquifers, in addition to regional unconfined ground-water bodies in all the principal outcron areas, and a perched water body in the outcrop of the Kalambaina Formation. Artesian aquifers occur at depth in the Gundumi Formation, the Rima Group, and the Gwandu Formation and are separated from one another by clay beds in the lower part of the Rima Group and the Dange Formation. In outcrop, clay in the Dange Formation also supports the perched water of the Kalambaina Formation. The Gundumi Formation, resting on the basement complex, is composed of varicolored clay, sand, and gravel and attains a thickness of 800 to 1,000 feet in its downdip extensions. Most of the formation is thin bedded and clayey and therefore does not yield large quantities of water to boreholes; the average yield is 2,700 gph (gallons per hour). (All gallons are imperial gallons.) Nevertheless, the upper part of the formation is sandy and more permeable and forms a regional artesian aquifer from which yields of as much as 6,600 gph are obtained from single boreholes. Clay in the lower part of the Rima Group confines the Gundumi aquifer downdip, so that at Rabah and Sokoto, for example, in the River Sokoto fadama (valley floor), artesian flow is found in boreholes screened in the Gundumi. Aquifer tests indicate low transmissivities, ranging from 300 to 5,000 gpd per ft (gallons per day per foot) in the lower part of the Gundumi Formation; but in the upper sandy zone the transmissivities are much higher, reaching 66,000 gpd per ft. In the western part of the Sokoto Basin, more productive aquifers with higher heads usually lie above the Gundumi aquifer so that it is not attractive for development, except in the River Sokoto fadama where artesian flow is possible. The Illo Group, which is in part contemporaneous with the Gundumi Formation, includes interbedded varicolored clay and grit in the southern part of the Sokoto Basin. The upper part of the Illo is known to be water-bearing; however, except for the test borehole at Mungadi, little is known of its subsurface extent and water-yielding potential. Overlying the Gundumi Formation in the central and northern part of the Sokoto Basin are interbedded fine gray sand and dark gray clay of the Wurno and Taloka Formations, separated in the extreme north by clay shale of the Dukamaje Formation. Collectively known as the Rima Group, these sediments attain a thickness of more than 1,000 feet near the Niger border. At depth and downdip the clayey beds practically disappear; the sandy beds become thicker and coar

Reactive Transport Modeling and Changes in Porosity at Reactive Interfaces in a HLW repository in Clay

NASA Astrophysics Data System (ADS)

Samper, J.; Mon, A.; Montenegro, L.; Naves, A.; Fernández, J.

2016-12-01

High-level radioactive waste disposal in a deep geological repository is based on a multibarrier concept which combines natural barriers such as the geological formation and artificial barriers such as metallic containers, bentonite and concrete buffers and sealing materials. The stability and performance of the bentonite barrier could be affected by the corrosion products at the canister-bentonite interface and the hyperalkaline conditions caused by the degradation of concrete at the bentonite-concrete interface. Additionally, the host clay formation could also be affected by the hyperalkaline plume at the concrete-clay interface. Here we present a nonisothermal reactive transport model of the long-term interactions of the compacted bentonite with the corrosion products of a carbon-steel canister and the concrete liner of the engineered barrier of a high-level radioactive waste repository in clay. This problem involves large pH changes with a hyperalkaline high-pH plume, complex mineral dissolution/precipitation patterns, cation exchange reactions and proton surface complexation. These reactions lead to large changes in porosity which can even lead to pore clogging. Model results show that magnetite, the main corrosion product, precipitates and reduces significantly the porosity of the bentonite near the canister. The degradation of the concrete liner leads to the precipitation of secondary minerals and the reduction of the porosity of the bentonite and the clay formation at their interfaces with the concrete liner. The zones affected by pore clogging at the canister-bentonite, bentonite-concrete and concrete-clay interfaces at 1 Ma are equal to 10, 25 and 25 mm thick, respectively. The results of our simulations share many of the features of the models reported by others for engineered barrier systems at similar chemical conditions, including: 1) Narrow alteration zones; and 2) Pore clogging at the canister-bentonite, bentonite-concrete and concrete-clay interfaces.

Influence of depositional environment on diagenesis in St. Peter sandstone, Michigan basin

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

Lundgren, C.E. Jr.; Barnes, D.A.

1989-03-01

The Middle Ordovician St. Peter Sandstone in the Michigan basin was deposited in marine peritidal to storm-dominated, outer shelf depositional environments that evolved in a regionally significant transgressive pattern. The formation is bounded by carbonate and shaly clastic strata of the Prairie du Chien Group below and is transitional to condensed sequence clastics and carbonates of the Glenwood Formation above. Sedimentologic and petrographic analysis of conventional core from 25 wells suggests that reservoir quality in the formation is strongly dependent on a complex diagenetic history, especially the nature and subsequent dissolution of intergranular carbonate in the sandstone. Petrographic evidence indicatesmore » that porosity in the formation formed by dissolution of precursor dolomite of various origins and, locally, the formation of pore-filling authigenic clay (chlorite-illite). Authigenic clay is the incongruent dissolution product of dolomite, detrital K-feldspar, and, possibly, muscovite and results in diminished reservoir quality where abundant in the St. Peter Sandstone. Authigenic clay is volumetrically more significant in the upper portions of the formation and is associated with higher concentrations of detrital K-feldspar. Depositional facies controlled the distribution and types of intergranular carbonate (now dolomite) and detrital K-feldspar in the St. Peter Sandstone and hence reservoir quality; both components were more significant in storm-shelf sandstone facies.« less

Hydrothermal Synthesis of Analcime from Kutingkeng Formation Mudstone

NASA Astrophysics Data System (ADS)

Hsiao, Yin-Hsiu; Chen, Kuan-Ting; Ray, Dah-Tong

2015-04-01

In southwest of Taiwan, the foothill located in Tainan-Kaohsiung city is the exposed area of Pliocene strata to early Pleistocene strata. The strata are about a depth of five thousand, named as Kutigkeng Formation. The outcrop of Kutigkeng Formation is typical badlands, specifically called 'Moon World.' It is commonly known as no important economic applications of agricultural land. The mineral compositions of Kutingkeng Formation are quartz, clay minerals and feldspar. The clay minerals consist of illite, clinochlore and swelling clays. To study how the phase and morphology of analcime formed by hydrothermal synthesis were affected, analcime was synthesized from the mudstone of Kutinkeng Formation with microwave hydrothermal reaction was investigated. The parameters of the experiment were the reaction temperature, the concentration of mineralizer, solids/liquid ratio and time. The sodium silicate (Na2SiO3) were used as mineralizer. The results showed that the analcime could be synthesized by hydrothermal reaction above 180° from Kutinkeng Formation mudstone samples. At the highest temperature (240°) of this study, the high purity analcime could be produced. When the concentration of Na2SiO3=3~6M, analcime could be synthesized at 240°. The best solids/liquid ratio was approximate 1 to 5. The hydrothermal reaction almost was completed after 4 hours.

Frictional properties of low-angle normal fault gouges and implications for low-angle normal fault slip

NASA Astrophysics Data System (ADS)

Haines, Samuel; Marone, Chris; Saffer, Demian

2014-12-01

The mechanics of slip on low-angle normal faults (LANFs) remain an enduring problem in structural geology and fault mechanics. In most cases, new faults should form rather than having slip occur on LANFs, assuming values of fault friction consistent with Byerlee's Law. We present results of laboratory measurements on the frictional properties of natural clay-rich gouges from low-angle normal faults (LANF) in the American Cordillera, from the Whipple Mts. Detachment, the Panamint range-front detachment, and the Waterman Hills detachment. These clay-rich gouges are dominated by neoformed clay minerals and are an integral part of fault zones in many LANFs, yet their frictional properties under in situ conditions remain relatively unknown. We conducted measurements under saturated and controlled pore pressure conditions at effective normal stresses ranging from 20 to 60 MPa (corresponding to depths of 0.9-2.9 km), on both powdered and intact wafers of fault rock. For the Whipple Mountains detachment, friction coefficient (μ) varies depending on clast content, with values ranging from 0.40 to 0.58 for clast-rich material, and 0.29-0.30 for clay-rich gouge. Samples from the Panamint range-front detachment were clay-rich, and exhibit friction values of 0.28 to 0.38, significantly lower than reported from previous studies on fault gouges tested under room humidity (nominally dry) conditions, including samples from the same exposure. Samples from the Waterman Hills detachment are slightly stronger, with μ ranging from 0.38 to 0.43. The neoformed gouge materials from all three localities exhibits velocity-strengthening frictional behavior under almost all of the experimental conditions we explored, with values of the friction rate parameter (a - b) ranging from -0.001 to +0.025. Clast-rich samples exhibited frictional healing (strength increases with hold time), whereas clay-rich samples do not. Our results indicate that where clay-rich neoformed gouges are present along LANFs, they provide a mechanically viable explanation for slip on faults with dips <20°, requiring only moderate (Pf <σ3) overpressures and/or correcting for ∼5° of footwall tilting. Furthermore, the low rates of frictional strength recovery and velocity-strengthening frictional behavior we observe provide an explanation for the lack of observed seismicity on these structures. We suggest that LANFs in the upper crust (depth <8 km) slip via a combination of a) reaction-weakening of initially high-angle fault zones by the formation of neoformed clay-rich gouges, and b) regional tectonic accommodation of rotating fault blocks.

Semianalytical Solutions for Transport in Aquifer and Fractured Clay Matrix System

EPA Science Inventory

A three-dimensional mathematical model that describes transport of contaminant in a horizontal aquifer with simultaneous diffusion into a fractured clay formation is proposed. A group of analytical solutions is derived based on specific initial and boundary conditions as well as ...

The Belterra Clay: The Last Terrestrial Connection Between the Brazilian Shield and the Guiana Shield

NASA Astrophysics Data System (ADS)

Campbell, K.

2016-12-01

The Belterra Clay is a sedimentary deposit that covers much of the eastern Amazon Basin in Brazil. It is notable in forming a very flat plain that occurs on both sides of the Amazon River, the Tapajos River, the Xingu River, and many smaller, tributary rivers east of 56° 32' W. The origin of the Belterra Clay is very controversial, with proponents of both allochthonous and autochthonous means of formation. There is little agreement as to its age. The fact that it occurs on both sides of the Amazon River indicates that its origin predates the formation of the modern Amazon River system, the timing of origin of which is itself highly controversial, with age estimates given for the river system formation that extend from the late Miocene, or 10 mya, to the late Pleistocene. From the time of origin of the Belterra Clay deposit until the modern Amazon River evolved, it formed an unbroken, terrestrial connection between the Brazilian Shield to the south and the Guiana Shield to the north, as well as east-west connections across what are today major river valleys, such as the Tapajos River and Xingu River. The formation and later severing of this once unbroken plain are predicted to have had major impacts on the distribution and evolutionary pathways of biotas inhabiting the region as once disparate communities were joined and later separated once again. Molecular clock ages for sister taxa north and south of the Amazon River have the potential of dating the time of formation of the Amazon River.

Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CH4 and CH4/CO2 Mixtures: Implications for CO2-Enhanced Gas Production

NASA Astrophysics Data System (ADS)

Loring, J.; Thompson, C.; Ilton, E. S.; McGrail, B. P.; Schaef, T.

2014-12-01

Injection of CO2 into low permeability shale formations leads to additional gas recovery and reduces the flux of CO2 into the atmosphere, thus combining a strong economic incentive with a permanent storage option for CO2. Reduced formation transmissivity due to clay swelling is a concern in CO2 -enhanced gas production. Clay minerals partly determine the physical (i.e. permeability, brittleness) and certain chemical properties (i.e. wetting ability, gas adsorption) of shales, and montmorillonites are of particular interest because they swell by the uptake of species in their interlayer. In this study, the hydration and expansion of a Na-saturated montmorillonite (Na-SWy-2) in high-pressure (90 bar) and moderate temperature (50 °C) methane and mixtures of methane and carbon dioxide were investigated usingCH4 IR spectroscopic titrations andCH4 XRD. The goals were to (1) determine if the hydration/expansion behavior of the clay in supercritical methane is different than in supercritical CO2, (2) determine if methane intercalates the clay, and (3) probe the effects of increasing CO2 concentrations. IR spectra were collected as Na-SWy-2 was titrated with water under several fluid exposures: pure methane, 25, 50, and 75 mole% CO2 in methane, and pure CO2. ComplementaryCH4 XRD experiments were conducted in the same fluids at discrete dissolved water concentrations to measure the d001 values of the clay and thus its volume change on hydration and CH4 and/or CO2 intercalation. In pure methane, no direct evidence of CH4 intercalation was detected in CH bending or stretching regions of the IR spectra. Similarly, in situ XRD indicated the montmorillonite structure was stable in the presence of CH4 and no measurable changes to the basal spacing were observed. However, under low water conditions where the montmorillonite structure was partially expanded (~sub 1W), the IR data indicated a rapid intercalation of CO2 into the interlayer, even with fluid mixtures containing the lowest concentrations of CO2. Likewise,CH4 XRD showed indirect evidence of CO2 intercalation from an increase in the basal spacing from 11.8 to 12.3 under identical conditions. These findings demonstrate that water and CO2 intercalation processes could lead to permeability changes that directly impact methane transmissivity in shales.

Reflectance Spectroscopy of Palagonite and Iron-Rich Montmorillonite Clay Mixtures: Implications for the Surface Composition of Mars

NASA Technical Reports Server (NTRS)

Orenberg, James; Handy, Jonathan

1992-01-01

Mixtures of a Hawaiian palagonite and an iron-rich, montmorillonite clay (15.8 +/- 0.4 wt% Fe as Fe2O3) were evaluated as Mars surface spectral analogs from their diffuse reflectance spectra. The presence of the 2.2 microns absorption band in the reflectance spectrum of clays and its absence in the Mars spectrum have been interpreted as indicating that highly crystalline aluminous hydroxylated clays cannot be a major mineral component of the soil on Mars. The palagonite sample used in this study does not show this absorption feature in its spectrum. In mixtures of palagonite and iron-rich montmorillonite, the 2.2 microns Al-OH clay lattice band is not seen below 15 wt% montmorillonite. This suggests the possibility that iron-rich montmorillonite clay may be present in the soil of Mars at up to 15 wt% in combination with palagonite, and remain undetected in remotely sensed spectra of Mars.

Lithostratigraphy of Upper Ordovician strata exposed in Kentucky

USGS Publications Warehouse

Weir, Gordon Whitney; Peterson, Warren Lee; Swadley, W.C.

1984-01-01

Ordovician formations above the Lexington Limestone crop out in the Blue Grass region of Kentucky and along the Cumberland River and its tributaries. The formations are all conformable and in places intertongue and intergrade. The major Ordovician units above the Lexington Limestone in the Blue Grass region are: The Clays Ferry Formation, the Kope Formation, the Garrard Siltstone, the Fairview Formation, the Calloway Creek Limestone, the Grant Lake Limestone, the Ashlock Formation, the Bull Fork Formation, and the Drakes Formation. The Clays Ferry Formation is made up of subequal amounts of fossiliferous limestone and shale and minor siltstone; the Clays Ferry is as much as 300 ft thick and intertongues with the Lexington Limestone and the Kope Formation. The Kope Formation resembles the partly equivalent Clays Ferry but has a higher shale content (60-80 percent) and thicker layers of shale; the Kope, as much as 275 ft thick, is mostly restricted to the northern part of the State. The Garrard Siltstone, which consists of very calcitic siltstone and minor shale, overlies the Clays Ferry Formation in the southeastern part of the Blue Grass region; the Garrard, as much as 100 ft thick, feathers out into the upper part of the Clays Ferry in southern central and northern east-central Kentucky. The Fairview Formation is characterized by even-bedded limestone interlayered with nearly equal amounts of shale and minor siltstone. The Fairview crops out in the northern part of the Blue Grass region, where it generally overlies the Kope Formation or the Garrard Siltstone; it grades southward into the Calloway Creek Limestone. The Calloway Creek contains more limestone (generally at least 70 percent) and is more irregularly and thinner bedded than the Fairview. The Grant Lake Limestone is composed of nodular-bedded limestone (70-90 percent), interlayered and intermixed with shale; it overlies the Fairview Formation in the northern part of the Blue Grass region and the Calloway Creek Limestone in the western and central parts. In east-central Kentucky, the Grant Lake is classified as a member of the Ashlock Formation, an assemblage of lithologically distinct units that were combined to facilitate mapping in the southeastern and southern part of the region. The Ashlock consists of the following members, in ascending order: The Tate (calcitic and dolomitic mudstone), the Grant Lake, the Gilbert (micrograined limestone and shale), the Stingy Creek (nodular-bedded mudstone and limestone), the Terrill (dolomitic and calcitic mudstone), the Sunset (micrograined limestone), and the Reba (nodular-bedded limestone and shale). The Bull Fork Formation, which overlies the Grant Lake Limestone, is made up of subequal amounts of thin-bedded highly fossiliferous limestone and shale; limestone makes up about 80 percent of the basal part of the formation and decreases in abundance irregularly upward to only 20 percent of the top part. On the east side of the Blue Grass region, the Bull Fork grades into the Reba Member of the Ashlock Formation; on the west side, it grades into the Grant Lake. The uppermost formation in the region is the Drakes Formation, which in east-central Kentucky consists of the Rowland Member (calcitic to dolomitic mudstone) overlain by the Preachersville Member (dolomitic to calcitic mudstone and dolomite and dolomitic siltstone). In northeast Kentucky, the Drakes is represented by only the Preachersville Member. In most of central and north-central Kentucky, the formation consists of three members: the Rowland at the base (dolomitic mudstone to muddy limestone), the Bardstown (fossiliferous limestone and shale), and the Saluda Dolomite (dolomite, in part calcitic and muddy). In northern north-central Kentucky, the Drakes is represented by only the Saluda Dolomite Member. The top of the Ordovician sequence in the Blue Grass region is generally formed by members of the Drakes Formation, which are overlain by str

Spatial Persistence of Macropores and Authigenic Clays in a Reservoir Sandstone: Implications for Enhanced Oil Recovery and CO2 Storage

NASA Astrophysics Data System (ADS)

Dewers, T. A.

2015-12-01

Multiphase flow in clay-rich sandstone reservoirs is important to enhanced oil recovery (EOR) and the geologic storage of CO2. Understanding geologic controls on pore structure allows for better identification of lithofacies that can contain, storage, and/or transmit hydrocarbons and CO2, and may result in better designs for EOR-CO2 storage. We examine three-dimensional pore structure and connectivity of sandstone samples from the Farnsworth Unit, Texas, the site of a combined EOR-CO2 storage project by the Southwest Regional Partnership on Carbon Sequestration (SWP). We employ a unique set of methods, including: robotic serial polishing and reflected-light imaging for digital pore-structure reconstruction; electron microscopy; laser scanning confocal microscopy; mercury intrusion-extrusion porosimetry; and relative permeability and capillary pressure measurements using CO2 and synthetic formation fluid. Our results link pore size distributions, topology of porosity and clay-rich phases, and spatial persistence of connected flow paths to multiphase flow behavior. The authors gratefully acknowledge the U.S. Department of Energy's National Energy Technology Laboratory for sponsoring this project through the SWP under Award No. DE-FC26-05NT42591. 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 National Nuclear Security Administration under contract DE-AC04-94AL85000.

In situ chemical osmosis experiment in the Boom Clay at the Mol underground research laboratory

NASA Astrophysics Data System (ADS)

Garavito, A. M.; De Cannière, P.; Kooi, H.

Studies on the compatibility of Boom Clay with large amounts of nitrate- bearing bituminized radioactive waste have recently raised a particular interest for osmosis-induced effects in this reference formation in Belgium. Indeed, water flow and solute transport may be associated with several types of driving forces, or gradients (chemical, electrical, thermal), in addition to the hydraulic forces, resulting in the so-called coupled flows. Fluid flow caused by driving forces different than hydraulic gradients is referred to as osmosis. Chemical osmosis, the water flow induced by a chemical gradient across a semi-permeable membrane, can generate pressure increase. The question thus arises if there is a risk to create high pore pressures that could damage the near-field of medium-level waste (MLW) galleries, if osmotically driven water flows towards the galleries are produced by the release of large amounts of NaNO 3 (750 t) in the formation. To what extent a low-permeability clay formation such as the Boom Clay acts as an osmotic membrane is thus a key issue to assess the relevance of osmosis phenomena for the disposal of medium-level waste. An in situ osmosis experiment has been conducted at the H ADES underground research laboratory to determine the osmotic efficiency of Boom Clay at the field scale. A recently developed chemical osmosis flow continuum model has been used to design the osmosis experiment, and to interpret the water pressure measurements. Experimental data could be reproduced quite accurately by the model, and the inferred parameter values are consistent with independent determinations for Boom Clay. A rapid water pressure increase (but limited to about a 2 m water column) was observed after 12 h in the filter containing the more saline water. Then, the osmotically induced water pressure slowly decays on several months. So, the experimental results obtained in situ confirm the occurrence of non-hydraulic flow phenomena (chemical osmosis) in a low-permeability plastic formation such as the Boom Clay. The osmotic efficiency of Boom Clay is high under undisturbed chemical conditions ( σ = 0.41 at 0.014 M NaHCO 3), but rapidly decreases when the dissolved salts concentration increases ( σ = 0.07 at 0.14 M NaHCO 3). A semi-permeable membrane behaviour of the Boom Clay (high efficiencies) may be expected for the disposal of nitrate-bearing radioactive waste. However, the presently observed osmotically induced pressure is too low to have a significant mechanical impact on the host rock. Finally, the short duration of the osmosis test performed suggests that the shut-in test method used is effective for osmosis testing.

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

Zheng, Liange; Li, Lianchong; Rutqvist, Jonny

Clay/shale has been considered as potential host rock for geological disposal of high-level nuclear waste throughout the world, because of its low permeability, low diffusion coefficient, high retention capacity for radionuclides, and capability to self-seal fractures induced by tunnel excavation. For example, Callovo-Oxfordian argillites at the Bure site, France (Fouche et al., 2004), Toarcian argillites at the Tournemire site, France (Patriarche et al., 2004), Opalinus Clay at the Mont Terri site, Switzerland (Meier et al., 2000), and Boom clay at the Mol site, Belgium (Barnichon and Volckaert, 2003) have all been under intensive scientific investigation (at both field and laboratorymore » scales) for understanding a variety of rock properties and their relationships to flow and transport processes associated with geological disposal of nuclear waste. Clay/shale formations may be generally classified as indurated or plastic clays (Tsang and Hudson, 2010). The latter (including Boom clay) is a softer material without high cohesion; its deformation is dominantly plastic. During the lifespan of a clay repository, the repository performance is affected by complex thermal, hydrogeological, mechanical, chemical (THMC) processes, such as heat release due to radionuclide decay, multiphase flow, formation of damage zones, radionuclide transport, waste dissolution, and chemical reactions. All these processes are related to each other. An in-depth understanding of these coupled processes is critical for the performance assessment (PA) of the repository. These coupled processes may affect radionuclide transport by changing transport paths (e.g., formation and evolution of excavation damaged zone (EDZ)) and altering flow, mineral, and mechanical properties that are related to radionuclide transport. While radionuclide transport in clay formation has been studied using laboratory tests (e,g, Appelo et al. 2010, Garcia-Gutierrez et al., 2008, Maes et al., 2008), short-term field tests (e.g. Garcia-Gutierrez et al. 2006, Soler et al. 2008, van Loon et al. 2004, Wu et al. 2009) and numerical modeling (de Windt et al. 2003; 2006), the effects of THMC processes on radionuclide transport are not fully investigated. The objectives of the research activity documented in this report are to improve a modeling capability for coupled THMC processes and to use it to evaluate the THMC impacts on radionuclide transport. This research activity addresses several key Features, Events and Processes (FEPs), including FEP 2.2.08, Hydrologic Processes, FEP 2.2.07, Mechanical Processes and FEP 2.2.09, Chemical Process— Transport, by studying near-field coupled THMC processes in clay/shale repositories and their impacts on radionuclide transport. This report documents the progress that has been made in FY12. Section 2 discusses the development of THMC modeling capability. Section 3 reports modeling results of THMC impacts on radionuclide transport. Planned work for the remaining months of FY12 and proposed work for FY13 are presented in Section 4.« less

Silica, Alumina and Clay Catalyzed Peptide Bond Formation: Enhanced Efficiency of Alumina Catalyst

NASA Astrophysics Data System (ADS)

Bujdák, Juraj; Rode, Bernd M.

1999-10-01

Catalytic efficiencies of clay (hectorite), silica and alumina were tested in peptide bond formation reactions of glycine (Gly), alanine (Ala), proline (Pro), valine (Val) and leucine (Leu). The reactions were performed as drying/wetting (hectorite) and temperature fluctuation (silica and alumina) experiments at 85 °C. The reactivity of amino acids decreased in order Gly > Ala > Pro ~ Val ~ Leu. The highest catalytic efficiency was observed for alumina, the only catalyst producing oligopeptides in all investigated reaction systems. The peptide bond formation on alumina is probably catalyzed by the same sites and via similar reaction mechanisms as some alumina-catalyzed dehydration reactions used in industrial chemistry.

Occurrence of Tourmaline in Metasedimentary Rocks of the Isua Supracrustal Belt, Greenland: Implications for Ribose Stabilization in Hadean Marine Sediments.

PubMed

Mishima, Shinpei; Ohtomo, Yoko; Kakegawa, Takeshi

2016-06-01

Abiotic formation of RNA was important for the emergence of terrestrial life, but the acknowledged difficulties of generating and stabilizing ribose have often raised questions regarding how the first RNA might have formed. Previous researchers have proposed that borate could have stabilized ribose; however, the availability of borate on the early Earth has been the subject of intense debate. In order to examine whether borate was available on the early Earth, this study examined metasedimentary rocks from the Isua Supracrustal Belt. Garnet, biotite, and quartz comprise the major constituents of the examined rocks. Field relationships and the chemical compositions of the examined rocks suggest sedimentary origin. The present study found that garnet crystals contain a number of inclusions of tourmaline (a type of borosilicate mineral). All tourmaline crystals are Fe-rich and categorized as schorl. Both garnet and tourmaline often contain graphite inclusions and this close association of tourmaline with garnet and graphite has not been recognized previously. Garnet-biotite and graphite geothermometers suggest that the tourmaline in garnet experienced peak metamorphic conditions (~500 °C and 5 kbar). The mineralogical characteristics of the tourmaline and the whole rock composition indicate that the tourmaline formed authigenically in the sediment during diagenesis and/or early metamorphism. Clay minerals in modern sediments have the capability to adsorb and concentrate borate, which could lead to boron enrichment during diagenesis, followed by tourmaline formation under metamorphic conditions. Clay minerals, deposited on the early Archean seafloor, were the precursors of the garnet and biotite in the examined samples. The studied tourmaline crystals were most likely formed in the same way as modern tourmaline in marine sediments. Therefore, boron enrichment by clays must have been possible even during the early Archean. Thus, similar enrichment could have been possible during the Hadean, providing a stabilization agent for ribose.

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.

Woody plant roots fail to penetrate a clay-lined landfill: Managment implications

NASA Astrophysics Data System (ADS)

Robinson, George R.; Handel, Steven N.

1995-01-01

In many locations, regulatory agencies do not permit tree planting above landfills that are sealed with a capping clay, because roots might penetrate the clay barrier and expose landfill contents to leaching. We find, however, no empirical or theoretical basis for this restriction, and instead hypothesize that plant roots of any kind are incapable of penetrating the dense clays used to seal landfills. As a test, we excavated 30 trees and shrubs, of 12 species, growing over a clay-lined municipal sanitary landfill on Staten Island, New York. The landfill had been closed for seven years, and featured a very shallow (10 to 30-cm) soil layer over a 45-cm layer of compacted grey marl (Woodbury series) clay. The test plants had invaded naturally from nearby forests. All plants examined—including trees as tall as 6 m—had extremely shallow root plates, with deformed tap roots that grew entirely above and parallel to the clay layer. Only occasional stubby feeder roots were found in the top 1 cm of clay, and in clay cracks at depths to 6 cm, indicating that the primary impediment to root growth was physical, although both clay and the overlying soil were highly acidic. These results, if confirmed by experimental research should lead to increased options for the end use of many closed sanitary landfills.

Survival of microorganisms in smectite clays - Implications for Martian exobiology

NASA Technical Reports Server (NTRS)

Moll, Deborah M.; Vestal, J. R.

1992-01-01

The survival of Baccillus subtilis, Azotobacter chroococcum, and the enteric bacteriophage MS2 has been examined in clays representing terrestrial (Wyoming type montmorillonite) and Martian (Fe3+ montmorillonite) soils exposed to terrestrial and Martian environmental conditions of temperature and atmospheric composition and pressure. An important finding is that MS2 survived simulated Mars conditions better than the terrestrial environment, probably owing to stabilization of the virus caused by the cold and dry conditions of the simulated Mars environment. This finding, the first published indication that viruses may be able to survive in Mars-type soils, may have important implications for future missions to Mars.

Frictional Properties of Opalinus Clay: Implications for Nuclear Waste Storage

NASA Astrophysics Data System (ADS)

Orellana, L. F.; Scuderi, M. M.; Collettini, C.; Violay, M.

2018-01-01

The kaolinite-bearing Opalinus Clay (OPA) is the host rock proposed in Switzerland for disposal of radioactive waste. However, the presence of tectonic faults intersecting the OPA formation put the long-term safety performance of the underground repository into question due to the possibility of earthquakes triggered by fault instability. In this paper, we study the frictional properties of the OPA shale. To do that, we have carried out biaxial direct shear experiments under conditions typical of nuclear waste storage. We have performed velocity steps (1-300 μm/s) and slide-hold-slide tests (1-3,000 s) on simulated fault gouge at different normal stresses (4-30 MPa). To establish the deformation mechanisms, we have analyzed the microstructures of the sheared samples through scanning electron microscopy. Our results show that peak (μpeak) and steady state friction (μss) range from 0.21 to 0.52 and 0.14 to 0.39, respectively, thus suggesting that OPA fault gouges are weak. The velocity dependence of friction indicates a velocity strengthening regime, with the friction rate parameter (a - b) that decreases with normal stress. Finally, the zero healing values imply a lack of restrengthening during interseismic periods. Taken together, if OPA fault reactivates, our experimental evidence favors an aseismic slip behavior, making the nucleation of earthquakes difficult, and long-term weakness, resulting in stable fault creeping over geological times. Based on the results, our study confirms the seismic safety of the OPA formation for a nuclear waste repository.

Interaction of metal ions and amino acids - Possible mechanisms for the adsorption of amino acids on homoionic smectite clays

NASA Technical Reports Server (NTRS)

Gupta, A.; Loew, G. H.; Lawless, J.

1983-01-01

A semiempirical molecular orbital method is used to characterize the binding of amino acids to hexahydrated Cu(2+) and Ni(2+), a process presumed to occur when they are adsorbed in the interlamellar space of homoionic smectite clays. Five alpha-amino acids, beta-alanine, and gamma-aminobutyric acid were used to investigate the metal ion and amino acid specificity in binding. It was assumed that the alpha, beta, and gamma-amino acids would bind as bidentate anionic ligands, forming either 1:1 or 1:2 six-coordinated five, six, and seven-membered-ring chelate complexes, respectively. Energies of complex formation, optimized geometries, and electron and spin distribution were determined; and steric constraints of binding of the amino acids to the ion-exchanged cations in the interlamellar spacing of a clay were examined. Results indicate that hexahydrated Cu(2+) forms more stable complexes than hexahydrated Ni(2+) with all the amino acids studied. However, among these amino acids, complex formation does not favor the adsorption of the biological subset. Calculated energetics of complex formation and steric constraints are shown to predict that 1:1 rather than 1:2 metal-amino acid complexes are generally favored in the clay.

To what extent clay mineralogy affects soil aggregation? Consequences for soil organic matter stabilization

NASA Astrophysics Data System (ADS)

Fernandez-Ugalde, O.; Barré, P.; Hubert, F.; Virto, I.; Chenu, C.; Ferrage, E.; Caner, L.

2012-12-01

Aggregation is a key process for soil functioning as it influences C storage, vulnerability to erosion and water holding capacity. While the influence of soil organic C on aggregation has been documented, much less is known about the role of soil mineralogy. Soils usually contain a mixture of clay minerals with contrasted surface properties, which should result on different abilities of clay minerals to aggregation. We took advantage of the intrinsic mineral heterogeneity of a temperate Luvisol to compare the role of clay minerals (illite, smectite, kaolinite, and mixed-layer illite-smectite) in aggregation. In a first step, grassland and tilled soil samples were fractionated in water in aggregate-size classes according to the hierarchical model of aggregation (Tisdall and Oades, 1982). Clay mineralogy and organic C in the aggregate-size classes were analyzed. The results showed that interstratified minerals containing swelling phases accumulated in aggregated fractions (>2 μm) compared to free clay fractions (<2 μm) in the two land-uses. The accumulation increased from large macro-aggregates (>500 μm) to micro-aggregates (50-250 μm). C concentration and C/N ratio followed the opposite trend. These results constitute a clay mineral-based evidence for the hierarchical model of aggregation, which postulates an increasing importance of the reactivity of clay minerals in the formation of micro-aggregates compared to larger aggregates. In the latter aggregates, formation relies on the physical enmeshment of particles by fungal hyphae, and root and microbial exudates. In a second step, micro-aggregates from the tilled soil samples were submitted to increasingly disaggregating treatments by sonication to evaluate the link between their water stability and clay mineralogy. Micro-aggregates with increasing stability showed an increase of interstratified minerals containing swelling phases and C concentration for low intensities of disaggregation (from 0 to 5 J mL-1). This suggests that swelling phases promote their stability. Swelling phases and organic C decreased for greater intensities of disaggregation. These results and the SEM images taken at different disaggregation intensities indicate that when increasing disaggregation intensity above 5 J mL-1, the recovered material consists on sand particles covered by physical coatings of illite and kaolinite. Our results show that different clay minerals have different contribution to soil aggregation. Swelling phases are especially important for water-stable aggregates formation, whereas illite and kaolinite can either contribute to aggregation or been coated to sand grains in "mineral aggregates", without porosity and organic C protection capability. In conclusion, soils with large proportion of swelling clay minerals have greater potential for carbon storage by occlusion in aggregates and greater resistance to erosion. Tisdall JM, Oades JM (1982) Organic matter and water-stable aggregates in soils. J Soil Sci 62: 141-163.

Analysis of Oligonucleotide DNA Binding and Sedimentation Properties of Montmorillonite Clay Using Ultraviolet Light Spectroscopy

PubMed Central

Beall, Gary W.; Sowersby, Drew S.; Roberts, Rachel D.; Robson, Michael H.; Lewis, L. Kevin

2009-01-01

Smectite clays such as montmorillonite form complexes with a variety of biomolecules, including the nucleic acids DNA and RNA. Most previous studies of DNA adsorption onto clay have relied upon spectrophotometric analysis after separation of free nucleic acids from bound complexes by centrifugation. In the current work we demonstrate that such studies produce a consistent error due to (a) incomplete sedimentation of montmorillonite and (b) strong absorbance of the remaining clay at 260 nm. Clay sedimentation efficiency was strongly dependent upon cation concentration (Na+ or Mg2+) and on the level of dispersion of the original suspension. An improved clay:DNA adsorption assay was developed and utilized to assess the impact of metal counterions on binding of single-stranded DNA to montmorillonite. X-ray diffraction demonstrated, for the first time, formation of intercalated structures consistent with orientation of the DNA strands parallel to the clay surface. Observed gallery spacings were found to closely match values calculated utilizing atomistic modeling techniques. PMID:19061334

Interphase vs confinement in starch-clay bionanocomposites.

PubMed

Coativy, Gildas; Chevigny, Chloé; Rolland-Sabaté, Agnès; Leroy, Eric; Lourdin, Denis

2015-03-06

Starch-clay bionanocomposites containing 1-10% of natural montmorillonite were elaborated by melt processing in the presence of water. A complex macromolecular dynamics behavior was observed: depending on the clay content, an increase of the glass transition temperature and/or the presence of two overlapped α relaxation peaks were detected. Thanks to a model allowing the prediction of the average interparticle distance, and its comparison with the average size of starch macromolecules, it was possible to associate these phenomena to different populations of macromolecules. In particular, it seems that for high clay content (10%), the slowdown of segmental relaxation due to confinement of the starch macromolecules between the clay tactoïds is the predominant phenomenon. While for lower clay contents (3-5%), a significant modification of chain relaxation seems to occur, due to the formation of an interphase by the starch macromolecules in the vicinity of clay nanoparticles coexisting with the bulk polymer. Copyright © 2014 Elsevier Ltd. All rights reserved.

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.

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.

Clays as possible catalysts for peptide formation in the prebiotic era

NASA Technical Reports Server (NTRS)

Paecht-Horowitz, M.

1976-01-01

From the point of view of prebiotic synthesis, clays might have performed functions of concentration, catalysis, and protection of molecules. The degrees of polymerization obtained, when amino acid adenylates are added to montmorillonite suspensions in water, are much higher than those obtained by polymerization in the absence of such a clay. In addition, they are of a discrete spectrum, usually multiples of 6 or 7, and reach values of up to 40 mers. In the absence of clay a continuous spectrum of degrees of polymerization is obtained, and usually up to 4-6 mers only. Copolymerization in the absence of clays yields mostly random copolymers, in their presence mostly block copolymers are obtained. Optical density measurements show that after adsorption has taken place on the clay, stacking of its layers occurs. Polymerization starts only after these stacked layers have been formed

Numerous nanopores developed in organo-clay complexes during the shale formations

NASA Astrophysics Data System (ADS)

Wang, Q.; Wang, T.; Lu, H.; Liao, J.

2017-12-01

Shale gas as new energy resource is either stored in nano pores and microfractures or absorbed on the surface of kerogen and clay aggregate (Chalmers et al., 2012). Nano pores developed in organic matters is very important, because these organic pores have better connectivity than inorganic pores (Loucks et al., 2012) and can form an effective pore system where shale gas flows dominantly (Curtis et al., 2010). In order to figure out how the organic pores is affected by shale compositions, we conduct in-situ FE-SEM and EDS analysis on organic-rich Longmaxi shales. The data indicate that 1) organic matter, mixed with clay minerals, can form an organo-clay complex containing many nanopores; 2)furthermore, larger organic pores are developed in organo-clay complexes with higher clay content than in those with lower clay content(Wang et al., 2017). It seems that the presence of organo-clay complex raises the heterogeneous than pure organic matters. Organo-clay complex may bring in lots of intergranular nanopores between organic matter and clay minerals. Another potential interpretation is that clay minerals may influence kerogen thermal decomposition, generation of hydrocarbons and thus the development of organic pores. The presence of numerous nanopores in organo-clay complexes may promote the connectivity of the pore network and enhance the hydrocarbon production efficiency for shale gas field.

Infrared analysis of clay bricks incorporated with spent shea waste from the shea butter industry.

PubMed

Adazabra, A N; Viruthagiri, G; Shanmugam, N

2017-04-15

The peculiar challenge of effective disposing abundant spent shea waste and the excellent compositional variation tolerance of clay material offered an impetus to examine the incorporation of spent shea waste into clay material as an eco-friendly disposal route in making clay bricks. For this purpose, the chemical constituent, mineralogical compositions and thermal behavior of both clay material and spent shea waste were initially characterized from which modelled brick specimens incorporating 5-20 wt% of the waste into the clay material were prepared. The clay material showed high proportions of SiO 2 (52.97 wt%) and Al 2 O 3 (27.10 wt%) indicating their rich kaolinitic content: whereas, the inert nature of spent shea waste was exhibited by their low oxide content. The striking similarities in infrared absorption bands of pristine clay material and clay materials incorporated with 15 wt% of spent shea waste showed that the waste incorporation had no impact on bond formation of the clay bricks. Potential performance benefits of developing bricks from clay material incorporated with spent shea waste included improved fluxing agents, economic sintering and making of sustainable bricks. Consequently, the analytical results authenticate the incorporation of spent shea waste into clay materials for various desired benefits aside being an environmental correct route of its disposal. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ultrasonically assisted single screw extrusion, film blowing and film casting of LLDPE/clay and PA6/clay nanocomposites

NASA Astrophysics Data System (ADS)

Niknezhad, Setareh

The major objective of this study was to investigate the effect of ultrasonic treatment on the dispersion of modified clay particles in LLDPE and PA6 matrices and the final properties of nanocomposites. LLDPE and PA6 are two polymers that are widely used in packaging industry. Blown and cast films were manufactured from the prepared nanocomposites. To achieve one step film processing, an online ultrasonic film casting was developed. Ultrasonic waves caused high-energy mixing and dispersion due to the acoustic cavitation, causing the clay agglomorates to separate into individual platelets in polymer matrix. Ultrasonic waves also broke down the polymer molecular chains reducing viscosity of the melt, facilating dispersion of the clay platelets throughout the matrix. Ultrasound also led to a breakage of the clay platelets reducing the particle size and improving their distribution. Clay particles acted as a heterogenous nucleation agent generating smaller size polymer crystals. In turn, these improved different properties including mechanical properties, oxygen permeability and transparency of films. In LLDPE/clay 20A nanocomposites, the effect of ultrasound was more obvious at higher clay loadings. Exfoliated structure for ultrasonically treated nanocomposites containing 2.5, 5 and 7.5 wt% of clay 20A and highly intercalated structure for ultrasonically treated nanocomposites containing 10 wt% of clay 20A were achieved. However, in blown films, the exfoliated structure transferred to the intercalated structure due to the addition of more shear and thermal degradation of surfactants of the clay particles. While, manufacturing cast films using the new developed online ultrasonic cast film machine revealed the exfoliated structure with ultrasonic treatment till 7.5 wt% of clay loadings. Cast films of nanocomposites containing 5 wt% of clay loadings were also prepared with addition of different compatibilizers. The compatibilizer containing higher amount of grafted maleic anhydride (MA) affected mechanical properties and oxygen permeability with ultrasonic treatment to higher extent. However, use of compatibilizers led to a higher die pressure and resulted in opaque cast films. The mechanical properties were in agreement with crystallinity of samples. The exfoliated structure was achieved for PA6/clay 30B nanocomposites prepared using ultrasonically assisted single screw extrusion except for untreated nanocomposites containing 10 wt% of clay 30B. Untreated 92.5/7.5 and 90/10 PA6/clay 30B blown films showed the intercalated structure, but the exfoliated structure was achieved with ultrasonic treatment. All cast films of PA6/clay 30B showed the exfoliated structure. FTIR spectroscopy along with XRD results confirmed the existence of alpha and gamma-type crystals in the cast films, with clay particles favoring the formation of gamma-type crystals, and ultrasonic treatment favoring the formation of alpha-type crystals. Both parameters increased crystallinity of cast films improving their mechanical properties and oxygen permeability.

Formation of stable nanocomposite clays from small peptides reacted with montmorillonite and illite-smectite mixed layer clays

NASA Astrophysics Data System (ADS)

Block, K. A.; Katz, A.; LeBlanc, J.; Peña, S.; Gottlieb, P.

2015-12-01

Understanding how organic compounds interact with clay minerals and which functional groups result in the strongest bonds is pivotal to achieving a better understanding of how mineral composition affects the residence time of carbon and nitrogen in soils. In this work, we describe how small peptides derived from tryptone casein digest are dissolved and suspended with clay minerals to examine the nature of OM adsorption to mineral surfaces and the resulting effect on clay mineral structure. XRD analyses indicate that peptides intercalation results in expansion of the d001 spacing of montmorillonite (Mt) and the smectite component of a 70-30 illite-smectite mixed layer clay (I-S) and poorer crystallinity overall as a result of exfoliation of tactoids. Peptide adsorption is concentration-dependent, however, surface adsorption appears to mediate interlayer adsorption in Mt reaching a maximum of 16% of the mass of the organoclay complex, indicating that at a critical concentration, peptide intercalation will supersede surface adsorption resulting in a more stable attachment. In I-S the degree of surface adsorption and intercalation is proportional to concentration, however, surface adsorption is not a priming mechanism for interlayer adsorption. Thermogravimetric analysis of the organoclay complexes determined by TGA coupled to GC-MS indicate that the most prominent product species measured was 1-(1-Trimethylsiloxyethenyl)-3-trimethylsiloxy-benzene, likely from tryptophan monomer decomposition. The compound was detected over a broad temperature range, greater than 300 oC, during pyrolysis and suggests a carbon-silicon covalent bond formed between the peptide and tetrahedral layers in the clay. An additional silicon-bearing VOC detected at lower pyrolysis temperature by GC was N,N-Diethyl-1-(trimethylsilyl)-9,10-didehydroergoline-8-carboxamide, likely derived from a lysine-bearing peptide derivative. We hypothesize that hydrophobic (non-ionic) peptides react with silanol at the clay platelet edges to induce exfoliation and subsequent formation of stable nanocomposite clays.

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.

Clay mineralogy, strontium and neodymium isotope ratios in the sediments of two High Arctic catchments (Svalbard)

NASA Astrophysics Data System (ADS)

Hindshaw, Ruth S.; Tosca, Nicholas J.; Piotrowski, Alexander M.; Tipper, Edward T.

2018-03-01

The identification of sediment sources to the ocean is a prerequisite to using marine sediment cores to extract information on past climate and ocean circulation. Sr and Nd isotopes are classical tools with which to trace source provenance. Despite considerable interest in the Arctic Ocean, the circum-Arctic source regions are poorly characterised in terms of their Sr and Nd isotopic compositions. In this study we present Sr and Nd isotope data from the Paleogene Central Basin sediments of Svalbard, including the first published data of stream suspended sediments from Svalbard. The stream suspended sediments exhibit considerable isotopic variation (ɛNd = -20.6 to -13.4; 87Sr / 86Sr = 0.73421 to 0.74704) which can be related to the depositional history of the sedimentary formations from which they are derived. In combination with analysis of the clay mineralogy of catchment rocks and sediments, we suggest that the Central Basin sedimentary rocks were derived from two sources. One source is Proterozoic sediments derived from Greenlandic basement rocks which are rich in illite and have high 87Sr / 86Sr and low ɛNd values. The second source is Carboniferous to Jurassic sediments derived from Siberian basalts which are rich in smectite and have low 87Sr / 86Sr and high ɛNd values. Due to a change in depositional conditions throughout the Paleogene (from deep sea to continental) the relative proportions of these two sources vary in the Central Basin formations. The modern stream suspended sediment isotopic composition is then controlled by modern processes, in particular glaciation, which determines the present-day exposure of the formations and therefore the relative contribution of each formation to the stream suspended sediment load. This study demonstrates that the Nd isotopic composition of stream suspended sediments exhibits seasonal variation, which likely mirrors longer-term hydrological changes, with implications for source provenance studies based on fixed end-members through time.

Enhanced sorption of trichloroethene by smectite clay exchanged with Cs+.

PubMed

Aggarwal, Vaneet; Li, Hui; Boyd, Stephen A; Teppen, Brian J

2006-02-01

Trichloroethene (TCE) is one of the most common pollutants in groundwater, and Cs+ can be a cocontaminant at nuclear facilities. Smectite clays have large surface areas, are common in soils, have high affinities for some organic contaminants, and hence can potentially influence the transport of organic pollutants entering soils and sediments. The exchangeable cations present near smectite clay surfaces can radically influence the sorption of organic pollutants by soil clays. This research was undertaken to determine the effect of Cs+, and other common interlayer cations, such as K+ and Ca2+, on the sorption of TCE by a reference smectite clay saponite. Cs-saturated clay sorbed the most TCE, up to 3500 mg/kg, while Ca-saturated smectite sorbed the least. We hypothesize that the stronger sorption of TCE by the Cs-smectite can be attributed to the lower hydration energy and hence smaller hydrated radius of Cs+, which expands the lateral clay surface domains available for sorption. Also, Cs-smectite interlayers are only one or two water layers thick, which may drive capillary condensation of TCE. Our results implicate enhanced retention of TCE in aquifer materials containing smectites accompanied by Cs+ cocontamination.

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.

ANALYSIS OF A GAS-PHASE PARTITIONING TRACER TEST CONDUCTED IN AN UNSATURATED FRACTURED-CLAY FORMATION

EPA Science Inventory

The gas-phase partitioning tracer method was used to estimate non-aqueous phase liquid (NAPL), water, and air saturations in the vadose zone at a chlorinated-solvent contaminated field site in Tucson, AZ. The tracer test was conducted in a fractured-clay system that is the confin...

In Situ Clay Formation: Evaluation of a Proposed New Technology for Stable Containment Barriers

DTIC Science & Technology

2004-03-01

situ layered double hydroxide precipitation........... 23 4.2.1 Solution preparation and column mixing...22 Table 4.2 Summary of in situ precipitation of layered double hydroxide (LDH...effect on permeability for the smallest volume precipitated is sheet silicates or layered -clay phases (hereafter called “clays”). In natural

Vegetable Oil-Based Hyperbranched Thermosetting Polyurethane/Clay Nanocomposites

PubMed Central

2009-01-01

The highly branched polyurethanes and vegetable oil-based polymer nanocomposites have been showing fruitful advantages across a spectrum of potential field of applications.Mesua ferreaL. seed oil-based hyperbranched polyurethane (HBPU)/clay nanocomposites were prepared at different dose levels by in situ polymerization technique. The performances of epoxy-cured thermosetting nanocomposites are reported for the first time. The partially exfoliated structure of clay layers was confirmed by XRD and TEM. FTIR spectra indicate the presence of H bonding between nanoclay and the polymer matrix. The present investigation outlines the significant improvement of tensile strength, scratch hardness, thermostability, water vapor permeability, and adhesive strength without much influencing impact resistance, bending, and elongation at break of the nanocomposites compared to pristine HBPU thermoset. An increment of two times the tensile strength, 6 °C of melting point, and 111 °C of thermo-stability were achieved by the formation of nanocomposites. An excellent shape recovery of about 96–99% was observed for the nanocomposites. Thus, the formation of partially exfoliated clay/vegetable oil-based hyperbranched polyurethane nanocomposites significantly improved the performance. PMID:20596546

Vegetable Oil-Based Hyperbranched Thermosetting Polyurethane/Clay Nanocomposites.

PubMed

Deka, Harekrishna; Karak, Niranjan

2009-04-25

The highly branched polyurethanes and vegetable oil-based polymer nanocomposites have been showing fruitful advantages across a spectrum of potential field of applications. Mesua ferrea L. seed oil-based hyperbranched polyurethane (HBPU)/clay nanocomposites were prepared at different dose levels by in situ polymerization technique. The performances of epoxy-cured thermosetting nanocomposites are reported for the first time. The partially exfoliated structure of clay layers was confirmed by XRD and TEM. FTIR spectra indicate the presence of H bonding between nanoclay and the polymer matrix. The present investigation outlines the significant improvement of tensile strength, scratch hardness, thermostability, water vapor permeability, and adhesive strength without much influencing impact resistance, bending, and elongation at break of the nanocomposites compared to pristine HBPU thermoset. An increment of two times the tensile strength, 6 degrees C of melting point, and 111 degrees C of thermo-stability were achieved by the formation of nanocomposites. An excellent shape recovery of about 96-99% was observed for the nanocomposites. Thus, the formation of partially exfoliated clay/vegetable oil-based hyperbranched polyurethane nanocomposites significantly improved the performance.

Smectite clays in Mars soil - Evidence for their presence and role in Viking biology experimental results

NASA Technical Reports Server (NTRS)

Banin, A.; Rishpon, J.

1979-01-01

Evidence for the presence of smectite clays in Martian soils is reviewed and results of experiments with certain active clays simulating the Viking biology experiments are reported. Analyses of Martian soil composition by means of X-ray fluorescence spectrometry and dust storm spectroscopy and Martian geological history strongly suggest the presence of a mixture of weathered ferro-silicate minerals, mainly nontronite and montmorillonite, accompanied by soluble sulphate salts, as major constituents. Samples of montmorillonite and nontronite incubated with (C-14)-formate or the radioactive nutrient medium solution used in the Viking Labeled Release experiment, were found to produce patterns of release of radioactive gas very similar to those observed in the Viking experiments, indicating the iron-catalyzed decomposition of formate as the reaction responsible for the Viking results. The experimental results of Hubbard (1979) simulating the results of the Viking Pyrolytic Release experiment using iron montmorillonites are pointed out, and it is concluded that many of the results of the Viking biology experiments can be explained in terms of the surface activity of smectite clays in catalysis and adsorption.

Ziegler-Natta Catalyst Based on MgCl₂/Clay/ID/TiCl₄ for the Synthesis of Spherical Particles of Polypropylene Nanocomposites.

PubMed

Cardoso, Renata da Silva; Oliveira, Jaqueline da Silva; Ramis, Luciana Bortolin; Marques, Maria de Fátima V

2018-07-01

In the present work, we have designed MgCl2/clay/internal donor (ID)/TiCl4 based bisupported Ziegler-Natta catalysts containing varying amounts of organoclay (montmorillonite) in order to synthesize spherical particles of polypropylene/clay nanocomposites (PCN). The organoclay was introduced into the catalyst support formulation and PCN was obtained using the in situ polymerization technique. Decreasing the reaction time, it was possible to obtain nanocomposites with high concentrations of clay (masterbatches). Micrographs of SEM confirmed the spherical morphology of the catalysts. In addition, XRD patterns show that the active sites for polymerization were inserted in the clay galleries. The catalytic performance was evaluated in slurry propylene polymerization using triethylaluminium as cocatalyst and silane as external electron donor at 70 °C, 4 bar, and different reaction times. The PCNs obtained containing different clay amounts were characterized by X-ray diffraction, thermal analyses, transmission electronic microscopy, and extractables in heptane. The results revealed that the synthesized PP/clay particles were also spherical showing that the morphological control is possible even using catalysts containing high amounts of clay. The PCN presented high degradation temperature (459 °C). The XRD peak related to the clay interlamellar distance has shifted to lower angles, and TEM images confirmed the formation of exfoliated/intercalated clay on the PP matrix and absence of microparticles of clay.

First Report of Microfaunal Remains from Lignitic Sequences of Bhavnagar Lignite Mine (khadsaliya Formation), Gujarat, India: Implication to Depositional Environments and Age

NASA Astrophysics Data System (ADS)

Maurya, A. S.

2016-12-01

FIRST REPORT OF MICROFAUNAL REMAINS FROM LIGNITIC SEQUENCES OF BHAVNAGAR LIGNITE MINE (KHADSALIYA FORMATION), GUJARAT, INDIA: IMPLICATION TO DEPOSITIONAL ENVIRONMENTS AND AGEABHAYANAND SINGH MAURYA1*, SANJAY KUMAR VERMA1, PRAGYA PANDEY11Department of Earth Sciences, Indian Institute of Technology Roorkee, Roorkee Moderately preserved fish otoliths, fish vertebra, bivalves, pteropods, ostracods and foraminifereral remains were recovered from the grey to greenish-grey clays of Khadsaliya Formation, Bhavnagar Lignite Mine (western India) and quantitatively analyzed to understand the depositional environment. The bio-facies assemblage is diverse and dominated by fauna Fishes, Bivalve, Pteropods and with rare occurrences of Ostracoda and Foraminifera. Fish fauna includes otoliths represented by Ambassidarum, Apogonidarum, Percoideorum and Gobiidarum vastani, out of which Gobiidarum vastani is possibly representing Ypresian (early Eocene). The Globanomalina ovalis a smaller planktic foraminifer is known to be a very short ranged species corresponds to Planktic Foranimiferal Zone 5 to 6 (P5-P6) i.e late Thanetian to early Yepresian. Presence of both fresh water (Lepisosteus, Osteoglossidae), fresh water (Cypridopsis) ostracods and shallow marine fauna (Enchodus, Egertonia and Stephanodus) of fish vertebra; (Cardita) bivalve, , marine water (Globanomalina, Eggrella, Pyrulinoides) foraminifer suggests that Bhavnagar lignite mine have an assemblage of admixed fauna and rocks of Khaldsiya formation at Bhavnagar Lignite mine deposited under marine transgressive-regressive cycles. Some of the microfauna from Bhavnagar lignite mine show close affinities with microfaunal assemblages of the Vastan lignite mine of Gujarat, India which is stated to be of Ypresian (early Eocene).

Clay Minerals

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

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 studiesmore » 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.« less

Frictional properties of the biogenic oozes from the CRISP drilling project: possible evidence of past slip-to-the-trench

NASA Astrophysics Data System (ADS)

Vannucchi, P.; Spagnuolo, E.; Aretusini, S.; Di Toro, G.; Tsutsumi, A.; Ujiie, K.; Namiki, Y.

2015-12-01

The 2011 Tohoku EQ revealed that co-seismic displacement along the megathrust can reach the deformation front of subduction zones. Since then the global significance of slip-to-the-trench has become an important field of study; hence investigation of past events at other active megathrusts is critical. Offshore SE Costa Rica the deformation front of the Caribbean forearc is formed by a ~10 km-wide accretionary wedge. Here, drill Site U141 has revealed a record of frontal thrusts detached along biogenic ooze, which correlates lithologically with the "reference" Site U1381. This biogenic ooze contains >70% of organic components.There are up to 15% silica-rich elements in the upper part of the formation, while clay increases downsection. The biogenic ooze is overlain by silty clay, in which smectite is the dominant mineral. Low- to high-velocity friction experiments were performed on the biogenic ooze and the silty clay to investigate the velocity dependence of friction and the micromechanical foundation of strain localization within fontal thrusts. These experiments were performed at slip-rates of 3 µms-1 to 3.5 ms-1and σn up to 12 MPa, under both room-humidity and water saturated conditions. These experimental results indicate that, at low slip-rates, the biogenic ooze is stronger than the silty clay. At increasing slip-rates silty clays have a positive dependence of friction, while biogenic oozes show a sharp decrease of their friction coefficient as slip-rate increases. This rate-weakening behavior of the biogenic oozes may enhance co-seismic slip along the megathrust. The implication of these mechanical measurements is that the geological structures found in the forearc toe offshore SE Costa Rica were formed by locally high slip-rates that have enhanced slip propagation to the trench. Under slow slip-rates, deformation can have localized easier by creeping within the clays than in the oozes as seen. As Tsunami earthquakes are known to form with pronounced slip-to-the trench, the presence of biogenic oozes could be an indicator for past and potential tsunamigenic events. If so, this would be the case for the MAT from Guatemala to Costa Rica where similar biogenic ooze is found at all drill sites. Specifically, biogenic ooze may have formed the slip surface of the 1992 Nicaragua tsunami EQ. This needs to be tested.

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.

Unraveling the mineralogy of delta deposits on Mars

NASA Astrophysics Data System (ADS)

Osterloo, Mikki; Kierein-Young, Kathryn

2017-04-01

Detailed geologic characterizations of three of 50+ fan deltas on Mars have yielded important information on their mineralogy as well as formation processes. Data returned from the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) have been used to identify spectroscopic signatures consistent with phyllosilicates in fans or deltas within paleolake basins (i.e., Eberswalde, Holden, and Jezero) that indicate sustained subaqueous sediment deposition. Based on these results, two periods of martian history have been identified when the surface or near surface may have been habitable: (1) during the formation of the iron-magnesium smectite clays, likely in the Early Noachian and (2) during the Late Noachian to Early Hesperian fluvial surface activity that led to the formation of Jezero lake. On Earth, rapid deposition of deltaic sediments can preserve organic materials; hence Martian fan deltas may be ideal environments to investigate the past habitability of the planet. Rapid burial coupled with the identification of phyllosilicates within at least some of the martian deltas makes an even more intriguing argument for further investigation of the remainder of deltas. This is because phyllosilicates, and specifically smectite clays, have the ability to trap organic matter in the interlayer sites of their mineral structures and in terrestrial settings are commonly associated with the most organic rich units. Organic materials that were transported into paleolakes would likely have been buried relatively quickly. Hence, the organics would have been protected within the clay-rich deltaic and lacustrine deposits from oxidation and photochemical dissociation. We will present the initial results of a comprehensive study designed to investigate the compositional and mineralogical variability of the remainder of dust-free, previously un-characterized deltas on Mars (of which, there are 33). Our study aims to provide key information regarding differences in formation and preservation processes between the fan delta deposits. Our initial survey of the deltas indicates that almost all sites contain minor phyllosilicate detections, however only nine sites have significant abundances (i.e., spatially cohesive mapped deposits). Most of the phyllosilicate deposits consist of Fe/Mg clays such as nontronite and saponite, with a few sites showing detections of minor amounts of Al clays. Geologic observations indicate that most of the clays outcrop along the bottom edge of the deltas with a few sites showing a larger band of clays located just beyond the base of the delta. HiRISE images provide additional small-scale geologic context and indicate that most of the clay deposits are exposed as thin erosional layers. When clay deposits are located beyond the base of the delta they are typically more massive in outcrop. Our ongoing morphological, watershed, and catchment basin investigations will provide additional constraints on the style and extent of hydrologic activity. Coupling our detailed spectroscopic characterization with our ongoing work will provide key information on the geologic processes that produced the mineralogical diversity of martian deltas and will likely provide important clues regarding the past habitability of these environments.

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

NASA Technical Reports Server (NTRS)

Orenberg, J. B.; Handy, J.

1991-01-01

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

A New Late Glacial Site in the Central Appalachians of Virginia. Preliminary Findings From Paleobotany, Palynology, and Geomorphology

NASA Astrophysics Data System (ADS)

Schwartz, B. F.; Upchurch, G. R.; Willard, D. A.; Bernhardt, C. E.; Valella, P. A.

2009-12-01

Thick clay deposits in a recently identified paleo-lake bed in a central Appalachian karst system in Highland County, Virginia have yielded well-preserved pollen and macroflora that provide the opportunity to refine the understanding of Pleistocene climate, vegetation dynamics, and erosion in the region. A radiocarbon date of 22,000 14C yr B.P. on wood fragments near the top of the sequence establishes the age of the sediments. Pollen and plant macrofloras characteristic of modern boreal forests are present in sediments at this site. Pollen assemblages show a dominance of conifers, mostly Pinus banksiana and Picea, with Lycopodium as important ground cover. Leaf fossils sieved from the clay show a dominance of Picea needles and common dicot leaf fragments, suggesting that Pinus is either over-represented in the pollen flora or more distal to the paleo-lake. Macrofossil assemblages sieved from the clay contain a variety of non-leaf remains, including fruits, seeds, mosses, insects, feathers, and fungi. Test augering and geophysical results indicate that these clay deposits are at least 9m and perhaps as much as 15m thick. The amount and temporal distribution of sediment loads to the paleo-lake (a depositional environment) from the surrounding landscape (an erosional environment) will be modeled using analysis of sediment facies in and above (>12m) these clays, combined with sediment volume calculations and drainage basin analysis, and constrained by dates from the sediments themselves. Due to the rare occurrence of still-water depositional environments in the Appalachians, this site provides paleo-climate and sedimentological data that will refine regional models of landscape evolution and incision. This work also has implications for the development and modification of a significant karst system that surrounds and underlies the paleo-lake bed. The same karst system is responsible both for the formation of the paleo-lake (after the drain in a blind valley became plugged), and its later draining and current removal of lake sediments through the underlying karst system.

Effects of a thermal perturbation on mineralogy and pore water composition in a clay-rock: An experimental and modeling study

NASA Astrophysics Data System (ADS)

Gailhanou, H.; Lerouge, C.; Debure, M.; Gaboreau, S.; Gaucher, E. C.; Grangeon, S.; Grenèche, J.-M.; Kars, M.; Madé, B.; Marty, N. C. M.; Warmont, F.; Tournassat, C.

2017-01-01

The physical and chemical properties of clay-rocks are, at least partly, controlled by the chemical composition of their pore water. In evaluating the concept of disposing of radioactive waste in clay-rock formations, determining pore water composition is an important step in predicting how a clay-rock will behave over time and as a function of external forces, such as chemical and thermal perturbations. This study aimed to assess experimental and modeling methodology to calculate pore water composition in a clay-rock as a function of temperature (up to 80 °C). Hydrothermal alteration experiments were carried out on clay-rock samples. We conducted comprehensive chemical and mineralogical characterization of the material before and after reaction, and monitored how the chemical parameters in the liquid and gas phases changed. We compared the experimental results with the a priori predictions made by various models that differed in their hypotheses on the reactivity of the minerals present in the system. Thermodynamic equilibrium could not be assessed unequivocally in these experiments and most of the predicted mineralogy changes were too subtle to be tracked quantitatively. However, from observing the neo-formation of minerals such as goethite we were able to assess the prominent role of Fe-bearing phases in the outcome of the experiments, especially for the measured pH and pCO2 values. After calibrating the amount of reacting Fe-bearing phases with our data, we proposed a thermodynamic model that was capable of predicting the chemical evolution of the systems under investigation as well as the evolution of other systems already published in the literature, with the same clay-rock material but with significant differences in experimental conditions.

Clay mineralogy of weathering profiles from the Carolina Piedmont.

USGS Publications Warehouse

Loferski, P.J.

1981-01-01

Saprolite profiles (12) that formed over various crystalline rocks from the Charlotte 1o X 2o quadrangle showed overall similarity in their clay mineralogy to depths of 6 to 45 m indicating control by weathering processes rather than by rock type. Most saprolite contained 10-25% clay, and ranged 3 to 70%. Kaolinite and halloysite composed = or >75% of the clay fraction of most samples. The ratio kaolinite:halloysite ranged widely, from 95% kaolinite to 90% halloysite, independent of depth. Clay-size mica was present in all profiles, and ranged 5-75% over a sericite schist. Mixed-layer mica-smectite and mica-vermiculite were subordinate; discrete smectite and vermiculite were rare. The abundance of halloysite indicates a continuously humid environment since the time of profile formation, because of the rapidity with which halloysite dehydrates irreversibly. -R.S.M.

Ionic strength-induced formation of smectite quasicrystals enhances nitroaromatic compound sorption.

PubMed

Li, Hui; Pereira, Tanya R; Teppen, Brian J; Laird, David A; Johnston, Cliff T; Boyd, Stephen A

2007-02-15

Sorption of organic contaminants by soils is a determinant controlling their transport and fate in the environment. The influence of ionic strength on nitroaromatic compound sorption by K+- and Ca2+ -saturated smectite was examined. Sorption of 1,3-dinitrobenzene by K-smectite increased as KCl ionic strength increased from 0.01 to 0.30 M. In contrast, sorption by Ca-smectite at CaCl2 ionic strengths of 0.015 and 0.15 M remained essentially the same. The "salting-out" effect on the decrease of 1,3-dinitrobenzene aqueous solubility within this ionic strength range was <1.5% relative to the solubility in pure water. This decrease of solubility is insufficient to account for the observed increase of sorption by K-smectite with increasing KCl ionic strength. X-ray diffraction patterns and light absorbance of K-clay suspensions indicated the aggregation of clay particles and the formation of quasicrystal structures as KCI ionic strength increased. Sorption enhancement is attributed to the formation of better-ordered K-clay quasicrystals with reduced interlayer distances rather than to the salting-out effect. Dehydration of 1,3-dinitrobenzene is apparently a significant driving force for sorption, and we show for the first time that sorption of small, planar, neutral organic molecules, namely, 1,3-dinitrobenzene, causes previously expanded clay interlayers to dehydrate and collapse in aqueous suspension.

Chemical models for martian weathering profiles: Insights into formation of layered phyllosilicate and sulfate deposits

NASA Astrophysics Data System (ADS)

Zolotov, Mikhail Yu.; Mironenko, Mikhail V.

2016-09-01

Numerical chemical models for water-basalt interaction have been used to constrain the formation of stratified mineralogical sequences of Noachian clay-bearing rocks exposed in the Mawrth Vallis region and in other places on cratered martian highlands. The numerical approaches are based on calculations of water-rock type chemical equilibria and models which include rates of mineral dissolution. Results show that the observed clay-bearing sequences could have formed through downward percolation and neutralization of acidic H2SO4-HCl solutions. A formation of weathering profiles by slightly acidic fluids equilibrated with current atmospheric CO2 requires large volumes of water and is inconsistent with observations. Weathering by solutions equilibrated with putative dense CO2 atmospheres leads to consumption of CO2 to abundant carbonates which are not observed in clay stratigraphies. Weathering by H2SO4-HCl solutions leads to formation of amorphous silica, Al-rich clays, ferric oxides/oxyhydroxides, and minor titanium oxide and alunite at the top of weathering profiles. Mg-Fe phyllosilicates, Ca sulfates, zeolites, and minor carbonates precipitate from neutral and alkaline solutions at depth. Acidic weathering causes leaching of Na, Mg, and Ca from upper layers and accumulation of Mg-Na-Ca sulfate-chloride solutions at depth. Neutral MgSO4 type solutions dominate in middle parts of weathering profiles and could occur in deeper layers owing to incomplete alteration of Ca minerals and a limited trapping of Ca to sulfates. Although salts are not abundant in the Noachian geological formations, the results suggest the formation of Noachian salty solutions and their accumulation at depth. A partial freezing and migration of alteration solutions could have separated sulfate-rich compositions from low-temperature chloride brines and contributed to the observed diversity of salt deposits. A Hesperian remobilization and release of subsurface MgSO4 type solutions into newly-formed depressions could account for formation of some massive layered sulfate deposits through freezing or evaporation. This scenario explains the observed deficiency of salts in Noachian formations, a paucity of Hesperian phyllosilicates, and the occurrence of sulfate deposits in Valles Marineris troughs, chaotic terrains, and some craters of the Hesperian age.

Formation and Coloring Mechanism of Typical Aluminosilicate Clay Minerals for CoAl2O4 Hybrid Pigment Preparation

PubMed Central

Zhang, Anjie; Mu, Bin; Wang, Xiaowen; Wen, Lixin; Wang, Aiqin

2018-01-01

Different kinds of aluminosilicate minerals were employed to fabricate CoAl2O4 hybrid pigment for studying its formation and coloring mechanism. It revealed that the color of the obtained hybrid pigments was determined by the content of Al2O3 and lightness of clay minerals. The higher the Al2O3 content and the lightness of clay minerals, the better the color parameters of hybrid pigments. During the preparation of hybrid pigments, CoAl2O4 nanoparticles were confined to be loaded on the surface of the aluminosilicate minerals, which effectively prevented from the aggregation and the size increase of CoAl2O4 nanoparticles. What's more, aluminosilicate mineral might be an ideal natural aluminum source to compensate the aluminum loss due to the dissolution of Al(OH)3 at alkaline medium during precursor preparation, keeping an optimum molar ratio of Co2+/Al3+ for formation of spinel CoAl2O4 pigments in the process of high-temperature crystallization. PMID:29725589

Formation and Coloring Mechanism of Typical Aluminosilicate Clay Minerals for CoAl2O4 Hybrid Pigment Preparation.

PubMed

Zhang, Anjie; Mu, Bin; Wang, Xiaowen; Wen, Lixin; Wang, Aiqin

2018-01-01

Different kinds of aluminosilicate minerals were employed to fabricate CoAl 2 O 4 hybrid pigment for studying its formation and coloring mechanism. It revealed that the color of the obtained hybrid pigments was determined by the content of Al 2 O 3 and lightness of clay minerals. The higher the Al 2 O 3 content and the lightness of clay minerals, the better the color parameters of hybrid pigments. During the preparation of hybrid pigments, CoAl 2 O 4 nanoparticles were confined to be loaded on the surface of the aluminosilicate minerals, which effectively prevented from the aggregation and the size increase of CoAl 2 O 4 nanoparticles. What's more, aluminosilicate mineral might be an ideal natural aluminum source to compensate the aluminum loss due to the dissolution of Al(OH) 3 at alkaline medium during precursor preparation, keeping an optimum molar ratio of Co 2+ /Al 3+ for formation of spinel CoAl 2 O 4 pigments in the process of high-temperature crystallization.

Preparation and Characterization of a Superparamagnetic Polymer Nanocomposite

NASA Astrophysics Data System (ADS)

Brenner, N.; Isseroff, R.; Rafailovich, M.; Rudomen, G.; Gambino, R.; Liang, S. S.; Sunil, D.; Si, M.; Collazo, L.; Pernodet, N.; Fang, X.

2006-03-01

Fe(CO)5 decomposition produced ferro- and superparamagnetic polymer nanocomposites. Fe(CO)5 and Cloisite 20A clay were combined in a closed vial for 12 hours, then opened to air for 2 hours. Mössbauer analysis indicated formation of Fe2O3 on clay; mass analysis indicated 12% Fe in clay. A Brabender mixed Fe2O3/clays with PMMA and EVA at ratios by mass of 9:4:36 and 1:1:4 respectively (Fe(CO)5:clay:polymer). TEM displayed Fe2O3 nanoparticles, 3.3 ^+ 0.8 nm in diameter, adsorbed on exfoliated clay platelet surfaces in polymer matrices. VSM data indicated superparamagnetism with moments of 510.3 emu/g(Fe2O3) (PMMA) and 8.46 emu/g(Fe2O3) (EVA). DMA showed 37% decreased dynamic modulus (EVA) and 11% (PMMA) due to Fe2O3. TGA indicated PMMA stability to 400^oC (9.3% mass residual) and EVA to 435^oC (11% mass residual). Cell adhesion tests showed Fe2O3/clay enhanced proliferation, promising applications in bone implants.

A review of biostratigraphic studies in the olistostrome deposits of Karangsambung Formation

NASA Astrophysics Data System (ADS)

Hendrizan, Marfasran

2018-02-01

Planktonic foraminifera is widely used for marine sediment biostratigraphy. Foraminiferal biostratigraphy of Karangsambung Formation is relatively rare to be investigated by previous researchers. A review of foraminiferal biostratigraphy is expected to be early work to perform a research about the ages of Tertiary rock formations in Karangsambung. The research area is formed by olistostrome process; a sedimentary slide deposit characterized by bodies of harder rock mixed and dispersed in a matrix. Biostratigraphic studies based on foraminifera and nannoplankton in Karangsambung Formation are still qualitative analysis using fossils biomarker. However, the age of this formation is still debatable based on foraminifera and nannofossil analysis. Two explanations of debatable ages in Karangsambung Formation that is possibly developed in Karangsambung area: firstly, Karangsambung Formation is characterized by normal sedimentation in some places and other regions such Kali Welaran and Clebok, Village as a product of olistostrome, and secondly, Karangsambung Formation is olistostrome deposit. However, micropaleontology sampling and analysis in matrix clays from olistostrome were ignored causing biostratigraphical results in those matrix clays occurred in normal sedimentation process and achieving the age of middle Eocene to Oligocene. We suppose previous authors picked samples in matrix of Karangsambung Formation from several river sections, which will make misinterpretation of the age of Karangsambung Formation. The age of middle to late Eocene probably is the dates of the older sediment that was reworked by sliding and sampling process and accumulated in Karangsambung Formation. The date of Karangsambung Fm is in Oligocene period based on a finding of several calcareous nannofossils. Detailed micropaleontological analysis of olistostrome deposits in Karangsambung Formation should be reevaluated for new finding of the accurate dating. Re-evaluation should start from detailed sedimentological mapping of Karangsambung Fm transects based on previous authors especially Kali Welaran, Jatibungkus transect and Clebok section followed by systematic sampling of normal sedimentation process from olistostrome products and matrix clays of olistostrome Karangsambung Formation. Finally, quantitative method of micropaleontological analysis can be applied to identify the age of Karangsambung Formation.

Environmental Assessment for Construction of a New Marina Operations Building and Associated Fuel Supply System, Hurlburt Field, Florida

DTIC Science & Technology

2005-12-01

Hurlburt Field’s climate is warm and subtropical. Annual precipitation is about 62 inches with peak rainfall occurring in July and August; October and...clay. The Alum Bluff Group and Pensacola Clay underlay the Citronelle Formation. Miocene and Oligocene age limestone lie under these units. All of the

Exfoliation restacking route to Au nanoparticle-clay nanohybrids

NASA Astrophysics Data System (ADS)

Paek, Seung-Min; Jang, Jae-Up; Hwang, Seong-Ju; Choy, Jin-Ho

2006-05-01

A novel gold-pillared aluminosilicate (Au-PILC) were synthesized with positively charged gold nanoparticles capped by mercaptoammonium and exfoliated silicate layers. Gold nanoparticles were synthesized by NaBH4 reduction of AuCl4- in the presence of N,N,N-Trimethyl (11-mercaptoundecyl)ammonium (HS(CH2)11NMe3+) protecting ligand in an aqueous solution, and purified by dialysis. The resulting positively charged and water-soluble gold nanoparticles were hybridized with exfoliated silicate sheets by electrostatic interaction. The formation of Au clay hybrids could be easily confirmed by the powder X-ray diffraction with the increased basal spacing of clay upon insertion of Au nanoparticles. TEM image clearly revealed that the Au particles with an average size of 4 nm maintain their structure even after intercalation. The Au nanoparticles supported by clay matrix were found to be thermally more stable, suggesting that the Au nanoparticles were homogeneously protected with clay nanoplates. The present synthetic route could be further applicable to various hybrid systems between metal nanoparticles and clays.

Surveying Clay Mineral Diversity in the Murray Formation, Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Bristow, T.F.; Blake, D. F..; Vaniman, D. T.; Chipera, S. J.; Rampe, E. B.; Grotzinger, J. P.; McAdam, A. C.; Ming, D. W..; Morrison, S. M.; Yen, A. S.;

Alteration in the Madera Limestone and Sandia Formation from core hole VC-1, Valles caldera, New Mexico

USGS Publications Warehouse

Keith, T.E.C.

1988-01-01

Core hole VC-1 penetrated the southwestern ring fracture zone of the 1.1 Ma Valles caldera and at a depth of 333 m intersected the top of the Paleozoic section including the Abo Formation, Madera Limestone, and Sandia Formation, reaching a total depth of 856 m. The Paleozoic rocks, which consist of thin-bedded limestone, siltstone, mudstone, sandstone, and local conglomerate, are overlain by volcanic rocks of the caldera moat that are less than 0.6 Ma. Diagenetic and at least three hydrothermal alteration stages were identified in the Madera Limestone and Sandia Formation. Diagenetic clay alteration was pervasive throughout the sedimentary rocks. Volcanic activity at 16.5 Ma and continuing through the formation of the Valles caldera resulted in high thermal gradients, which caused recrystallization of diagenetic clay minerals. Interstratified smectite-illite is the most diagnostic clay mineral throughout the section; structurally, the illite component in the ordered interstratified illite-smectite changes gradationally from 70% at the top of the Madera Limestone to 95% at the base of the section in the Sandia Formation. Pyrite that occurs as small clots and lenses as well as finely disseminated is interpreted as being of diagenetic origin, especially in organic-rich beds. Low permeability of much of the paleozoic section precluded the deposition of hydrothermal minerals except in fractures and intergranular space in some of the more permeable sandstone and brecciated horizons. Three stages of hydrothermal mineral deposition are defined. -from Author

Heteroaggregation of titanium dioxide nanoparticles with natural clay colloids.

PubMed

Labille, Jérôme; Harns, Carrie; Bottero, Jean-Yves; Brant, Jonathan

2015-06-02

To better understand and predict the fate of engineered nanoparticles in the water column, we assessed the heteroaggregation of TiO2 nanoparticles with a smectite clay as analogues for natural colloids. Heteroaggregation was evaluated as a function of water salinity (10(-3) and 10(-1) M NaCl), pH (5 and 8), and selected nanoparticle concentration (0-4 mg/L). Time-resolved laser diffraction was used, coupled to an aggregation model, to identify the key mechanisms and variables that drive the heteroaggregation of the nanoparticles with colloids. Our data show that, at a relevant concentration, nanoparticle behavior is mainly driven by heteroaggregation with colloids, while homoaggregation remains negligible. The affinity of TiO2 nanoparticles for clay is driven by electrostatic interactions. Opposite surface charges and/or high ionic strength favored the formation of primary heteroaggregates via the attachment of nanoparticles to the clay. The initial shape and dispersion state of the clay as well as the nanoparticle/clay concentration ratio also affected the nature of the heteroaggregation mechanism. With dispersed clay platelets (10(-3) M NaCl), secondary heteroaggregation driven by bridging nanoparticles occurred at a nanoparticle/clay number ratio of greater than 0.5. In 10(-1) M NaCl, the clay was preaggregated into larger and more spherical units. This favored secondary heteroaggregation at lower nanoparticle concentration that correlated to the nanoparticle/clay surface area ratio. In this latter case, a nanoparticle to clay sticking efficiency could be determined.

Reducing firing of an early pottery making kiln at Batán Grande, Peru: A Mössbauer study

NASA Astrophysics Data System (ADS)

Wagner, U.; Gebhard, R.; Häusler, W.; Hutzelmann, T.; Riederer, J.; Shimada, I.; Sosa, J.; Wagner, F. E.

1999-11-01

Material from field firing experiments using a 2,700-year old Formative kiln at Batán Grande, Peru, was studied by X-ray diffraction and Mössbauer spectroscopy. The experiments explore the technology involved in producing the gray and black reduced ware for which Cupisnique and other Formative ceramics are justly known. During firing, the iron-bearing compounds in clays undergo characteristic changes which depend on kiln temperature and atmosphere. These changes can be observed in the Mössbauer spectra. By comparing spectra of an appropriate clay fired in field experiments and in the laboratory with the spectra of ancient ceramics, a description of Formative firing techniques in a reducing environment is attempted.

The Sunny Point Formation: a new Upper Cretaceous subsurface unit in the Carolina Coastal Plain

USGS Publications Warehouse

Balson, Audra E.; Self-Trail, Jean; Terry, Dennis O.

2013-01-01

This paper formally defines the Sunny Point Formation, a new Upper Cretaceous subsurface unit confined to the outer Atlantic Coastal Plain of North and South Carolina. Its type section is established in corehole NH-C-1-2001 (Kure Beach) from New Hanover County, North Carolina. The Sunny Point Formation consists of light-olive-gray to greenish-gray, fine to coarse micaceous sands and light-olive-brown and grayish-red silty, sandy clays. The clay-rich sections typically include ironstone, lignitized wood, root traces, hematite concretions, goethite, limonite, and sphaerosiderites. The Sunny Point Formation is also documented in cores from Bladen County, North Carolina, and from Dorchester and Horry Counties, South Carolina. Previously, strata of the Sunny Point Formation had been incorrectly assigned to the Cape Fear and Middendorf Formations. The Sunny Point occupies a stratigraphic position above the Cenomanian marine Clubhouse Formation and below an upper Turonian unnamed marine unit. Contacts between these units are sharp and unconformable. Calcareous nannofossil and palynomorph analyses indicate that the Sunny Point Formation is Turonian.

Study of shale reservoir nanometer-sized pores in Member 1 of Shahejie Formation in JX area, Liaozhong sag

NASA Astrophysics Data System (ADS)

Cheng, Yong; Zhang, Yu; Wen, Yiming

2018-02-01

The microscopic pore structure is the key of the shale reservoir study; however, traditional Scanning Electron Microscopy (SEM) methods cannot identify the irregular morphology caused by mechanical polishing. In this work, Scanning Electron Microscopy combined argon ion polishing technology was taken to study the characteristics of shale reservoir pores of Member 1 of Shahejie Formation (E3s1) located in JX1-1 area of Liaozhong Sag. The results show that pores between clay platelets, intraplatelet pores within clay aggregates and organic-matter pores are very rich in the area and with good pore connectivity, so these types of pores are of great significance for oil-gas exporation. Pores between clay platelets are formed by directional or semi-directional contact between edge and surface, edge and edge or surface and surface of laminated clay minerals, whose shapes are linear, mesh, and irregular with the size of 500 nm to 5 μm. The intraplatelet pores within clay aggregates are formed in the process of the transformation and compaction of clay minerals, whose shapes are usually linear with the width of 30 to 500 nm and the length of 2 to 50 μm. The organic-matter pores are from the process of the conversion from organic matters to the hydrocarbon under thermal evolution, whose shapes are gneissic, irregular, pitted and elliptical with the size of 100 nm to 2 μm. This study is of certain guiding significance to selecting target zones, evaluating resource potential and exploring & developing of shale gas in this region.

Anodic activation of iron corrosion in clay media under water-saturated conditions at 90 degrees C: characterization of the corrosion interface.

PubMed

Schlegel, Michel L; Bataillon, Christian; Blanc, Cécile; Prêt, Dimitri; Foy, Eddy

2010-02-15

To understand the process governing iron corrosion in clay over centuries, the chemical and mineralogical properties of solids formed by free or anodically activated corrosion of iron in water-saturated clay at 90 degrees C over 4 months were probed using microscopic and spectroscopic techniques. Free corrosion led to the formation of an internal discontinuous thin (<3 microm thick) magnetite layer, an external layer of Fe-rich phyllosilicate, and a clay transformation layer containing Ca-doped siderite (Ca(0.2)Fe(0.8)CO(3)). The thickness of corroded iron equaled approximately 5-7 microm, consistent with previous studies. Anodic polarization resulted in unequally distributed corrosion, with some areas corrosion-free and others heavily corroded. Activated corrosion led to the formation of an inner magnetite layer, an intermediate Fe(2)CO(3)(OH)(2) (chukanovite) layer, an outer layer of Fe-rich 7 A-phyllosilicate, and a transformed matrix layer containing siderite (FeCO(3)). The corroded thickness was estimated to 85 microm, less than 30% of the value expected from the supplied anodic charge. The difference was accounted for by reoxidation at the anodically polarized surface of cathodically produced H(2)(g). Thus, free or anodically activated corroding conditions led to structurally similar interfaces, indicating that anodic polarization can be used to probe the long-term corrosion of iron in clay. Finally, corrosion products retained only half of Fe oxidized by anodic activation. Missing Fe probably migrated in the clay, where it could interact with radionuclides released by alteration of nuclear glass.

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.

Improving the Mechanical Performance and Thermal Stability of a PVA-Clay Nanocomposite by Electron Beam Irradiation

NASA Astrophysics Data System (ADS)

Shokuhi Rad, A.; Ebrahimi, D.

2017-07-01

The effects of electron beam irradiation and presence of clay on the mechanical properties and thermal stability of montmorillonite clay-modified polyvinyl alcohol nanocomposites were studied. By using the X-ray diffraction (XRD) and transmission electron microscopy (TEM), the microstructure of the nanocomposites was investigated. The results obtained from TEM and XRD tests showed that montmorillonite clay nanoparticles were located in the polyvinyl alcohol phase. The XRD analysis confirmed the formation of an exfoliated structure in nanocomposites samples. Increasing the amount of clay to 20 wt.% increased the tensile strength and modulus of the nanocomposite. Irradiation up to an absorbed dose of 100 kGy increased its mechanical properties and thermal stability, but at higher irradiation levels, the mechanical strength and thermal stability declined. The sample with 20 wt.% of the nanofiller, exposed to 100 kGy, showed the highest mechanical strength and thermal stability.

Clays causing adhesion with tool surfaces during mechanical tunnel driving

NASA Astrophysics Data System (ADS)

Spagnoli, G.; Fernández-Steeger, T.; Stanjek, H.; Feinendegen, M.; Post, C.; Azzam, R.

2009-04-01

During mechanical excavation with a tunnel boring machine (TBM) it is possible that clays stick to the cutting wheel and to other metal parts. The resulting delays in the progress of construction work, cause great economic damage and often disputes between the public awarding authorities and executing companies. One of the most important factors to reduce successfully the clay adhesion is the use of special polymers and foams. But why does the clay stick to the metal parts? A first step is to recognize which kind of clay mineralogy shows serious adhesion problems. The mechanical properties of clay and clay suspensions are primarily determined by surface chemistry and charge distribution at the interfaces, which in turn affect the arrangement of the clay structure. As we know, clay is a multi-phase material and its behaviour depends on numerous parameters such as: clay mineralogy, clay fraction, silt fraction, sand fraction, water content, water saturation, Atterberg limits, sticky limit, activity, cation exchange capacity, degree of consolidation and stress state. It is therefore likely that adhesion of clay on steel is also affected by these clay parameters. Samples of clay formations, which caused problems during tunnel driving, will be analyzed in laboratory. Mineralogical analyses (diffractometry, etc.) will be carried out to observe which minerals are responsible for adherence problems. To manipulate the physical properties, batch tests will be carried out in order to eliminate or reduce the adhesion on tool surfaces through variation of the zeta potential. Second step is the performance of vane shear tests on clay samples. Different pore fluid (distilled water, pure NaCl solution, ethanol and methanol) will be used to study the variation of the mechanical behaviour of clay depending on the dielectric constant of the fluids. This project is funded by the German Federal Ministry of Education and Research (BMBF) and the DFG (German Research Foundation) in the frame of the programme GEOTECHNOLOGIEN.

Exploring biotic vs. abiotic controls on syngenetic carbonate and clay mineral precipitation

NASA Astrophysics Data System (ADS)

Nascimento, Gabriela S.; McKenzie, Judith A.; Martinez Ruiz, Francisca; Bontognali, Tomaso R. R.; Vasconcelos, Crisogono

2016-04-01

A possible syngenetic relationship between carbonate and clay mineral precipitation has been reported for sedimentary rocks deposited in both lacustrine and marine sedimentary environments throughout the geological record. In particular, the mineral dolomite is often found associated with Mg-rich clays, such as stevensite. It is notable that this carbonate/clay association has been recorded in numerous samples taken from modern dolomite precipitating environments; for example, the Coorong lakes, South Australia, coastal sabkhas, Abu Dhabi, UAE and coastal hypersaline lagoons (Lagoa Vermelha and Brejo do Espinho) east of Rio de Janeiro, Brazil. An HRTEM study of samples from these three locations indicates a possible physical/chemical association between the Ca-dolomite and Mg-rich clays, demonstrating a probable co-precipitation. To test this hypothesis, we have conducted a series of biotic and abiotic laboratory experiments. If this syngenesis actually occurs in nature, what, if any, are the biogeochemical processes controlling these precipitation reactions? Our experiments were designed to determine the extent of the biotic versus abiotic component influencing the mineral precipitation and, in the case of a biotic influence, to understand the mechanism through which microorganisms might mediate the formation of clay minerals. The experiments were carried out in the Geomicrobiology Laboratory of ETH Zürich using cultures of living microbes and artificial organic compounds that simulate functional groups present in natural biofilms formed under both aerobic and anaerobic conditions. In addition, pure inorganic experiments were designed to understand possible physico-chemical conditions for diagenetic processes that could induce dissolution of Mg-carbonates and precipitation of Mg-rich clays. Our results show a remarkable biotic influence during the formation of clay minerals. Specifically, extracellular polymeric substances (EPS), released by microbes in their surrounding environments, appear to play a key role in the mineralization process, by binding and concentrating silica and by stabilizing cations in specific co-ordination positions. This step may be essential for the initial nucleation of the clay mineral. Also, the conditions of the biotic experiments probably helped to lower kinetic barriers and promote the reactions, which apparently remained kinetically constrained in the abiotic experiments. These initial experimental results provide information to understand the syngenetic relationship between dolomite and Mg-rich clay precipitation and furnish additional information to help reconstruct paleoenviromental conditions for similar deposits found in the geological record.

The role of impact events play in redistributing and sequestering water on Early Mars

NASA Astrophysics Data System (ADS)

Osinski, G.; Tornabene, L. L.

2017-12-01

Impact cratering is one of the most fundamental geological process in the Solar System. Several workers have considered the effect that impact events may have had on the climate of Early Mars. The proposed effects range from impact-induced precipitation to the production of runaway stable climates to the impact delivery of climatically active gases. The role of impact events in forming hydrated minerals has been touched upon but remains debated. In this contribution, we focus on the role that impact events may have played in redistributing and sequestering water on Early Mars; a record that may still be preserved in the Noachian crust. It has been previously proposed that the sequestration of significant quantities of water may have occurred within various hydrated minerals, in particular clays, in the martian crust. There is undoubtedly no single origin for clay-bearing rocks on Mars and the purpose of this contribution is not to review all the possible formation mechanisms. What we do propose, however, is that it is theoretically possible for impact events to create all known occurrences of clays on Mars. We show that clays can form within and around impact craters in two main ways: through the solid-state devitrification of hydrous impact melts and/or impact-generated hydrothermal alteration. Neither of these mechanisms requires a warmer or wetter climate scenario on Early Mars. Notwithstanding the original origin of clays, any clays may be widely redistributed over the Martian surface in the ejecta deposits of large impact craters. However, ejecta deposits are much more complex than commonly thought, with evidence in many instances for two different types of ejecta deposits around martian craters. The first is a ballistic ejecta layer that is low-shock, melt-poor and low-temperature; it will likely not induce the formation of new clays through the mechanisms described above, but could redistribute pre-impact clays over 100's and 1000's of km over the martian surface. Overlying ballistic ejecta deposits is a second ejecta type that is more melt-rich and higher temperature and that has been shown (on Earth) to form new primary clays and other hydrated minerals. This potential to form clays in situ many 100's of km away from the source crater in melt-rich ejecta deposits should be considered in any study of the Noachian crust.

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.

Primordial clays on Mars formed beneath a steam or supercritical atmosphere.

PubMed

Cannon, Kevin M; Parman, Stephen W; Mustard, John F

2017-12-06

On Mars, clay minerals are widespread in terrains that date back to the Noachian period (4.1 billion to 3.7 billion years ago). It is thought that the Martian basaltic crust reacted with liquid water during this time to form hydrated clay minerals. Here we propose, however, that a substantial proportion of these clays was formed when Mars' primary crust reacted with a dense steam or supercritical atmosphere of water and carbon dioxide that was outgassed during magma ocean cooling. We present experimental evidence that shows rapid clay formation under conditions that would have been present at the base of such an atmosphere and also deeper in the porous crust. Furthermore, we explore the fate of a primordial clay-rich layer with the help of a parameterized crustal evolution model; we find that the primordial clay is locally disrupted by impacts and buried by impact-ejected material and by erupted volcanic material, but that it survives as a mostly coherent layer at depth, with limited surface exposures. These exposures are similar to those observed in remotely sensed orbital data from Mars. Our results can explain the present distribution of many clays on Mars, and the anomalously low density of the Martian crust in comparison with expectations.

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

2014-07-28

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.

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

PubMed Central

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

Smectite clays in Mars soil: evidence for their presence and role in Viking biology experimental results.

PubMed

Banin, A; Rishpon, J

1979-12-01

Various chemical, physical and geological observations indicate that smectite clays are probably the major components of the Martian soil. Satisfactory ground-based chemical simulation of the Viking biology experimental results was obtained with the smectite clays nontronite and montmorillonite when they contained iron and hydrogen as adsorbed ions. Radioactive gas was released from the medium solution used in the Viking Labeled Release (LR) experiment when interacted with the clays, at rates and quantities similar to those measured by Viking on Mars. Heating of the active clay (mixed with soluble salts) to 160 degrees C in CO2 atmosphere reduced the decomposition activity considerably, again, as was observed on Mars. The decomposition reaction in LR experiment is postulated to be iron-catalyzed formate decomposition on the clay surface. The main features of the Viking Pyrolytic Release (PR) experiment were also simulated recently (Hubbard, 1979) which the iron clays, including a relatively low '1st peak' and significant '2nd peak'. The accumulated observations on various Martian soil properties and the results of simulation experiments, thus indicate that smectite clays are major and active components of the Martian soil. It now appears that many of the results of the Viking biology experiments can be explained on the basis of their surface activity in catalysis and adsorption.

Synthesis of hectorite-TiO2 and kaolinite-TiO2 nanocomposites with photocatalytic activity for the degradation of model air pollutants

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

Destaillats, Hugo; Kibanova, D.; Trejo, M.

2008-03-01

We studied the synthesis and photocatalytic activity of small-sized TiO{sub 2} supported on hectorite and kaolinite. Deposition of TiO{sub 2} on the clay mineral surface was conducted by using a sol-gel method with titanium isopropoxide as precursor. Anatase TiO{sub 2} particles formation was achieved by hydrothermal treatment at 180 C. Material characterization was conducted using XRD, SEM, XPS, ICP-OES, BET and porosimetry analysis. Efficiency in synthesizing clay-TiO{sub 2} composites depended strongly on the clay mineral structure. Incorporation of anatase in hectorite, an expandable clay mineral, was found to be very significant (> 36 wt.% Ti) and to be followed bymore » important structural changes at the clay mineral surface. Instead, no major structural modifications of the clay were observed for kaolinite-TiO{sub 2}, as compared with the untreated material. Photocatalytic performance of clay-TiO{sub 2} composites was evaluated with ATR-FTIR following the oxidation of adsorbed toluene and d-limonene, two model air pollutants. In either case, the photocatalytic removal efficiency of these hydrophobic substrates by the synthesized clay-TiO{sub 2} composites was comparable to that observed using pure commercial TiO{sub 2} (Degussa P25).« less

Primordial clays on Mars formed beneath a steam or supercritical atmosphere

NASA Astrophysics Data System (ADS)

Cannon, Kevin M.; Parman, Stephen W.; Mustard, John F.

2017-12-01

On Mars, clay minerals are widespread in terrains that date back to the Noachian period (4.1 billion to 3.7 billion years ago). It is thought that the Martian basaltic crust reacted with liquid water during this time to form hydrated clay minerals. Here we propose, however, that a substantial proportion of these clays was formed when Mars’ primary crust reacted with a dense steam or supercritical atmosphere of water and carbon dioxide that was outgassed during magma ocean cooling. We present experimental evidence that shows rapid clay formation under conditions that would have been present at the base of such an atmosphere and also deeper in the porous crust. Furthermore, we explore the fate of a primordial clay-rich layer with the help of a parameterized crustal evolution model; we find that the primordial clay is locally disrupted by impacts and buried by impact-ejected material and by erupted volcanic material, but that it survives as a mostly coherent layer at depth, with limited surface exposures. These exposures are similar to those observed in remotely sensed orbital data from Mars. Our results can explain the present distribution of many clays on Mars, and the anomalously low density of the Martian crust in comparison with expectations.

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

PubMed

Williams, Lynda B; Haydel, Shelley E

2010-07-01

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 degrees C), then dehydroxylation (550 degrees C or more), and finally to destruction of the clay mineral structure by (~900 degrees 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.

Hydro-mechanical properties of the Red Salt Clay (T4) - Relevancy of the minimum stress criterion for barrier integrity

NASA Astrophysics Data System (ADS)

Minkley, W.; Popp, T.; Salzer, K.; Gruner, M.; Böttge, V.

The so-called Red Salt Clay (T4) is deposited as clay-rich clastic sediment at the base of the Aller-series forming a persistent lateral layer of up to 20 m thickness above the lower Zechstein-series. The clay layers may act as a protective shield in the hanging wall of gas storages or underground repositories in salt formations, thus resulting in a multi-barrier system. As a proof of its reliability comprehensive hydro-mechanical investigations were performed on clay samples recovered at different sites in Germany. Most important, rock tightness against various fluids was confirmed in the lab and field-scale. Remarkably, only if the fluid pressure equalises the acting minimal stress (i.e. violence of the “minimum stress criterion”) a significant increase of permeability is observed (“pathway dilatation”) but no macro-frac. However, the material properties from different locations showed a significant variability according to different burial depths. Thus the Red Salt Clay may act as natural analogue, representing the material variability of various indurated clays. In addition, the existing knowledge gained from practical mining activities can be used to evaluate extreme in situ loading conditions.

Correlation between thermal behavior of clays and their chemical and mineralogical composition: a review

NASA Astrophysics Data System (ADS)

Dwi Yanti, Evi; Pratiwi, I.

2018-02-01

Clay's abundance has been widely used as industrial raw materials, especially ceramic and tile industries. Utilization of these minerals needs a thermal process for producing ceramic products. Two studies conducted by Septawander et al. and Chin C et al., showed the relationship between thermal behavior of clays and their chemical and mineralogical composition. Clays are characterized by XRD analysis and thermal analysis, ranging from 1100°C to 1200°C room temperature. Specimen of raw materials of clay which is used for the thermal treatment is taken from different geological conditions and formation. In raw material, Quartz is almost present in all samples. Halloysite, montmorillonite, and feldspar are present in Tanjung Morawa raw clay. KC and MC similar kaolinite and illite are present in the samples. The research illustrates the interrelationships of clay minerals and chemical composition with their heat behavior. As the temperature of combustion increases, the sample reduces a significant weight. The minerals which have undergone a transformation phase became mullite, cristobalite or illite and quartz. Under SEM analysis, the microstructures of the samples showed irregularity in shape; changes occurred due the increase of heat.

Iridium, sulfur isotopes and rare earth elements in the Cretaceous-Tertiary boundary clay at Stevns Klint, Denmark

NASA Astrophysics Data System (ADS)

Schmitz, Birger; Andersson, Per; Dahl, Jeremy

1988-01-01

Microbial activity and redox-controlled precipitation have been of major importance in the process of metal accumulation in the strongly Ir-enriched Cretaceous-Tertiary (K-T) boundary clay, the Fish Clay, at Stevns Klint in Denmark. Two important findings support this view: 1) Kerogen, recovered by leaching the Fish Clay in HCl and HF, shows an Ir concentration of 1100 ppb; this represents about 50% of the Ir present in the bulk sample Fish Clay. Strong organometallic complexes is the most probable carrier phase for this fraction of Ir. Kerogen separated from the K-T boundary clay at Caravaca, Spain, similarly exhibits enhanced Ir concentrations. 2) Sulfur isotope analyses of metal-rich pyrite spherules, which occur in extreme abundance (about 10% by weight) in the basal Fish Clay, give a δ 34S value of -32%.. This very low value shows that sulfide formation by anaerobic bacteria was intensive in the Fish Clay during early diagenesis. Since the pyrite spherules are major carriers of elements such as Ni, Co, As, Sb and Zn, microbial activity may have played an important role for concentrating these elements. In the Fish Clay large amounts of rare earth elements have precipitated from sea water on fish scales. Analyses reveal that, compared with sea water, the Fish Clay is only about four times less enriched in sea-water derived lanthanides than in Ir. This shows that a sea-water origin is plausible for elements that are strongly enriched in the clay, but whose origin cannot be accounted for by a lithogenic precursor.

Geotechnical characterization of mined clay from Appalachian Ohio: challenges and implications for the clay mining industry.

PubMed

Moran, Anthony R; Hettiarachchi, Hiroshan

2011-07-01

Clayey soil found in coal mines in Appalachian Ohio is often sold to landfills for constructing Recompacted Soil Liners (RSL) in landfills. Since clayey soils possess low hydraulic conductivity, the suitability of mined clay for RSL in Ohio is first assessed by determining its clay content. When soil samples are tested in a laboratory, the same engineering properties are typically expected for the soils originated from the same source, provided that the testing techniques applied are standard, but mined clay from Appalachian Ohio has shown drastic differences in particle size distribution depending on the sampling and/or laboratory processing methods. Sometimes more than a 10 percent decrease in the clay content is observed in the samples collected at the stockpiles, compared to those collected through reverse circulation drilling. This discrepancy poses a challenge to geotechnical engineers who work on the prequalification process of RSL material as it can result in misleading estimates of the hydraulic conductivity of the samples. This paper describes a laboratory investigation conducted on mined clay from Appalachian Ohio to determine how and why the standard sampling and/or processing methods can affect the grain-size distributions. The variation in the clay content was determined to be due to heavy concentrations of shale fragments in the clayey soils. It was also concluded that, in order to obtain reliable grain size distributions from the samples collected at a stockpile of mined clay, the material needs to be processed using a soil grinder. Otherwise, the samples should be collected through drilling.

Geotechnical Characterization of Mined Clay from Appalachian Ohio: Challenges and Implications for the Clay Mining Industry

PubMed Central

Moran, Anthony R.; Hettiarachchi, Hiroshan

2011-01-01

Clayey soil found in coal mines in Appalachian Ohio is often sold to landfills for constructing Recompacted Soil Liners (RSL) in landfills. Since clayey soils possess low hydraulic conductivity, the suitability of mined clay for RSL in Ohio is first assessed by determining its clay content. When soil samples are tested in a laboratory, the same engineering properties are typically expected for the soils originated from the same source, provided that the testing techniques applied are standard, but mined clay from Appalachian Ohio has shown drastic differences in particle size distribution depending on the sampling and/or laboratory processing methods. Sometimes more than a 10 percent decrease in the clay content is observed in the samples collected at the stockpiles, compared to those collected through reverse circulation drilling. This discrepancy poses a challenge to geotechnical engineers who work on the prequalification process of RSL material as it can result in misleading estimates of the hydraulic conductivity of the samples. This paper describes a laboratory investigation conducted on mined clay from Appalachian Ohio to determine how and why the standard sampling and/or processing methods can affect the grain-size distributions. The variation in the clay content was determined to be due to heavy concentrations of shale fragments in the clayey soils. It was also concluded that, in order to obtain reliable grain size distributions from the samples collected at a stockpile of mined clay, the material needs to be processed using a soil grinder. Otherwise, the samples should be collected through drilling. PMID:21845150

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

Liu, H.H.; Li, L.; Zheng, L.

Clay/shale has been considered as potential host rock for geological disposal of high-level radioactive waste throughout the world, because of its low permeability, low diffusion coefficient, high retention capacity for radionuclides, and capability to self-seal fractures. For example, Callovo-Oxfordian argillites at the Bure site, France (Fouche et al., 2004), Toarcian argillites at the Tournemire site, France (Patriarche et al., 2004), Opalinus Clay at the Mont Terri site, Switzerland (Meier et al., 2000), and Boom clay at the Mol site, Belgium (Barnichon and Volckaert, 2003) have all been under intensive scientific investigation (at both field and laboratory scales) for understanding amore » variety of rock properties and their relationships to flow and transport processes associated with geological disposal of radioactive waste. Figure 1-1 presents the distribution of clay/shale formations within the USA.« less

Rigid palm oil-based polyurethane foam reinforced with diamine-modified montmorillonite nanoclay

NASA Astrophysics Data System (ADS)

Haziq Dzulkifli, Mohd; Yazid Yahya, Mohd; Majid, Rohah A.

2017-05-01

This paper presents work on organically-modified montmorillonite (MMT) nanoclay embedded in rigid palm oil-based polyurethane (PU) foam. MMT was modified with organic surfactant diamino propane (DAP). PU foam was fabricated in closed mold, and the amount of DAP-MMT was varied in each foam formulation. The obtained foam was tested for its microstructure and morphology. Appearance of peaks from infra-red spectra corresponding to N-H, C=O, and C-N confirms the formation of PU networks. Scanning electron microscopy (SEM) revealed fine, closed-cellular structure at low clay loading; increasing DAP-MMT content induced larger cell sizes with blowholes. X-ray diffraction (XRD) indicates fully-exfoliated clays at 1 wt. % and partial-exfoliation at 3 wt. % clay loading, suggesting clumping of clays as DAP-MMT content increased.

Overview of the evolution of clay mineralogy in the Gulf of Mexico: implications for regional climate and drainage history of the Mississippi and Brazos-Trinity Rivers

NASA Astrophysics Data System (ADS)

Adatte, T.; John, C. M.; Flemings, P. B.; Behrmann, J.

2005-12-01

In this paper we present the overview and preliminary results of the analysis of clay minerals in two mini basins drilled during IODP Expedition 308. The goal of our project is to explore the vertical and temporal trends in clay mineralogy in the Ursa Basin and the Brazos-Trinity basin #4. The Brazos-Trinity basin was the sink for sands and clays carried by the Brazos and Trinity Rivers, while the Ursa basin was the sink for sediments carried by the Mississippi river. Reconstructing clay minerals (phyllosilicates <2μm in size) accumulations at these locations could thus potentially yield information on changes in the transport and the source of the siliclastic material transported in the course of the Pleistocene by these three rivers. Moreover, because the type of clay formed in soils through weathering processes largely depend on temperature and amount of precipitation, the dataset generated could provide clues on past climate changes. Some of the mechanisms that are hypothesized to play a major role in controlling clay accumulation in the basins investigated are reworking of clays on the American continent (controlled at the time-scale investigated here by changes in precipitation) and turbidity current deposition (controlled mainly by sea-level changes and thus glacio-eustasy). Finally, a major focusing point of Expedition 308 was sediment physical properties in an overpressured basin. Because each clay mineral specie has a specific average grain sizes, physical properties and cation exchange capacity, the clay mineral composition of the sediment investigated here (dominated by clay-sized particles) may partly control how these sediments react to changes in pressure and temperature. Thus, clay mineral data could contribute to our understanding of the physical properties of the sediments in overpressured basins, and collaborations with geotechnical scientist are planned.

Stochastic Approach to Determine CO2 Hydrate Induction Time in Clay Mineral Suspensions

NASA Astrophysics Data System (ADS)

Lee, K.; Lee, S.; Lee, W.

2008-12-01

A large number of induction time data for carbon dioxide hydrate formation were obtained from a batch reactor consisting of four independent reaction cells. Using resistance temperature detector(RTD)s and a digital microscope, we successfully monitored the whole process of hydrate formation (i.e., nucleation and crystal growth) and detected the induction time. The experiments were carried out in kaolinite and montmorillonite suspensions at temperatures between 274 and 277 K and pressures ranging from 3.0 to 4.0 MPa. Each set of data was analyzed beforehand whether to be treated by stochastic manner or not. Geochemical factors potentially influencing the hydrate induction time under different experimental conditions were investigated by stochastic analyses. We observed that clay mineral type, pressure, and temperature significantly affect the stochastic behavior of the induction times for CO2 hydrate formation in this study. The hydrate formation kinetics along with stochastic analyses can provide basic understanding for CO2 hydrate storage in deep-sea sediment and geologic formation, securing its stability under the environments.

Acyl silicates and acyl aluminates as activated intermediates in peptide formation on clays

NASA Technical Reports Server (NTRS)

White, D. H.; Kennedy, R. M.; Macklin, J.

1984-01-01

Glycine reacts with heating on dried clays and other minerals to give peptides in much better yield than in the absence of mineral. This reaction was proposed to occur by way of an activated intermediate such as an acyl silicate or acyl aluminate analogous to acyl phosphates involved in several biochemical reactions including peptide bond synthesis. The proposed mechanism has been confirmed by trapping the intermediate, as well as by direct spectroscopic observation of a related intermediate. The reaction of amino acids on periodically dried mineral surfaces represents a widespead, geologically realistic setting for prebiotic peptide formation via in situ activation.

Influence of miscibility phenomenon on crystalline polymorph transition in poly(vinylidene fluoride)/acrylic rubber/clay nanocomposite hybrid.

PubMed

Abolhasani, Mohammad Mahdi; Naebe, Minoo; Jalali-Arani, Azam; Guo, Qipeng

2014-01-01

In this paper, intercalation of nanoclay in the miscible polymer blend of poly(vinylidene fluoride) (PVDF) and acrylic rubber(ACM) was studied. X-ray diffraction was used to investigate the formation of nanoscale polymer blend/clay hybrid. Infrared spectroscopy and X-ray analysis revealed the coexistence of β and γ crystalline forms in PVDF/Clay nanocomposite while α crystalline form was found to be dominant in PVDF/ACM/Clay miscible hybrids. Flory-Huggins interaction parameter (B) was used to further explain the miscibility phenomenon observed. The B parameter was determined by combining the melting point depression and the binary interaction model. The estimated B values for the ternary PVDF/ACM/Clay and PVDF/ACM pairs were all negative, showing both proper intercalation of the polymer melt into the nanoclay galleries and the good miscibility of PVDF and ACM blend. The B value for the PVDF/ACM blend was almost the same as that measured for the PVDF/ACM/Clay hybrid, suggesting that PVDF chains in nanocomposite hybrids interact with ACM chains and that nanoclay in hybrid systems is wrapped by ACM molecules.

Polyethylene organo-clay nanocomposites: the role of the interface chemistry on the extent of clay intercalation/exfoliation.

PubMed

Mainil, Michaël; Alexandre, Michaël; Monteverde, Fabien; Dubois, Philippe

2006-02-01

High density polyethylene (HDPE)/clay nanocomposites have been prepared using three different functionalized polyethylene compatibilizers: an ethylene/vinyl acetate copolymer, a polyethylene grafted with maleic anhydride functions and a (styrene-b-ethylene/butylene-b-styrene) block copolymer. The nanocomposites were prepared via two different routes: (1) the dispersion in HDPE of a masterbatch prepared from the compatibilizer and the clay or (2) the direct melt blending of the three components. For each compatibilizer, essentially intercalated nanocomposites were formed as determined by X-ray diffraction and transmission electron microscopy. With the ethylene/vinyl acetate copolymer, a significant delamination of the intercalated clay in thin stacks was observed. This dispersion of thin intercalated stacks within the polymer matrix allowed increasing significantly the stiffness and the flame resistance of the nanocomposite. A positive effect of shear rate and blending time has also been put into evidence, especially for the process based on the masterbatch preparation, improving both the formation of thin stacks of intercalated clay and the mechanical properties and the flame resistance of the formed nanocomposites.

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

Technical Report for Proposed Ordnance Clearance at Fort George G. Meade

DTIC Science & Technology

1991-03-01

Potomac Group (including the Patapsco, Arundel Clay, and Patuxent Formations), the Magothy Formation and the Patuxent River terraces and associated...alluvium. The youngest geologic unit in theI stratigraphic sequence underlying Fort Meade is the Magothy Formation of Late Cretaceous age. This formation...Department of the Army, 1981). The Magothy Formation unconformably overlies the sediments of the Lower Cretaceous Potomac Group. i The formations of the

Geothermal alteration of basaltic core from the Snake River Plain, Idaho

NASA Astrophysics Data System (ADS)

Sant, Christopher J.

The Snake River Plain is located in the southern part of the state of Idaho. The eastern plain, on which this study focuses, is a trail of volcanics from the Yellowstone hotspot. Three exploratory geothermal wells were drilled on the Snake River Plain. This project analyzes basaltic core from the first well at Kimama, north of Burley, Idaho. The objectives of this project are to establish zones of geothermal alteration and analyze the potential for geothermal power production using sub-aquifer resources on the axial volcanic zone of the Snake River Plain. Thirty samples from 1,912 m of core were sampled and analyzed for clay content and composition using X-ray diffraction. Observations from core samples and geophysical logs are also used to establish alteration zones. Mineralogical data, geophysical log data and physical characteristics of the core suggest that the base of the Snake River Plain aquifer at the axial zone is located 960 m below the surface, much deeper than previously suspected. Swelling smectite clay clogs pore spaces and reduces porosity and permeability to create a natural base to the aquifer. Increased temperatures favor the formation of smectite clay and other secondary minerals to the bottom of the hole. Below 960 m the core shows signs of alteration including color change, formation of clay, and filling of other secondary minerals in vesicles and fractured zones of the core. The smectite clay observed is Fe-rich clay that is authigenic in some places. Geothermal power generation may be feasible using a low temperature hot water geothermal system if thermal fluids can be attained near the bottom of the Kimama well.

FT-IR study of CO 2 interaction with Na-rich montmorillonite

DOE PAGES

Krukowski, Elizabeth G.; Goodman, Angela; Rother, Gernot; ...

2015-05-27

Here, carbon capture, utilization and storage (CCUS) in saline reservoirs in sedimentary formations has the potential to reduce the impact of fossil fuel combustion on climate change by reducing CO 2 emissions to the atmosphere and storing the CO 2 in geologic formations in perpetuity. At pressure and temperature (PT) conditions relevant to CCUS, CO 2 is less dense than the pre-existing brine in the formation, and the more buoyant CO 2 will migrate to the top of the formation where it will be in contact with cap rock. Interactions between clay-rich shale cap rocks and CO 2 are poorlymore » understood at PT conditions appropriate for CCUS in saline formations. In this study, the interaction of CO 2 with clay minerals in the cap rock overlying a saline formation has been examined using Na + exchanged montmorillonite (Mt) (Na +-STx-1) (Na + Mt) as an analog for clay-rich shale. Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR) was used to discern mechanistic information for CO 2 interaction with hydrated (both one- and two-water layers) and relatively dehydrated (both dehydrated layers and one-water layers) Na+-STx-1 at 35 °C and 50 C and CO 2 pressure from 0 5.9 MPa. CO 2-induced perturbations associated with the water layer and Na+-STx-1 vibrational modes such as AlAlOH and AlMgOH were examined. Data indicate that CO 2 is preferentially incorporated into the interlayer space, with relatively dehydrated Na +-STx-1 capable of incorporating more CO 2 compared to hydrated Na +-STx-1. Spectroscopic data provide no evidence of formation of carbonate minerals or the interaction of CO 2 with sodium cations in the Na +-STx-1 structure.« less

Role of Organic Acids in Bioformation of Kaolinite: Results of Laboratory Experiments

NASA Astrophysics Data System (ADS)

Bontognali, T. R. R.; Vasconcelos, C.; McKenzie, J. A.

2012-04-01

Clay minerals and other solid silica phases have a broad distribution in the geological record and greatly affect fundamental physicochemical properties of sedimentary rocks, including porosity. An increasing number of studies suggests that microbial activity and microbially produced organic acids might play an important role in authigenic clay mineral formation, at low temperatures and under neutral pH conditions. In particular, early laboratory experiments (Linares and Huertas, 1971) reported the precipitation of kaolinite in solutions of SiO2 and Al2O3 with different molar ratios SiO2/Al2O3, together with fulvic acid (a non-characterized mixture of many different acids containing carboxyl and phenolate groups) that was extracted from peat soil. Despite many attempts, these experiments could not be reproduced until recently. Fiore et al. (2011) hypothesized that the non-sterile fulvic acid might have contained microbes that participated in the formation of kaolinite. Using solutions saturated with Si and Al and containing oxalate and/or mixed microbial culture extracted from peat-moss soil, they performed incubation experiments, which produced kaolinite exclusively in solutions containing oxalate and microbes. We proposed to test the role of specific organic acids for kaolinite formation, conducting laboratory experiments at 25˚C, with solutions of sodium silicate, aluminum chloride and various organic compounds (i.e. EDTA, citric acid, succinic acid and oxalic acid). Specific organic acids may stabilize aluminum in octahedral coordination positions, which is crucial for the initial nucleation step. In our experiments, a poorly crystalline mineral that is possibly a kaolinite precursor formed exclusively in the presence of succinic acid. In experiments with other organic compounds, no incorporation of Al was observed, and amorphous silica was the only precipitated phase. In natural environments, succinic acid is produced by a large variety of microbes as an intermediate product of the tricarboxylic acid cycle. Our results demonstrate, for the first time, that the formation of a specific clay mineral (proto-kaolinite) occurs in the presence of a specific organic compound (succinic acid). This implies that microbial species capable of excreting succinate among their EPS may promote authigenic kaolinite formation at low temperature and neutral pH. This biological degradation process might play a crucial role for the formation of authigenic kaolinite, which is a widespread clay mineral in sedimentary environments. Fiore, S., Dumontet, S., Huertas, F.J., and Pasquale, V., 2011. Bacteria-induced crystallization of kaolinite. Applied Clay Science, 53:566-571. Linares, J., and Huertas, F., 1971. Kaolinite: Synthesis at room temperature. Science 171: 896-897.

Neoformation of clay in lateral root catchments of mallee eucalypts: a chemical perspective

PubMed Central

Verboom, William H.; Pate, John S.; Aspandiar, Mehrooz

2010-01-01

Background and Aims A previous paper (Annals of Botany 103: 673–685) described formation of clayey pavements in lateral root catchments of eucalypts colonizing a recently formed sand dune in south-west Western Australia. Here chemical and morphological aspects of their formation at the site are studied. Methods Chemical and physical examinations of soil cores through pavements and sand under adjacent heath assessed build-up of salts, clay and pH changes in or below pavements. Relationships of root morphology to clay deposition were examined and deposits subjected to scanning electron microscopy and energy-dispersive X-ray analysis. Xylem transport of mineral elements in eucalypt and non-eucalypt species was studied by analysis of xylem (tracheal) sap from lateral roots. Key Results The columns of which pavements are composed develop exclusively on lower-tier lateral roots. Such sites show intimate associations of fine roots, fungal filaments, microbiota and clay deposits rich in Si, Al and Fe. Time scales for construction of pavements by eucalypts were assessed. Cores through columns of pavemented profiles showed gross elevations of bulk density, Al, Fe and Si in columns and related increases in pH, Mg and Ca status in lower profiles. A cutting through the dune exhibited pronounced alkalinity (pH 7–10) under mallee woodland versus acidity (pH 5–6·5) under proteaceous heath. Xylem sap analyses showed unusually high concentrations of Al, Fe, Mg and Si in dry-season samples from column-bearing roots. Conclusions Deposition of Al–Fe–Si-rich clay is pivotal to pavement construction by eucalypts and leads to profound chemical and physical changes in relevant soil profiles. Microbial associates of roots are likely to be involved in clay genesis, with parent eucalypts supplying the required key mineral elements and carbon sources. Acquisition of the Al and Fe incorporated into clay derives principally from hydraulic uplift from ground water via deeply penetrating tap roots. PMID:19897459

Montmorillonite protection of an UV-irradiated hairpin ribozyme: evolution of the RNA world in a mineral environment

PubMed Central

Biondi, Elisa; Branciamore, Sergio; Maurel, Marie-Christine; Gallori, Enzo

2007-01-01

Background The hypothesis of an RNA-based origin of life, known as the "RNA world", is strongly affected by the hostile environmental conditions probably present in the early Earth. In particular, strong UV and X-ray radiations could have been a major obstacle to the formation and evolution of the first biomolecules. In 1951, J. D. Bernal first proposed that clay minerals could have served as the sites of accumulation and protection from degradation of the first biopolymers, providing the right physical setting for the evolution of more complex systems. Numerous subsequent experimental studies have reinforced this hypothesis. Results The ability of the possibly widespread prebiotic, clay mineral montmorillonite to protect the catalytic RNA molecule ADHR1 (Adenine Dependent Hairpin Ribozyme 1) from UV-induced damages was experimentally checked. In particular, the self-cleavage reaction of the ribozyme was evaluated after UV-irradiation of the molecule in the absence or presence of clay particles. Results obtained showed a three-fold retention of the self-cleavage activity of the montmorillonite-protected molecule, with respect to the same reaction performed by the ribozyme irradiated in the absence of the clay. Conclusion These results provide a suggestion with which RNA, or RNA-like molecules, could have overcame the problem of protection from UV irradiation in the RNA world era, and suggest that a clay-rich environment could have favoured not only the formation of first genetic molecules, but also their evolution towards increasingly complex molecular organization. PMID:17767730

Quantifying structural states of soft mudrocks

NASA Astrophysics Data System (ADS)

Li, B.; Wong, R. C. K.

2016-05-01

In this paper, a cm model is proposed to quantify structural states of soft mudrocks, which are dependent on clay fractions and porosities. Physical properties of natural and reconstituted soft mudrock samples are used to derive two parameters in the cm model. With the cm model, a simplified homogenization approach is proposed to estimate geomechanical properties and fabric orientation distributions of soft mudrocks based on the mixture theory. Soft mudrocks are treated as a mixture of nonclay minerals and clay-water composites. Nonclay minerals have a high stiffness and serve as a structural framework of mudrocks when they have a high volume fraction. Clay-water composites occupy the void space among nonclay minerals and serve as an in-fill matrix. With the increase of volume fraction of clay-water composites, there is a transition in the structural state from the state of framework supported to the state of matrix supported. The decreases in shear strength and pore size as well as increases in compressibility and anisotropy in fabric are quantitatively related to such transition. The new homogenization approach based on the proposed cm model yields better performance evaluation than common effective medium modeling approaches because the interactions among nonclay minerals and clay-water composites are considered. With wireline logging data, the cm model is applied to quantify the structural states of Colorado shale formations at different depths in the Cold Lake area, Alberta, Canada. Key geomechancial parameters are estimated based on the proposed homogenization approach and the critical intervals with low strength shale formations are identified.

Quality evaluation of processed clay soil samples.

PubMed

Steiner-Asiedu, Matilda; Harrison, Obed Akwaa; Vuvor, Frederick; Tano-Debrah, Kwaku

2016-01-01

This study assessed the microbial quality of clay samples sold on two of the major Ghanaian markets. The study was a cross-sectional assessing the evaluation of processed clay and effects it has on the nutrition of the consumers in the political capital town of Ghana. The items for the examination was processed clay soil samples. Staphylococcus spp and fecal coliforms including Klebsiella, Escherichia, and Shigella and Enterobacterspp were isolated from the clay samples. Samples from the Kaneshie market in Accra recorded the highest total viable counts 6.5 Log cfu/g and Staphylococcal count 5.8 Log cfu/g. For fecal coliforms, Madina market samples had the highest count 6.5 Log cfu/g and also recorded the highest levels of yeast and mould. For Koforidua, total viable count was highest in the samples from the Zongo market 6.3 Log cfu/g. Central market samples had the highest count of fecal coliforms 4.6 Log cfu/g and yeasts and moulds 6.5 Log cfu/g. "Small" market recorded the highest staphylococcal count 6.2 Log cfu/g. The water activity of the clay samples were low, and ranged between 0.65±0.01 and 0.66±0.00 for samples collected from Koforidua and Accra respectively. The clay samples were found to contain Klebsiella spp. Escherichia, Enterobacter, Shigella spp. staphylococcus spp., yeast and mould. These have health implications when consumed.

Geological modeling of a fault zone in clay rocks at the Mont-Terri laboratory (Switzerland)

NASA Astrophysics Data System (ADS)

Kakurina, M.; Guglielmi, Y.; Nussbaum, C.; Valley, B.

2016-12-01

Clay-rich formations are considered to be a natural barrier for radionuclides or fluids (water, hydrocarbons, CO2) migration. However, little is known about the architecture of faults affecting clay formations because of their quick alteration at the Earth's surface. The Mont Terri Underground Research Laboratory provides exceptional conditions to investigate an un-weathered, perfectly exposed clay fault zone architecture and to conduct fault activation experiments that allow explore the conditions for stability of such clay faults. Here we show first results from a detailed geological model of the Mont Terri Main Fault architecture, using GoCad software, a detailed structural analysis of 6 fully cored and logged 30-to-50m long and 3-to-15m spaced boreholes crossing the fault zone. These high-definition geological data were acquired within the Fault Slip (FS) experiment project that consisted in fluid injections in different intervals within the fault using the SIMFIP probe to explore the conditions for the fault mechanical and seismic stability. The Mont Terri Main Fault "core" consists of a thrust zone about 0.8 to 3m wide that is bounded by two major fault planes. Between these planes, there is an assembly of distinct slickensided surfaces and various facies including scaly clays, fault gouge and fractured zones. Scaly clay including S-C bands and microfolds occurs in larger zones at top and bottom of the Mail Fault. A cm-thin layer of gouge, that is known to accommodate high strain parts, runs along the upper fault zone boundary. The non-scaly part mainly consists of undeformed rock block, bounded by slickensides. Such a complexity as well as the continuity of the two major surfaces are hard to correlate between the different boreholes even with the high density of geological data within the relatively small volume of the experiment. This may show that a poor strain localization occurred during faulting giving some perspectives about the potential for reactivation and leakage of faults affecting clay materials.

Hydrogeologic investigations of the Miocene Nogales Formation in the Nogales Area, Upper Santa Cruz Basin, Arizona

USGS Publications Warehouse

Page, William R.; Gray, Floyd; Bultman, Mark W.; Menges, Christopher M.

2016-07-28

Hydrogeologic investigations were conducted to evaluate the groundwater resource potential for the Miocene Nogales Formation in the Nogales area, southern Arizona. Results indicate that parts of the formation may provide new, deeper sources of groundwater for the area. Geologic mapping determined the hydrogeologic framework of the formation by defining lithologic, mineralogic, and stratigraphic characteristics; identifying potential aquifers and confining units; and mapping faults and fractures which likely influence groundwater flow. Geophysical modeling was used to determine the basin geometry and thickness of the Nogales Formation and younger alluvial aquifers and to identify target areas (deep subbasins) which may prove to be productive aquifers.Volcaniclastic sandstone samples from the formation were analyzed for porosity, bulk density, saturated hydraulic conductivity, and fabric. Effective porosity ranges from 16 to 42 percent, bulk density from 1.6 to 2.47 grams per cubic centimeter, and saturated hydraulic conductivity (SHC) from 4 to 57 centimeters per day (4.9×10-5 to 6.7×10-4 centimeters per second). Thin sections show that sandstone framework grains consist of quartz, feldspar, biotite, hornblende, pumice, volcanic glass, and opaque minerals. The matrix in most samples consists of pumice fragments, and some contain predominantly silt and clay. Samples with a mostly silt and clay matrix have lower porosity and SHC compared to samples with mostly pumice, which have higher and wider ranges of porosity and SHC. Pore space in the Nogales Formation sediments includes moldic, intercrystalline, and fracture porosity. Some intercrystalline pore space is partially filled with calcite cement. About one third of the samples contain fractures, which correspond to fractures noted in outcrops in all members of the formation.Scanning electron microscope (SEM) and x-ray diffraction (XRD) analyses indicate that most of the samples contained the zeolite clinoptilolite and mixed-layer clay. X-ray diffraction analyses verified clinoptilolite as the only zeolite in Nogales Formation samples; they also verified the presence of smectite and illite clay and some kaolinite. Samples which contain greater amounts of clinoptilolite and lesser amounts of smectite have high porosity and SHC in narrow ranges. However, samples with abundant smectite and lesser amounts of clinoptilolite span the entire ranges of porosity and SHC for the formation.All members of the Nogales Formation are fractured and faulted as a result of Tertiary Basin and Range extensional deformation, which was broadly contemporaneous with deposition of the formation. These structures may have significant influence on groundwater flow in the upper Santa Cruz basin because, although many of the sediments in the formation have characteristics indicating they may be productive aquifers based only on porous-media flow, fracturing in these sediments may further enhance permeability and groundwater flow in these basin-fill aquifers by orders of magnitude.

Eogenetic siderite as an indicator for fluctuations in sedimentation rate in the Oligocene Boom Clay Formation (Belgium)

NASA Astrophysics Data System (ADS)

Laenen, B.; De Craen, M.

2004-01-01

Horizons with septarian concretions are a salient feature of the marine Boom Clay Formation. At most horizons, the concretions consist of ferroan calcite with variable amounts of pyrite, but at stratigraphic level S60 they also contain siderite. S60 is situated at the centre of an intensely bioturbated zone that is underlain by a pyrite-rich layer. Furthermore, the enclosing clay is strongly enriched in iron, manganese and phosphorous. The sedimentological and chemical zoning is indicative for low sedimentation rates, which allowed the concentration of iron in the aerobic zone of the sediment. Concentration of iron was the prerequisite for the formation of the siderite-containing concretions. The co-precipitation with pyrite is an argument for a formation in the sulphate reduction zone, and is indicative for a high rate of iron-reduction. The latter was due to the rapid burial of the iron-enriched layer below the redox boundary. The abrupt fluctuations in sedimentation rate were a response to the maximum flooding event of the second Rupelian third-order relative sea-level cycle, which caused a brief pushback of the detrital sediment wedge to its source areas. As this response is logically explained by the general sequence stratigraphic model [Spec. Publ.-Soc. Econ. Paleontol. Mineral. 42 (1988) 109], early diagenetic siderite may be widespread at maximum flooding surfaces in rapidly prograding marine mudstones.

Formation and Stabilization of Environmentally Persistent Free Radicals Induced by the Interaction of Anthracene with Fe(III)-Modified Clays.

PubMed

Jia, Hanzhong; Nulaji, Gulimire; Gao, Hongwei; Wang, Fu; Zhu, Yunqing; Wang, Chuanyi

2016-06-21

Environmentally persistent free radicals (EPFRs) are occasionally detected in Superfund sites but the formation of EPFRs induced by polycyclic aromatic hydrocarbons (PAHs) is not well understood. In the present work, the formation of EPFRs on anthracene-contaminated clay minerals was quantitatively monitored via electron paramagnetic resonance (EPR) spectroscopy, and surface/interface-related environmental influential factors were systematically explored. The obtained results suggest that EPFRs are more readily formed on anthracene-contaminated Fe(III)-montmorillonite than in other tested systems. Depending on the reaction condition, more than one type of organic radicals including anthracene-based radical cations with g-factors of 2.0028-2.0030 and oxygenic carbon-centered radicals featured by g-factors of 2.0032-2.0038 were identified. The formed EPFRs are stabilized by their interaction with interlayer surfaces, and such surface-bound EPFRs exhibit slow decay with 1/e-lifetime of 38.46 days. Transformation pathway and possible mechanism are proposed on the basis of experimental results and quantum mechanical simulations. Overall, the formation of EPFRs involves single-electron-transfer from anthracene to Fe(III) initially, followed by H2O addition on formed aromatic radical cation. Because of their potential exposure in soil and atmosphere, such clay surface-associated EPFRs might induce more serious toxicity than PAHs and exerts significant impacts on human health.

Shear Strength of Remoulding Clay Samples Using Different Methods of Moulding

NASA Astrophysics Data System (ADS)

Norhaliza, W.; Ismail, B.; Azhar, A. T. S.; Nurul, N. J.

2016-07-01

Shear strength for clay soil was required to determine the soil stability. Clay was known as a soil with complex natural formations and very difficult to obtain undisturbed samples at the site. The aim of this paper was to determine the unconfined shear strength of remoulded clay on different methods in moulding samples which were proctor compaction, hand operated soil compacter and miniature mould methods. All the samples were remoulded with the same optimum moisture content (OMC) and density that were 18% and 1880 kg/m3 respectively. The unconfined shear strength results of remoulding clay soils for proctor compaction method was 289.56kPa with the strain 4.8%, hand operated method was 261.66kPa with the strain 4.4% and miniature mould method was 247.52kPa with the strain 3.9%. Based on the proctor compaction method, the reduction percentage of unconfined shear strength of remoulded clay soil of hand operated method was 9.66%, and for miniature mould method was 14.52%. Thus, because there was no significant difference of reduction percentage of unconfined shear strength between three different methods, so it can be concluded that remoulding clay by hand operated method and miniature mould method were accepted and suggested to perform remoulding clay samples by other future researcher. However for comparison, the hand operated method was more suitable to form remoulded clay sample in term of easiness, saving time and less energy for unconfined shear strength determination purposes.

Oil biodegradation: Interactions of artificial marine snow, clay particles, oil and Corexit.

PubMed

Rahsepar, Shokouh; Langenhoff, Alette A M; Smit, Martijn P J; van Eenennaam, Justine S; Murk, Albertinka J; Rijnaarts, Huub H M

2017-12-15

During the Deepwater Horizon (DwH) oil spill, interactions between oil, clay particles and marine snow lead to the formation of aggregates. Interactions between these components play an important, but yet not well understood, role in biodegradation of oil in the ocean water. The aim of this study is to explore the effect of these interactions on biodegradation of oil in the water. Laboratory experiments were performed, analyzing respiration and n-alkane and BTEX biodegradation in multiple conditions containing Corexit, alginate particles as marine snow, and kaolin clay. Two oil degrading bacterial pure cultures were added, Pseudomonas putida F1 and Rhodococcus qingshengii TUHH-12. Results show that the presence of alginate particles enhances oil biodegradation. The presence of Corexit alone or in combination with alginate particles and/or kaolin clay, hampers oil biodegradation. Kaolin clay and Corexit have a synergistic effect in increasing BTEX concentrations in the water and cause delay in oil biodegradation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Early Pottery Making in Northern Coastal Peru. Part I: Mössbauer Study of Clays

NASA Astrophysics Data System (ADS)

Shimada, I.; Häusler, W.; Hutzelmann, T.; Wagner, U.

2003-09-01

We report on an investigation of several ancient clays which were used for pottery making in northern coastal Peru at a kiln site from the Formative period (ca. 2000-800 BC) in the Poma Canal and at a Middle Sicán pottery workshop in use between ca. AD 950 and 1050 at Huaca Sialupe in the lower La Leche valley. Neutron activation analysis, 57Fe Mössbauer spectroscopy and X-ray diffraction were used for the characterisation of the clays. The changes that occur in iron-bearing compounds in the clays depending on the kiln atmosphere and on the maximum firing temperature were studied by Mössbauer spectroscopy and X-ray diffraction. Laboratory firing series under varying controlled conditions were performed to obtain a basic understanding of the different reactions taking place in the clays during firing. The results can be used as models in the interpretation of the Mössbauer spectra observed in ancient ceramics from the same context.

Origin and evolution of phyllosilicate deformation bands in the poorly lithified sandstones of the Rio do Peixe Basin, NE Brazil

NASA Astrophysics Data System (ADS)

Nogueira, Francisco; Nicchio, Matheus; Balsamo, Fabrizio; Bezerra, Francisco; Souza, Jorge; Carvalho, Bruno; Storti, Fabrizio

2017-04-01

In this work we describe the genetic processes and the microstructural evolution of phylossilicate deformation bands developed in poorly lithified, high porosity sandstones of the Rio do Peixe Basin, Northeast Brazil. The studied deformation bands occur in damage zones of NE-SW and NW-SE transtensional faults that exhibit well developed anastomosed clusters, with a thickness varying from tens of centimeters to 1 meter. The Host rocks are arkosic to lithic arkosic coarse sandstones to fine conglomerate and with less than 1% of clay content in the matrix. Based on (i) field observations, (ii) clay amount in deformation band cores and (iii) clay mineral arrangements in deformation bands cores, we identified two types of phyllosilicate deformation bands: (1) clay smearing deformation bands and (2) phyllosilicate deformation bands formed by clay authigenesis. The former occur only in fault zones that cut across clay-rich layers and are characterized by 45-50% of clay content. Single element chemical analysis indicates that the composition of clay minerals in clay smearing deformation bands is similar to that of clay-rich layers in the host rocks. The dominant deformation mechanism is particulate flow, which produces preferential alignments of grains and clay minerals. Only subordinate cataclasis occurs. Based on microstructural fabrics, three evolutionary stages can be identified for phyllosilicate deformation bands formed by clay authigenesis. The first one is characterized by preferentially cataclasis and weathering of feldspars. Clay concentration is relatively low, reaching 15-20%, with preferential concentration where crushed feldspar abundance is higher. The second stage is characterized by clay migration within deformation bands, to form continuous films with more than 20-25% of clay concentration. In the last stage clay mineral fabric re-organization occurs, forming well a developed S-C foliation. Clay concentration exceeds 35%. Single element chemical analysis indicates that the only external element present in phyllosilicate deformation bands formed by clay authigenesis is iron oxide. This feature suggests formation at very shallow depth, in the vadose zone where fluid flow preferentially occurs by capillarity in deformation band cores. Petrophysical analysis shows that both types of phyllosilicate deformation bands have high sealing potential. Clay smearing deformation bands reduce rock permeability by three orders of magnitude whereas phyllosilicate deformation bands formed by authigenesis causes permeability reduction of about two orders of magnitude with respect to the corresponding host rock.

2,3,7,8-DIBENZO-P-DIOXINS IN MINED CLAY PRODUCTS ...

EPA Pesticide Factsheets

Ball clay was the source of dioxin contamination discovered in selected chickens analyzed as part of a joint U.S. Department of Agriculture/U.S. Environmental Protection Agency national survey of the U.S. poultry supply conducted in 1997. The affected animals, which had been raised in the southern United States, represented approximately 5% of the national poultry production . All of these chickens and other animal food sources (i.e., farm-raised catfish), similarly contaminated, were fed a diet of animal feed containing ball clay as an anti-caking additive. The clay was mined in northwestern Mississippi within a geological formation referred to as the Mississippi Embayment. Individual raw and processed ball clay samples were analyzed for the presence of the 2,3,7,8-PCDDs/PCDFs. The average toxic equivalents (TEQs) for the raw and processed samples were 1513 and 996 ppt dry weight, respectively. Other mined clay-based products used in animal feeds revealed lower TEQs. All of the products exhibited either an absence of detectable concentrations of 2,3,7,8-PCDFs or concentrations 2-3 orders of magnitude lower than the PCDDs. The isomer distribution, specific isomer identification, and congener profile of the PCDDs in the clay were established and compared to known sources of dioxin contamination. Several unique features of this isomer distribution are characteristic of the clays and are distinguishable from those other known sources. These characteristic

The formation of technic soil in a revegetated uranium ore waste rock pile (Limousin, France)

NASA Astrophysics Data System (ADS)

Boekhout, Flora; Gérard, Martine; Kanzari, Aisha; Calas, Georges; Descostes, Michael

2014-05-01

Mining took place in France between 1945 and 2001 during which time ~210 different sites were exploited and/or explored. A total of 76 Kt of uranium was produced, 52 Mt of ore was extracted, but also 200 Mt of waste rocks was produced, the majority of which, with uranium levels corresponding to the natural environment. So far, the processes of arenisation and technic soil formation in waste rock piles are not well understood but have important implications for understanding the environmental impact and long-term speciation of uranium. Understanding weathering processes in waste rock piles is essential to determine their environmental impact. The main objectives of this work are to assess 1) the micromorphological features and neo-formed U-bearing phases related to weathering and 2) the processes behind arenisation of the rock pile. The site that was chosen is the Vieilles Sagnes waste rock pile in Fanay (Massif Central France) that represents more or less hydrothermally altered granitic rocks that have been exposed to weathering since the construction of the waste rock pile approximately 50 years ago. Two trenches were excavated to investigate the vertical differentiation of the rock pile. This site serves as a key location for studying weathering processes of waste rock piles, as it has not been reworked after initial construction and has therefore preserved information on the original mineralogy of the waste rock pile enabling us to access post emplacement weathering processes. The site is currently overgrown by moss, meter high ferns and small trees. At present day the rock pile material can be described as hydrothermally altered rocks and rock fragments within a fine-grained silty clay matrix exposed to surface conditions and weathering. A sandy "paleo" technic soil underlies the waste rock pile and functions as a natural liner by adsorption of uranium on clay minerals. Post-mining weathering of rock-pile material is superimposed on pre-mining hydrothermal and possible supergene alteration. Clay minerals present are kaolinite, smectite and chlorite. The formation of these minerals is however ambiguous, and can form during both hydrothermal as weathering processes, calling for a detailed micromorphological study. Micromorphological investigations on undisturbed samples by microscopic and ultramicroscopic techniques allow us to interpretate the processes behind the formation of technic soil in the matrix of the waste rock pile, as well as the rate and chronology of mineral formation and arenisation related to weathering (formation of protosoil and saprolitisation). By studying the formation of weathering aureaoles in between the different granitic blocks, we quantify the anthropogenic influence on weathering of this rock pile and their impacts on local ecosystem by comparing our site with natural occuring outcrops of granites currently subjected to weathering. Electron microscope imaging and microgeochemical mapping permits us to make detailed micromorphological observations linking nanoscale processes to petrolographical macroscopic features and field observations. Different petrographic and electronic images of the mineral paragenesis in the micromass associated to their microgeochemical characteristics will be presented. Also, the impact of previous hydrothermal alteration will be highlighted.

Origins of saline fluids at convergent margins

NASA Astrophysics Data System (ADS)

Martin, Jonathan B.; Kastner, Miriam; Egeberg, Per Kr.

The compositions of pore and venting fluids at convergent margins differ from seawater values, reflecting mixing and diagenesis. Most significantly, the concentration of Cl-, assumed to be a conservative ion, differs from its seawater value. Chloride concentrations could be elevated by four processes, although two, the formation of gas hydrate and ion filtration by clay membranes, are insignificant in forming saline fluids at convergent margins. During the formation of gas hydrate, the resulting Cl--rich fluids, estimated to contain an average excess of ˜140 mM Cl- over seawater value, probably would be flushed from the sediment when the pore fluids vent to seawater. Ion filtration by clay membranes requires compaction pressures typical of >2 km burial depths. Even at these depths, the efficiency of ion filtration will be negligible because (1) fluids will flow through fractures, thereby bypassing clay membranes, (2) concentrations of clay minerals are diluted by other phases, and (3) during burial, smectite converts to illite, which has little capacity for ion filtration. A third process, mixing with subaerially evaporated seawater, elevates Cl- concentrations to 1043 mM in forearc basins along the Peru margin. Evaporation of seawater, however, will be important only in limited geographic regions that are characterized by enclosed basins, arid climates, and permeable sediments. At the New Hebrides and Izu-Bonin margins, Cl- concentrations are elevated to a maximum of 1241 mM. The process responsible for this increase is the alteration of volcanic ash to hydrous clay and zeolite minerals. Mass balance calculations, based on the decrease in δ18O values to -9.5‰ (SMOW), suggest that the Cl- concentrations could increase solely from the formation of smectite in a closed system. The diagenesis of volcanic ash also alters the concentrations of most dissolved species in addition to Cl-. Depending on the volume of this altered fluid, it could influence seawater chemistry when vented from the sediment.

The Multi-Stage History of Mt. Sharp

NASA Technical Reports Server (NTRS)

Allen, C.; Dapremont, A.

2013-01-01

The Curiosity rover is exploring Gale crater and Mt. Sharp, Gale's 5-km high central mound. We are investigating the history of alteration and erosion of Mt. Sharp using orbital imagery, spectroscopy and rover observations. Our results suggest a significant time gap between emplacement of the upper and lower sections of the mound. Crater counts show that the lower mound was formed soon after Gale itself, and that it contains distinct units ranging in altitude from approximately -4,500 to -1,800 m. Spectral data suggest that many units contain phyllosilicates. We found that these clay-bearing rocks occur in distinct layers concentrated below -2,900 m. Parts of the lower mound exhibit a transition from clays to sulfates with increasing altitude. The lower mound shows evidence of flowing water, including canyons and inverted channels. Wind erosion produced km-scale yardangs and scalloped cliffs. Our mapping shows that many yardangs in the lower mound are clay-bearing, with a predominant orientation of around N-S. Curiosity's ground-level images show myriad fine-scale, mainly horizontal layers in the lower mound. The rover has found stream beds and conglomerates, indicating that water once flowed on the crater floor. Drilling near the deepest point in Gale produced abundant clay, providing additional evidence of aqueous alteration. Upper mound units range in altitude from -2,100 m to +500 m, and mantle the lower mound above an angular unconformity. Most upper mound units are composed of layers. The formation age of the upper mound is unknown, since few craters are preserved. Clay-bearing layers are detectable in several locations, mainly at altitudes near -2,000 m. There is no evidence of water flow, but wind erosion has scalloped the surfaces and edges of layers, and fine-scale yardangs are common. Correlations between yardangs and clay spectra are apparent only in the lowermost units of the upper mound. Yardang orientations vary, and include N-S, NW-SE, and NE-SW. Upper mound units resemble the planet-wide Medusae Fossae formation, dated as Hesperian and argued to be composed of ignimbrites. Medusae Fossae layers are easily eroded by wind, and our mapping demonstrates their resemblance to upper mound fine-scale yardangs. The history of Mt. Sharp started with deposition and lithification of sediments shortly after crater formation. Some lower mound layers were partially altered to clays and sulfates, and water formed streams and canyons. Wind erosion of the lower mound produced large-scale yardangs, particularly in clay-rich layers, oriented generally N-S. Upper mound units were emplaced following a considerable period of wind erosion. The absence of water flow on the upper mound suggests that these units were emplaced after atmospheric loss rendered water unstable at the surface. The shift in dominant wind direction, as indicated by yardang orientations, also argues for a time gap between erosion of the lower and upper mound. These observations are consistent with upper mound units being related to the Hesperian Medusae Fossae formation. During 2014 Curiosity is expected to reach the foot of Mt. Sharp and ascend through the clay-rich layers, into the sulfate-rich layers, and possibly past the interface with the upper mound. This will be a unique opportunity to field check geologic models on the surface of Mars.

Quantifying the clay content with borehole depth and impact on reservoir flow

NASA Astrophysics Data System (ADS)

Sarath Kumar, Aaraellu D.; Chattopadhyay, Pallavi B.

2017-04-01

This study focuses on the application of reservoir well log data and 3D transient numerical model for proper optimization of flow dynamics and hydrocarbon potential. Fluid flow through porous media depends on clay content that controls porosity, permeability and pore pressure. The pressure dependence of permeability is more pronounced in tight formations. Therefore, preliminary clay concentration analysis and geo-mechanical characterizations have been done by using wells logs. The assumption of a constant permeability for a reservoir is inappropriate and therefore the study deals with impact of permeability variation for pressure-sensitive formation. The study started with obtaining field data from available well logs. Then, the mathematical models are developed to understand the efficient extraction of oil in terms of reservoir architecture, porosity and permeability. The fluid flow simulations have been done using COMSOL Multiphysics Software by choosing time dependent subsurface flow module that is governed by Darcy's law. This study suggests that the reservoir should not be treated as a single homogeneous structure with unique porosity and permeability. The reservoir parameters change with varying clay content and it should be considered for effective planning and extraction of oil. There is an optimum drawdown for maximum production with varying permeability in a reservoir.

Mineralogy and geochemistry of the Lower Cretaceous siliciclastic rocks of the Morita Formation, Sierra San José section, Sonora, Mexico

NASA Astrophysics Data System (ADS)

Madhavaraju, J.; Pacheco-Olivas, S. A.; González-León, Carlos M.; Espinoza-Maldonado, Inocente G.; Sanchez-Medrano, P. A.; Villanueva-Amadoz, U.; Monreal, Rogelio; Pi-Puig, T.; Ramírez-Montoya, Erik; Grijalva-Noriega, Francisco J.

2017-07-01

Clay mineralogy and geochemical studies were carried out on sandstone and shale samples collected from the Sierra San José section of the Morita Formation to infer the paleoclimate and paleoweathering conditions that prevailed in the source region during the deposition of these sediments. The clay mineral assemblages (fraction < 2 μm) of the Sierra San José section are composed of chlorite and illite. The abundance of illite and chlorite in the studied samples suggest that the physical weathering conditions were dominant over chemical weathering. Additionally, the illite and chlorite assemblages reflect arid or semi-arid climatic conditions in the source regions. K2O/Al2O3 ratio of shales vary between 0.15 and 0.26, which lie in the range of values for clay minerals, particularly illite composition. Likewise, sandstones vary between 0.06 and 0.13, suggesting that the clay minerals are mostly kaolinte and illite types. On the chondrite-normalized diagrams, sandstone and shale samples show enriched light rare earth elements (LREE), flat heavy rare earth elements (HREE) patterns and negative Eu anomalies. The CIA and PIA values and A-CN-K plot of shales indicate low to moderate degree of weathering in the source regions. However, the sandstones have moderate to high values of CIA and PIA suggesting a moderate to intense weathering in the source regions. The SiO2/Al2O3 ratios, bivariate and ternary plots, discriminant function diagram and elemental ratios indicate the felsic source rocks for sandstone and shale of the Morita Formation.

Mixed-layer kerolite/stevensite from the Amargosa Desert, Nevada

USGS Publications Warehouse

Eberl, Dennis D.; Jones, Blair F.; Khoury, Hani N.

1982-01-01

Mixed-layer clays composed of randomly interstratified kerolite/stevensite occur as lake and/or spring deposits of probable Pliocene and Pleistocene age in the Amargosa Desert of southern Nevada, U.S.A. The percentage of expandable layers of these clays, determined from computer-simulated X-ray diffractograms, ranges from almost 0 to about 80%. This range in expandabilities most likely results from differences in solution chemistry and/or temperature at the time of formation. An average structural formula for the purest clay (sample P-7), a clay with about 70% expandable layers, is:[(Mg2.72Al0.07Fe0.03Li0.09)(Si3.96Al0.04)O10(OH)0.2]-0.21[X+0.21]+0.21The data suggest that talc, kerolite, and stevensite form a continuous structural series based on layer charge.

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.

Nanostructures and radionuclide transport in clay formations (Invited)

NASA Astrophysics Data System (ADS)

Wang, Y.

2010-12-01

Nanostructures are widely present in geologic materials and are expected to directly affect the interactions of these materials with geologic fluids. The study of mineral-water interface chemistry as controlled by nanostructures is a necessary step to bridge the existing gap between the molecular level understanding of a geochemical process and the macro-scale laboratory and field observations. In this presentation, I will review the recent progresses in nanoscience and provide a perspective on how these progresses can potentially impact geochemical studies. My presentation will be focused the following areas: (1) the characterization of nanostructures in natural systems, (2) the study of water and chemical species in nanoconfinement, (3) the effects of nanopores on geochemical reaction and mass transfers, and (4) the use nanostructured materials for environmental remediation and cleanup. Specifically, I will demonstrate that the nanopore confinement can significantly modify geochemical reactions in porous geologic media. As the pore size is reduced to a few nanometers, the difference between surface acidity constants (pK2 - pK1) decreases, giving rise to a higher surface charge density on a nanopore surface than that on an unconfined mineral-water interface. The change in surface acidity constants results in a shift of ion sorption edges and enhances ion sorption on nanopore surfaces. This effect causes preferential enrichment of trace elements in nanopores and therefore directly impacts the bioavailability of these elements. The implication of these processes to radionuclide transport in clay formations will be discussed. This work was performed at Sandia National Laboratories, which is a multiprogram laboratory operated by Sandia Corporation, a Lockheed-Martin Company, for the DOE under contract DE-AC04-94AL8500.

Characterization of clay scales forming in Philippine geothermal wells

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

Reyes, A.G.; Cardile, C.M.

1989-01-01

Smectite scales occur in 24 out of the 36 blocked wells located in Tongonan, Palinpinon and Bacon-Manito. These comprise 2-85% of the well scales and form at depths of 33-2620 m, where measured and fluid inclusion temperatures are 40-320{sup 0}C. Most, however, occur below the production casing show where temperatures are {ge}230{sup 0}C, often at depths coinciding with aquifers. The clay scales are compositionally and structurally different from the bentonite used in drilling, which is essentially sodium-rich montmorillonite. The clay deposits are expanding, generally disordered, and combine the characteristics of a montmorillonite, saponite and vermiculite in terms of reaction tomore » cationic exchange treatments, structure and composition. Six types of clay scales are identified, but the predominant one, comprising 60-100% of the clay deposits in a well, is Mg- and Fe-rich and referred to as a vermiculitic species. The crystallinity, degree of disorder, textures, optical characteristics, structure and relative amounts of structural Al, Mg and Fe vary with time, temperature and fluid composition, but not with depth and measured pressure. Despite its variance from bentonite characteristics, one of the dominant suggested mechanisms of clay scale formation uses the drilling mud in the well as a substrate, from which the Mg- and Fe-rich clay evolves.« less

Effect of Palygorskite Clay, Fertilizers, and Lime on the Degradation of Oil Products in Oligotrophic Peat Soil under Laboratory Experimental Conditions

NASA Astrophysics Data System (ADS)

Tolpeshta, I. I.; Erkenova, M. I.

2018-02-01

The effect of native palygorskite clay and that modified with dodecyltrimethylammonium chloride on the degradation of oil products in an oligotrophic peat soil under complete flooding at the application of lime and mineral fertilizers has been studied under laboratory conditions. It has been shown that the incubation of oil-contaminated soil with unmodified clay and fertilizers at the application of lime under complete flooding with water affects the dynamics of pH and Eh and slows the development of reducing conditions compared to the use of clay without fertilizers. The addition of organoclay under similar conditions favors the formation of potential-determining system with a high redox capacity, which is capable of retaining the potential on a level of 100-200 mV at pH ˜ 7 for two months. It has been found that, under the experimental conditions, unmodified and modified clay, which has no toxic effect on the bacterial complex, does not increase the biodegradation efficiency of oil products in the oligotrophic peat soil compared to the experimental treatments without clay addition. Possible reasons for no positive effect of palygorskite clay on the biodegradation rate of oil products under experimental conditions have been analyzed.

Bentonite Clay Evolution at Elevated Pressures and Temperatures: An experimental study for generic nuclear repositories

NASA Astrophysics Data System (ADS)

Caporuscio, F. A.; Cheshire, M.; McCarney, M.

2012-12-01

The Used Fuel Disposition Campaign is presently engaged in looking at various generic repository options for disposal of used fuel. Of interest are the disposal of high heat load canisters ,which may allow for a reduced repository footprint. The focus of this experimental work is to characterize Engineered Barrier Systems (EBS) conditions in repositories. Clay minerals - as backfill or buffer materials - are critical to the performance of the EBS. Experiments were performed in Dickson cells at 150 bar and sequentially stepped from 125 oC to 300 oC over a period of ~1 month. An unprocessed bentonite from Colony, Wyoming was used as the buffer material in each experiment. An K-Ca-Na-Cl-rich brine (replicating deep Stripa groundwater) was used at a 9:1 water:rock ratio. The baseline experiment contained brine + clay, while three other experiments contained metals that could be used as waste form canisters (brine +clay+304SS, brine+clay+316SS, brine+clay+Cu). All experiments were buffered at the Mt-Fe oxygen fugacity univarient line. As experiment temperature increased and time progressed, pH, K and Ca ion concentrations dropped, while Si, Na, and SO4 concentrations increased. Silicon was liberated into the fluid phase (>1000 ppm) and precipitated during the quenching of the experiment. The precipitated silica transformed to cristobalite as cooling progressed. Potassium was mobilized and exchanged with interlayer Na, transitioning the clay from Na-montmorillonite to K-smectite. Though illitization was not observed in these experiments, its formation may be kinetically limited and longer-term experiments are underway to evaluate the equilibrium point in this reaction. Clinoptilolite present in the starting bentonite mixture is unstable above 150 oC. Hence, the zeolite broke down at high temperatures but recrystallized as the quench event occurred. This was borne out in SEM images that showed clinoptilolite as a very late stage growth mineral. Both experimental runs containing steel exhibit the generation of a chlorite / Fe-saponite layer at the clay-metal boundary. The formation of minor amounts of pentlandite [(Fe,Ni)9S8] also occurs on both steel plates. Chalcocite (Cu2S) formed as a corrosion product on the Cu plates. The two sulfide phases have been produced by the generation of H2S gas during the experimental runs. The H2S is formed by the breakdown of pyrite framboids at high temperature in the bentonite. Such experiments on representative EBS materials at elevated P,T repository conditions are providing useful information for generic repository studies. Lack of illite formation is common in clay experiments and may be related to kinetics or K concentration. Precipitated SiO2 may potentially seal heating cracks in the clay backfill. The chlorite layer generated on steel may act as a passivation material and prevent corrosion of the steel canister wall. Finally, even if zeolites break down during the high temperature thermal pulse of a repository, zeolites may form again as the repository inventory cools off and perform as radionuclide sorbing phases.

Mont Terri Underground Rock Laboratory, Switzerland-Research Program And Key Results

NASA Astrophysics Data System (ADS)

Nussbaum, C. O.; Bossart, P. J.

2012-12-01

Argillaceous formations generally act as aquitards because of their low hydraulic conductivities. This property, together with the large retention capacity of clays for cationic contaminants and the potential for self-sealing, has brought clay formations into focus as potential host rocks for the geological disposal of radioactive waste. Excavated in the Opalinus Clay formation, the Mont Terri underground rock laboratory in the Jura Mountains of NW Switzerland is an important international test site for researching clay formations. Research is carried out in the underground facility, which is located adjacent to the security gallery of the Mont Terri motorway tunnel. Fifteen partners from European countries, USA, Canada and Japan participate in the project. The objectives of the research program are to analyze the hydrogeological, geochemical and rock mechanical properties of the Opalinus Clay, to determine the changes induced by the excavation of galleries and by heating of the rock formation, to test sealing and container emplacement techniques and to evaluate and improve suitable investigation techniques. For the safety of deep geological disposal, it is of key importance to understand the processes occurring in the undisturbed argillaceous environment, as well as the processes in a disturbed system, during the operation of the repository. The objectives are related to: 1. Understanding processes and mechanisms in undisturbed clays and 2. Experiments related to repository-induced perturbations. Experiments of the first group are dedicated to: i) Improvement of drilling and excavation technologies and sampling methods; ii) Estimation of hydrogeological, rock mechanical and geochemical parameters of the undisturbed Opalinus Clay. Upscaling of parameters from laboratory to in situ scale; iii) Geochemistry of porewater and natural gases; evolution of porewater over time scales; iv) Assessment of long-term hydraulic transients associated with erosion and thermal scenarios and v) Evaluation of diffusion and retention parameters for long-lived radionuclides. Experiments related to repository-induced perturbations are focused on: i) Influence of rock liner on the disposal system and the buffering potential of the host rock; ii) Self-sealing processes in the excavation damaged zone; iii) Hydro-mechanical coupled processes (e.g. stress redistributions and pore pressure evolution during excavation); iv) Thermo-hydro-mechanical-chemical coupled processes (e.g. heating of bentonite and host rock) and v) Gas-induced transport of radionuclides in porewater and along interfaces in the engineered barrier system. A third research direction is to demonstrate the feasibility of repository construction and long-term safety after repository closure. Demonstration experiments can contribute to improving the reliability of the scientific basis for the safety assessment of future geological repositories, particularly if they are performed on a large scale and with a long duration. These experiments include the construction and installation of engineered barriers on a 1:1 scale: i) Horizontal emplacement of canisters; ii) Evaluation of the corrosion of container materials; repository re-saturation; iii) Sealing of boreholes and repository access tunnels and iv) Long-term monitoring of the repository. References Bossart, P. & Thury, M. (2008): Mont Terri Rock Laboratory. Project, Programme 1996 to 2007 and Results. - Rep. Swiss Geol. Surv. 3.

Seismic Velocities Contain Information About Depth, Lithology, Fluid Content, and Microstructure

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

Berge, P A; Bonner, B P

2002-01-03

Recent advances in field and laboratory methods for measuring elastic wave velocities provide incentive and opportunity for improving interpretation of geophysical data for engineering and environmental applications. Advancing the state-of-the-art of seismic imaging requires developing petrophysical relationships between measured velocities and the hydrogeology parameters and lithology. Our approach uses laboratory data and rock physics methods. Compressional (Vp) and shear (Vs) wave velocities, Vp/Vs ratios, and relative wave amplitudes show systematic changes related to composition, saturation, applied stress (analogous to depth), and distribution of clay for laboratory ultrasonic measurements on soils. The artificial soils were mixtures of Ottawa sand and amore » second phase, either Wyoming bentonite or peat moss used to represent clay or organic components found in natural soils. Compressional and shear wave velocities were measured for dry, saturated, and partially-saturated conditions, for applied stresses between about 7 and 100 kPa, representing approximately the top 5 m of the subsurface. Analysis of the results using rock physics methods shows the link between microstructure and wave propagation, and implications for future advances in seismic data interpretation. For example, we found that Vp in dry sand-clay mixtures initially increases as clay cements the sand grains and fills porosity, but then Vp decreases when the clay content is high enough that the clay matrix controls the elastic response of the material. Vs decreases monotonically with increasing clay content. This provides a method for using Vp/Vs ratios to estimate clay content in a dry soil.« less

National Dam Safety Program. Whitehead Dam (NJ00559), Delaware River Basin, Assunpink Creek, Mercer County, New Jersey. Phase I Inspection Report.

DTIC Science & Technology

1980-03-01

Magothy and Raritan Formations. These marine formations are comprised of alternating beds of clay and sand. Assunpink Creek is near the westerly extent...of the Magothy and Raritan formations and their overall thickness may be as little as twenty five feet. Precambrian bedrock underlies these

Aqueous processing of organic compounds in carbonaceous asteroids

NASA Astrophysics Data System (ADS)

Trigo-Rodríguez, Josep Maria; Rimola, Albert; Martins, Zita

2015-04-01

There is growing evidence pointing towards a prebiotic synthesis of complex organic species in water-rich undifferentiated bodies. For instance, clays have been found to be associated with complex organic compounds (Pearson et al. 2002; Garvie & Buseck 2007; Arteaga et al. 2010), whereas theoretical calculations have studied the interaction between the organic species and surface minerals (Rimola et al., 2013) as well as surface-induced reactions (Rimola at al. 2007). Now, we are using more detailed analytical techniques to study the possible processing of organic molecules associated with the mild aqueous alteration in CR, CM and CI chondrites. To learn more about these processes we are studying carbonaceous chondrites at Ultra High-Resolution Transmission Electron Microscopy (UHR-TEM). We are particularly interested in the relationship between organics and clay minerals in carbonaceous chondrites (CCs) matrixes (Trigo-Rodríguez et al. 2014, 2015).We want to address two goals: i) identifying the chemical steps in which the organic molecules could have increased their complexity (i.e., surface interaction and catalysis); and ii) studying if the organic matter present in CCs experienced significant processing concomitant to the formation of clays and other minerals at the time in which these planetary bodies experienced aqueous alteration. Here, these two points are preliminarily explored combing experimental results with theoretical calculations based on accurate quantum mechanical methods. References Arteaga O, Canillas A, Crusats J, El-Hachemi Z, Jellison GE, Llorca J, Ribó JM (2010) Chiral biases in solids by effect of shear gradients: a speculation on the deterministic origin of biological homochirality. Orig Life Evol Biosph 40:27-40. Garvie LAJ, Buseck PR (2007) Prebiotic carbon in clays from Orgueil and Ivuna (CI) and Tagish lake (C2 ungrouped) meteorites. Meteorit Planet Sci 42:2111-2117. Pearson VK, Sephton MA, Kearsley AT, Bland AP, Franchi IA, Gilmour A (2002) Clay mineral-organic matter relationships in the early solar system. Meteorit Planet Sci 37:1829-1833. Rimola A, Costa D, Sodupe M, Lambert JF, Ugliengo P (2013) Silica surface features and their role in the adsorption of biomolecules: computational modeling and experiments. Chem Rev 113:4216-4313. Rimola A, Sodupe M, Ugliengo P (2007) Aluminosilicate as promoters for peptide bond formation: an assessment of Bernal's hypothesis by ab initio methods. J Am Chem soc 129:8333-8344 Trigo-Rodríguez JM, Moyano-Cambero CE, Llorca J, Formasier S, Barucci MA, Belskaya I, Martins Z, Rivkin AS, Dotto E, Madiedo JM, Alonso-Azcárate J (2014) UV to far-IR reflectance spectra of carbonaceous chondrites - I. Implications for remote characterization of dark primitive asteroids targeted by sample-return missions. Mon Not R Astron Soc 437:227-240. Trigo-Rodríguez JM, Alonso-Azcárate J, Abad MM, Lee MR (2015) Ultra high resolution Transmission Electron Microscopy of matrix mineral grains in CM chondrites: preaccretionary or parent body aqueous processing? LPI constribution, 46th LPSC, abstract #1198.

Bacillus subtilis biofilm development in the presence of soil clay minerals and iron oxides.

PubMed

Ma, Wenting; Peng, Donghai; Walker, Sharon L; Cao, Bin; Gao, Chun-Hui; Huang, Qiaoyun; Cai, Peng

2017-01-01

Clay minerals and metal oxides, as important parts of the soil matrix, play crucial roles in the development of microbial communities. However, the mechanism underlying such a process, particularly on the formation of soil biofilm, remains poorly understood. Here, we investigated the effects of montmorillonite, kaolinite, and goethite on the biofilm formation of the representative soil bacteria Bacillus subtilis . The bacterial biofilm formation in goethite was found to be impaired in the initial 24 h but burst at 48 h in the liquid-air interface. Confocal laser scanning microscopy showed that the biofilm biomass in goethite was 3-16 times that of the control, montmorillonite, and kaolinite at 48 h. Live/Dead staining showed that cells had the highest death rate of 60% after 4 h of contact with goethite, followed by kaolinite and montmorillonite. Atomic force microscopy showed that the interaction between goethite and bacteria may injure bacterial cells by puncturing cell wall, leading to the swarming of bacteria toward the liquid-air interface. Additionally, the expressions of abrB and sinR , key players in regulating the biofilm formation, were upregulated at 24 h and downregulated at 48 h in goethite, indicating the initial adaptation of the cells to minerals. A model was proposed to describe the effects of goethite on the biofilm formation. Our findings may facilitate a better understanding of the roles of soil clays in biofilm development and the manipulation of bacterial compositions through controlling the biofilm in soils.

Influence of Miscibility Phenomenon on Crystalline Polymorph Transition in Poly(Vinylidene Fluoride)/Acrylic Rubber/Clay Nanocomposite Hybrid

PubMed Central

Abolhasani, Mohammad Mahdi; Naebe, Minoo; Jalali-Arani, Azam; Guo, Qipeng

2014-01-01

In this paper, intercalation of nanoclay in the miscible polymer blend of poly(vinylidene fluoride) (PVDF) and acrylic rubber(ACM) was studied. X-ray diffraction was used to investigate the formation of nanoscale polymer blend/clay hybrid. Infrared spectroscopy and X-ray analysis revealed the coexistence of β and γ crystalline forms in PVDF/Clay nanocomposite while α crystalline form was found to be dominant in PVDF/ACM/Clay miscible hybrids. Flory-Huggins interaction parameter (B) was used to further explain the miscibility phenomenon observed. The B parameter was determined by combining the melting point depression and the binary interaction model. The estimated B values for the ternary PVDF/ACM/Clay and PVDF/ACM pairs were all negative, showing both proper intercalation of the polymer melt into the nanoclay galleries and the good miscibility of PVDF and ACM blend. The B value for the PVDF/ACM blend was almost the same as that measured for the PVDF/ACM/Clay hybrid, suggesting that PVDF chains in nanocomposite hybrids interact with ACM chains and that nanoclay in hybrid systems is wrapped by ACM molecules. PMID:24551141

Microscopic Mechanism and Kinetics of Ice Formation at Complex Interfaces: Zooming in on Kaolinite

PubMed Central

2016-01-01

Most ice in nature forms because of impurities which boost the exceedingly low nucleation rate of pure supercooled water. However, the microscopic details of ice nucleation on these substances remain largely unknown. Here, we have unraveled the molecular mechanism and the kinetics of ice formation on kaolinite, a clay mineral playing a key role in climate science. We find that the formation of ice at strong supercooling in the presence of this clay is about 20 orders of magnitude faster than homogeneous freezing. The critical nucleus is substantially smaller than that found for homogeneous nucleation and, in contrast to the predictions of classical nucleation theory (CNT), it has a strong two-dimensional character. Nonetheless, we show that CNT describes correctly the formation of ice at this complex interface. Kaolinite also promotes the exclusive nucleation of hexagonal ice, as opposed to homogeneous freezing where a mixture of cubic and hexagonal polytypes is observed. PMID:27269363

Quality evaluation of processed clay soil samples

PubMed Central

Steiner-Asiedu, Matilda; Harrison, Obed Akwaa; Vuvor, Frederick; Tano-Debrah, Kwaku

2016-01-01

Introduction This study assessed the microbial quality of clay samples sold on two of the major Ghanaian markets. Methods The study was a cross-sectional assessing the evaluation of processed clay and effects it has on the nutrition of the consumers in the political capital town of Ghana. The items for the examination was processed clay soil samples. Results Staphylococcus spp and fecal coliforms including Klebsiella, Escherichia, and Shigella and Enterobacterspp were isolated from the clay samples. Samples from the Kaneshie market in Accra recorded the highest total viable counts 6.5 Log cfu/g and Staphylococcal count 5.8 Log cfu/g. For fecal coliforms, Madina market samples had the highest count 6.5 Log cfu/g and also recorded the highest levels of yeast and mould. For Koforidua, total viable count was highest in the samples from the Zongo market 6.3 Log cfu/g. Central market samples had the highest count of fecal coliforms 4.6 Log cfu/g and yeasts and moulds 6.5 Log cfu/g. “Small” market recorded the highest staphylococcal count 6.2 Log cfu/g. The water activity of the clay samples were low, and ranged between 0.65±0.01 and 0.66±0.00 for samples collected from Koforidua and Accra respectively. Conclusion The clay samples were found to contain Klebsiella spp. Escherichia, Enterobacter, Shigella spp. staphylococcus spp., yeast and mould. These have health implications when consumed. PMID:27642456

Shear-induced morphology transition and microphase separation in a lamellar phase doped with clay particles.

PubMed

Nettesheim, Florian; Grillo, Isabelle; Lindner, Peter; Richtering, Walter

2004-05-11

We report on the influence of shear on a nonionic lamellar phase of tetraethyleneglycol monododecyl ether (C12E4) in D2O containing clay particles (Laponite RD). The system was studied by means of small-angle light scattering (SALS) and small-angle neutron scattering (SANS) under shear. The SANS experiments were conducted using a H2O/D2O mixture of the respective scattering length density to selectively match the clay scattering. The rheological properties show the familiar shear thickening regime associated with the formation of multilamellar vesicles (MLVs) and a shear thinning regime at higher stresses. The variation of viscosity is less pronounced as commonly observed. In the shear thinning regime, depolarized SALS reveals an unexpectedly strong variation of the MLV size. SANS experiments using the samples with lamellar contrast reveal a change in interlamellar spacing of up to 30% at stresses that lead to MLV formation. This change is much more pronounced than the change observed, when shear suppresses thermal bilayer undulations. Microphase separation occurs, and as a consequence, the lamellar spacing decreases drastically. The coincidence of the change in lamellar spacing and the onset of MLV formation is a strong indication for a morphology-driven microphase separation.

Nanoparticles prepared by the sol gel method and their use in the formation of nanocomposites with polypropylene

NASA Astrophysics Data System (ADS)

Moncada, E.; Quijada, R.; Retuert, J.

2007-08-01

Hybrid layered aluminosilicate nanoparticles (HLNP) containing octadecylamine (ODA) as the organic part, and silica nanoparticles with spherical morphology containing ODA (HSNP) or without ODA (SNP) were prepared by the sol-gel method and used for the formation of nanocomposites with polypropylene. The polypropylene matrices, of different molecular weight and polydispersity, were prepared using polymers obtained via Ziegler-Natta or metallocene catalysts. A strong influence of the morphology and the presence of ODA on the surface of the nanoparticles was found on the formation and characteristics of the nanocomposites. The mechanical properties and thermal stability of these materials were determined and compared with those of nanocomposites prepared with 2:1 phylosilicate clays such as montmorillonite and hectorite in similar polymer matrices. X-ray diffraction, transmission electron microscopy, and the study of mechanical properties showed that the use of HLNP allows nanocomposites with considerably improved mechanical properties to be obtained, compared with nanocomposites prepared with exfoliated clays. In the case of nanocomposites prepared with spherical particles functionalized with ODA (HSNP), materials with high specific strength combined with high elongation before rupture were obtained. The thermal stabilization of polypropylene matrices containing the synthesized nanoparticles (HLNP, HSNP or SNP) occurs about 50 °C higher than that attained with clays.

Synthesis of highly reactive subnano-sized zero-valent iron using smectite clay templates.

PubMed

Gu, Cheng; Jia, Hanzhong; Li, Hui; Teppen, Brian J; Boyd, Stephen A

2010-06-01

A novel method was developed for synthesizing subnano-sized zero-valent iron (ZVI) using smectite clay layers as templates. Exchangeable Fe(III) cations compensating the structural negative charges of smectites were reduced with NaBH(4), resulting in the formation of ZVI. The unique structure of smectite clay, in which isolated exchangeable Fe(III) cations reside near the sites of structural negative charges, inhibited the agglomeration of ZVI resulting in the formation of subnanoscale ZVI particles in the smectite interlayer regions. X-ray diffraction revealed an interlayer spacing of approximately 5 A. The non-structural iron content of this clay yields a calculated ratio of two atoms of ZVI per three cation exchange sites, in full agreement with the X-ray diffraction (XRD) results since the diameter of elemental Fe is 2.5 A. The clay-templated ZVI showed superior reactivity and efficiency compared to other previously reported forms of ZVI as indicated by the reduction of nitrobenzene; structural Fe within the aluminosilicate layers was nonreactive. At a 1:3 molar ratio of nitrobenzene/non-structural Fe, a reaction efficiency of 83% was achieved, and over 80% of the nitrobenzene was reduced within one minute. These results confirm that non-structural Fe from Fe(III)-smectite was reduced predominantly to ZVI which was responsible for the reduction of nitrobenzene to aniline. This new form of subnanoscale ZVI may find utility in the development of remediation technologies for persistent environmental contaminants, for example, as components of constructed reactive domains such as reactive caps for contaminated sediments.

Synthesis of Highly Reactive Subnano-sized Zero-valent Iron using Smectite Clay Templates

PubMed Central

Gu, Cheng; Jia, Hanzhang; Li, Hui; Teppen, Brian J.; Boyd, Stephen A.

2010-01-01

A novel method was developed for synthesizing subnano-sized zero-valent iron (ZVI) using smectite clay layers as templates. Exchangeable Fe(III) cations compensating the structural negative charges of smectites were reduced with NaBH4, resulting in the formation of ZVI. The unique structure of smectite clay, in which isolated exchangeable Fe(III) cations reside near the sites of structural negative charges, inhibited the agglomeration of ZVI resulting in the formation of discrete regions of subnanoscale ZVI particles in the smectite interlayer regions. X-ray diffraction revealed an interlayer spacing of ~ 5 Å. The non-structural iron content of this clay yields a calculated ratio of two atoms of ZVI per three cation exchange sites, in full agreement with the XRD results since the diameter of elemental Fe is 2.5 Å. The clay-templated ZVI showed superior reactivity and efficiency compared to other previously reported forms of ZVI as indicated by the reduction of nitrobenzene; structural Fe within the aluminosilicate layers was nonreactive. At a 1:3 molar ratio of nitrobenzene:non-structural Fe, a reaction efficiency of 83% was achieved, and over 80% of the nitrobenzene was reduced within one minute. These results confirm that non-structural Fe from Fe(III)-smectite was reduced predominantly to ZVI which was responsible for the reduction of nitrobenzene to aniline. This new form of subnano-scale ZVI may find utility in the development of remediation technologies for persistent environmental contaminants, e.g. as components of constructed reactive domains such as reactive caps for contaminated sediments. PMID:20446730

Revision of Hopewellian trading patterns in Midwestern North America based on mineralogical sourcing

USGS Publications Warehouse

Hughes, R.E.; Berres, T.E.; Moore, D.M.; Farnsworth, K.B.

1998-01-01

Traditional exchange models purport that all Hopewell-style platform pipes of flint clay were quarried and crafted in southern Ohio by Native Americans from a local kaolinitic flint clay, and that those found in the Havana Hopewell region of western Illinois were transported from southern Ohio along an Ohio River trade network. However, the results of this study show that berthierine-rich flint clay from northwestern Illinois was the only source for pipestone artifacts of the Havana Hopewell region. We base this on (1) X-ray diffraction analysis of quickly made smears, (2) spatiotemporal distribution of artifacts in the Sterling-Rock Falls, Illinois area, and (3) petrographic, X-ray fluorescence, Mo??ssbauer, and SEM/EDX analyses. This understanding of the source of this material made it possible to visually identify the source of large numbers of curated artifacts as having been made of material from the Sterling-Rock Falls area. This discovery has implications for understanding cultural and material exchange among Hopewellian societies. Also, it is the first report of berthierine flint clay and of flint clay that formed before the evolution of terrestrial plants. ?? 1998 John Wiley & Sons, Inc.

Speciation of uranium in surface-modified, hydrothermally treated, (UO{sub 2}){sup 2+}-exchanged smectite clays

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

Giaquinta, D.M.; Soderholm, L.; Yuchs, S.E.

1997-08-01

A successful solution to the problem of disposal and permanent storage of water soluble radioactive species must address two issues: exclusion of the radionuclides from the environment and the prevention of leaching from the storage media into the environment. Immobilization of radionuclides in clay minerals has been studied. In addition to the use of clays as potential waste forms, information about the interactions of radionuclides with clays and how such interactions affect their speciations is crucial for successful modeling of actinide-migration. X-ray absorption spectroscopy (XAS) is used to determine the uranium speciation in exchanged and surface-modified clays. The XAS datamore » from uranyl-loaded bentonite clay are compared with those obtained after the particle surfaces have been coated with alkylsilanes. These silane films, which render the surface of the clay hydrophobic, are added in order to minimize the ability of external water to exchange with the water in the clay interlayer, thereby decreasing the release rate of the exchanged-uranium species. Mild hydrothermal conditions are used in an effort to mimic potential geologic conditions that may occur during long-term radioactive waste storage. The XAS spectra indicate that the uranyl monomer species remain unchanged in most samples, except in those samples that were both coated with an alkylsilane and hydrothermally treated. When the clay was coated with an organic film, formed by the acidic deposition of octadecyltrimethoxysilane, hydrothermal treatment results in the formation of aggregated uranium species in which the uranium is reduced from U{sup VI} to U{sup IV}.« less

Turbulent Coagulation of Particles Smaller Than the Length Scales of Turbulence and Equilibrium Sorption of Phenanthrene to Clay: Implications for Pollutant Transport in the Estuarine Water Column

DTIC Science & Technology

1997-05-01

estuaries was modeled using phenanthrene, bacterial extracellular polymer and kaolinite clay as surrogates for a hydrophobic organic pollutant...coefficients obtained for phenanthrene sorption to kaolinite and bentonite in the presence of varying amounts of DOM represented by alginic acid and tannic...acid. 333 Table B.3: Literature values for sorption between phenanthrene, humic acid and kaolinite for [DOM]a = 10 mg/L 334 Table E.1: Sample output data

Major and Trace Element Variations in Impact Crater Clay from Chicxulub, Lonar, and Mistastin, Implications for the Martian Soil

NASA Technical Reports Server (NTRS)

Newsom, H. E.; Nelson, M. J.; Shearer, C. K.; Rietmeijer, F. J. M.; Gakin, R.; Lee, K.

2004-01-01

The catastrophic Chicxulub event should have generated a large hydrothermal system with volatile element mobilization, producing interesting alteration materials and clays. The Yaxcopoil-1 (YAX) drill hole is located in the annular trough, about 70 km southwest of the crater center, in an area where the impactite layers are relatively thin (approx. 100 m thick). We have analyzed samples from the YAX drill core and from other impact craters including Mistastin and Lonar to determine the nature of alteration and trace element mobilization.

Surveying Clay Mineral Diversity in the Murray Formation, Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Bristow, T. F.; Blake, D. F.; Vaniman, D. T.; Chipera, S. J.; Rampe, E. B.; Grotzinger, J. P.; McAdam, A. C.; Ming, D. W.; Morrison, S. M.; Yen, A. S.;

Flocculation of Clay Colloids Induced by Model Polyelectrolytes: Effects of Relative Charge Density and Size.

PubMed

Sakhawoth, Yasine; Michot, Laurent J; Levitz, Pierre; Malikova, Natalie

2017-10-06

Flocculation and its tuning are of utmost importance in the optimization of several industrial protocols in areas such as purification of waste water and civil engineering. Herein, we studied the polyelectrolyte-induced flocculation of clay colloids on a model system consisting of purified clay colloids of well-defined size fractions and ionene polyelectrolytes presenting regular and tunable chain charge density. To characterize ionene-induced clay flocculation, we turned to the combination of light absorbance (turbidity) and ζ-potential measurements, as well as adsorption isotherms. Our model system allowed us to identify the exact ratio of positive and negative charges in clay-ionene mixtures, the (c+/c-) ratio. For all samples studied, the onset of efficient flocculation occurred consistently at c+/c- ratios significantly below 1, which indicated the formation of highly ionene-deficient aggregates. At the same time, the ζ-potential measurements indicated an apparent zero charge on such aggregates. Thus, the ζ-potential values could not provide the stoichiometry inside the clay-ionene aggregates. The early onset of flocculation in clay-ionene mixtures is reminiscent of the behavior of multivalent salts and contrasts that of monovalent salts, for which a large excess amount of ions is necessary to achieve flocculation. Clear differences in the flocculation behavior are visible as a function of the ionene charge density, which governs the conformation of the ionene chains on the clay surface. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Identification and characterization of hydrothermally altered zones in granite by combining synthetic clay content logs with magnetic mineralogical investigations of drilled rock cuttings

NASA Astrophysics Data System (ADS)

Meller, Carola; Kontny, Agnes; Kohl, Thomas

2014-10-01

Clay minerals as products of hydrothermal alteration significantly influence the hydraulic and mechanical properties of crystalline rock. Therefore, the localization and characterization of alteration zones by downhole measurements is a great challenge for the development of geothermal reservoirs. The magnetite bearing granite of the geothermal site in Soultz-sous-Forêts (France) experienced hydrothermal alteration during several tectonic events and clay mineral formation is especially observed in alteration halos around fracture zones. During the formation of clay minerals, magnetite was oxidized into hematite, which significantly reduces the magnetic susceptibility of the granite from ferrimagnetic to mostly paramagnetic values. The aim of this study was to find out if there exists a correlation between synthetic clay content logs (SCCLs) and measurements of magnetic susceptibility on cuttings in the granite in order to characterize their alteration mineralogy. Such a correlation has been proven for core samples of the EPS1 reference well. SCCLs were created from gamma ray and fracture density logs using a neural network. These logs can localize altered fracture zones in the GPK1-4 wells, where no core material is available. Mass susceptibility from 261 cutting samples of the wells GPK1-GPK4 was compared with the neural network derived synthetic logs. We applied a combination of temperature dependent magnetic susceptibility measurements with optical and electron microscopy, and energy dispersive X-ray spectroscopy to discriminate different stages of alteration. We found, that also in the granite cuttings an increasing alteration grade is characterized by an advancing oxidation of magnetite into hematite and a reduction of magnetic susceptibility. A challenge to face for the interpretation of magnetic susceptibility data from cuttings material is that extreme alteration grades can also display increased susceptibilities due to the formation of secondary magnetite. Low magnetic susceptibility can also be attributed to primary low magnetite content, if the granite facies changes. In order to interpret magnetic susceptibility from cuttings, contaminations with iron from wear debris of the drilling tools must be eliminated. Provided that the magnetic mineralogy of the granite is known in detail, this method in combination with petrographic investigations is suited to indicate and characterize hydrothermal alteration and the appearance of clay.

The nature of porosity in organic-rich mudstones of the Upper Jurassic Kimmeridge Clay Formation, North Sea, offshore United Kingdom

USGS Publications Warehouse

Fishman, Neil S.; Hackley, Paul C.; Lowers, Heather; Hill, Ronald J.; Egenhoff, Sven O.; Eberl, Dennis D.; Blum, Alex E.

2012-01-01

Analyses of organic-rich mudstones from wells that penetrated the Upper Jurassic Kimmeridge Clay Formation, offshore United Kingdom, were performed to evaluate the nature of both organic and inorganic rock constituents and their relation to porosity in this world-class source rock. The formation is at varying levels of thermal maturity, ranging from immature in the shallowest core samples to mature in the deepest core samples. The intent of this study was to evaluate porosity as a function of both organic macerals and thermal maturity. At least four distinct types of organic macerals were observed in petrographic and SEM analyses and they all were present across the study area. The macerals include, in decreasing abundance: 1) bituminite admixed with clays; 2) elongate lamellar masses (alginite or bituminite) with small quartz, feldspar, and clay entrained within it; 3) terrestrial (vitrinite, fusinite, semifusinite) grains; and 4) Tasmanites microfossils. Although pores in all maceral types were observed on ion-milled surfaces of all samples, the pores (largely nanopores with some micropores) vary as a function of maceral type. Importantly, pores in the macerals do not vary systematically as a function of thermal maturity, insofar as organic pores are of similar size and shape in both the immature and mature Kimmeridge rocks. If any organic pores developed during the generation of hydrocarbons, they were apparently not preserved, possibly because of the highly ductile nature of much of the rock constituents of Kimmeridge mudstones (clays and organic material). Inorganic pores (largely micropores with some nanopores) have been observed in all Kimmeridge mudstones. These pores, particularly interparticle (i.e., between clay platelets), and intraparticle (i.e., in framboidal pyrite, in partially dissolved detrital K-feldspar, and in both detrital and authigenic dolomite) are noteworthy because they compose much of the observable porosity in the shales in both immature and mature samples. The absence of a systematic increase in organic porosity as a function of either maceral type or thermal maturity indicates that such porosity was probably unrelated to hydrocarbon generation. Instead, much of the porosity within mudstones of the Kimmeridge appears to be largely intraparticle and interparticle (adjacent to inorganic constituents), so the petroleum storage potential in these organic-rich mudstones largely resides in inorganic pores.

Adsorption effect on the degradation of 4,6-o-dinitrocresol and p-nitrophenol in a montmorillonite clay slurry by AFT.

PubMed

Ye, Peng; Lemley, Ann T

2009-03-01

The adsorption and degradation of 4,6-o-dinitrocresol (DNOC) and p-nitrophenol (PNP) in SWy-2 montmorillonite clay slurry were investigated. The pH and type of cation of the slurry were varied. Results showed that adsorption of DNOC and PNP increased at lower pH values, and when pH < pKa(4.4) of DNOC, DNOC was almost completely adsorbed on the clay under given experimental conditions. The specific cation also had a significant effect on adsorption, which was dramatically enhanced in the presence of K+ and NH4+, compared with the presence of Na+ or Ca2+. Anodic Fenton treatment (AFT) degradation of DNOC and PNP in the clay slurry was studied, and it was found that DNOC degradation rates were greatly affected by the initial pH and the types of electrolytes. Due to the higher adsorption, the degradation rate substantially decreased in the clay slurry system in the presence of K+ and low pH, with a large amount of DNOC residue remaining after 60 min treatment. AFT degradation of PNP was completed within 30 min treatment. Based on LC-MS data, a DNOC degradation pathway was proposed. Overall, the results showed the inhibition effect of adsorption on the degradation of nitroaromatic compounds in montmorillonite clay slurry by AFT, providing important implications for water and soil remediation.

Ultrafiltration by a compacted clay membrane-II. Sodium ion exclusion at various ionic strengths

USGS Publications Warehouse

Hanshaw, B.B.; Coplen, T.B.

1973-01-01

Several recent laboratory studies and field investigations have indicated that shales and compacted clay minerals behave as semipermeable membranes. One of the properties of semipermeable membranes is to retard or prevent the passage of charged ionic species through the membrane pores while allowing relatively free movement of uncharged species. This phenomenon is termed salt filtering, reverse osmosis, or ultrafiltration. This paper shows how one can proceed from the ion exchange capacity of clay minerals and, by means of Donnan membrane equilibrium concept and the Teorell-Meyer-Siever theory, develop a theory to explain why and to what extent ultrafiltration occurs when solutions of known concentration are forced to flow through a clay membrane. Reasonable agreement between theory and laboratory results were found. The concentration of the ultrafiltrate was always greater than predicted because of uncertainty in values of some parameters in the equations. Ultrafiltration phenomena may be responsible for the formation of some subsurface brines and mineral deposits. The effect should also be taken into consideration in any proposal for subsurface waste emplacement in an environment containing large quantities of clay minerals. ?? 1973.

Adsorption of acetanilide herbicides on soil and its components. II. Adsorption and catalytic hydrolysis of diethatyl-ethyl on saturated Na(+)-, K(+)-, Ca(2+)-, and Mg(2+)-montmorillonite.

PubMed

Liu, W P; Fang, Z; Liu, H J; Yang, W C

2001-04-01

Adsorption and catalytic hydrolysis of the herbicide diethatyl-ethyl [N-chloroacetyl-N-(2,6-diethylphenyl)glycine ethyl ester] on homoionic Na(+)-, K(+)-, Ca(2+)-, and Mg(2+)-montmorillonite clays were investigated in water solution. The Freundlich adsorption coefficient, Ki, got from isotherms on clay followed the order of Na+ approximately K+ > Mg2+ approximately Ca2+. Analysis of FT-IR spectra of diethatyl-ethyl adsorbed on clay suggests probable bonding at the carboxyl and amide carbonyl groups of the herbicide. The rate of herbicide hydrolysis in homoionic clay suspensions followed the same order as that for adsorption, indicating that adsorption may have preceded and thus caused hydrolysis. Preliminary product identification showed that hydrolysis occurred via nucleophilic substitution at the carboxyl carbon, causing the cleavage of the ester bond and formation of diethatyl and its dechlorinated derivative, and at the amide carbon, yielding an ethyl ester derivative and its acid. These pathways also suggest that hydrolysis of diethatyl-ethyl was catalyzed by adsorption on the clay surface.

Model System Study of Environmentally Persistent Free Radicals Formation in a Semiconducting Polymer Modified Copper Clay System at Ambient Temperature

PubMed Central

Nwosu, Ugwumsinachi G.; Khachatryan, Lavrent; Youm, Sang Gil; Roy, Amitava; dela Cruz, Albert Leo N.; Nesterov, Evgueni E.; Dellinger, Barry; Cook, Robert L.

2016-01-01

This paper systematically investigates how environmentally persistent free radicals (EPFRs) are formed in a phenol contaminated model soil. Poly-p-phenylene (PPP) modified and copper-loaded montmorillonite (MMT) clays were developed and used as models of soil organic matter and the clay mineral component, respectively, with phenol being employed as a precursor pollutant. The polymer modification of the clays was carried out via surface-confined Kumada catalyst-transfer chain-growth polymerization. The presence and location of the polymer were confirmed by a combination of thermogravimetric analysis (TGA), Raman spectroscopy, and X-ray diffraction data. EPFRs were formed by the Cu(II)-clay (Cu(II)CaMMT) and poly-p-phenylene-Cu(II)clay (PPP-Cu(II)CaMMT) composite systems under environmentally relevant conditions. The g-factor and concentration of EPFRs formed by the Cu(II)CaMMT and PPP-Cu(II)CaMMT systems were found to be 2.0034 and 1.22 × 1017 spins/g and 2.0033 and 1.58 × 1017spins/g, respectively. These g-factors are consistent with the formation of phenoxyl radicals. Extended X-Ray absorption fine structure (EXAFS) analysis shows that there are distinct differences in the local stuctures of the phenoxyl radicals associated with only the Cu(II) redox centers and those formed in the presences of the PPP polymer. X-ray absorption near edge spectroscopy (XANES) results provided evidence for the reduction of Cu(II) to Cu(I) in the EPFR forming process. The 1/e lifetimes of the formed EPFRs revealed a decay time of ~20 h for the Cu(II)CaMMT system and a two-step decay pattern for the PPP-Cu(II)CaMMT system with decay times of ~13.5 h and ~55.6 h. Finally, the generation of reactive oxygen species (hydroxyl radical; •OH) by these clay systems was also investigated, with higher concentrations of •OH detected for the phenol-dosed Cu(II)CaMMT and PPP-Cu(II)CaMMT systems, compared to the non-EPFR containing undosed PPP-Cu(II)CaMMT system. PMID:28670444

Consequences of the Thermal Transient on the Evolution of the Damaged Zone Around a Repository for Heat-Emitting High-Level Radioactive Waste in a Clay Formation: a Performance Assessment Perspective

NASA Astrophysics Data System (ADS)

Yu, Li; Weetjens, Eef; Sillen, Xavier; Vietor, Tim; Li, Xiangling; Delage, Pierre; Labiouse, Vincent; Charlier, Robert

2014-01-01

A proper evaluation of the perturbations of the host rock induced by the excavation and the emplacement of exothermic wastes is essential for the assessment of the long-term safety of high-level radioactive waste disposals in clay formations. The impact of the thermal transient on the evolution of the damaged zone (DZ) has been explored in the European Commission project TIMODAZ (thermal impact on the damaged zone around a radioactive waste disposal in clay host rocks, 2006-2010). This paper integrates the scientific results of the TIMODAZ project from a performance assessment (PA) point of view, showing how these results support and justify key PA assumptions and the values of PA model parameters. This paper also contextualises the significance of the thermal impact on the DZ from a safety case perspective, highlighting how the project outcomes result into an improved understanding of the thermo-hydro-mechanical behaviour of the clay host rocks. The results obtained in the TIMODAZ project strengthen the assessment basis of the safety evaluation of the current repository designs. There was no evidence throughout the TIMODAZ experimental observations of a temperature-induced additional opening of fractures nor of a significant permeability increase of the DZ. Instead, thermally induced plasticity, swelling and creep seem to be beneficial to the sealing of fractures and to the recovery of a very low permeability in the DZ, close to that of an undisturbed clay host rock. Results from the TIMODAZ project indicate that the favourable properties of the clay host rock, which guarantee the effectiveness of the safety functions of the repository system, are expected to be maintained after the heating-cooling cycle. Hence, the basic assumptions usually made in PA calculations so far are expected to remain valid, and the performance of the system should not be affected in a negative way by the thermal evolution of the DZ around a radioactive waste repository in clay host rock.

The influence of authigenic clay formation on the mineralogy and stable isotopic record of lacustrine carbonates

NASA Astrophysics Data System (ADS)

Bristow, Thomas F.; Kennedy, Martin J.; Morrison, Keith D.; Mrofka, David D.

2012-08-01

The mineralogical, compositional and stable isotopic variability of lacustrine carbonates are frequently used as proxies for ancient paleoenvironmental change in continental settings, under the assumption that precipitated carbonates reflect conditions and chemistry of ancient lake waters. In some saline and alkaline lake systems, however, authigenic clay minerals, forming at or near the sediment water interface, are a major sedimentary component. Often these clays are rich in Mg, influencing the geochemical budget of lake waters, and are therefore expected to influence the properties of contemporaneous authigenic carbonate precipitates (which may also contain Mg). This paper documents evidence for a systematic feedback between clay mineral and carbonate authigenesis through multiple precessionally driven, m-scale sedimentary cycles in lacustrine oil-shale deposits of the Eocene Green River Formation from the Uinta Basin (NE Utah). In the studied section, authigenic, Mg-rich, trioctahedral smectite content varies cyclically between 9 and 39 wt.%. The highest concentrations occur in oil-shales and calcareous mudstones deposited during high lake level intervals that favored sedimentary condensation, lengthening the time available for clay diagenesis and reducing dilution by other siliciclastic phases. An inverse relation between dolomite percentage of carbonate and trioctahedral smectite abundance suggests the Mg uptake during clay authigenesis provides a first order control on carbonate mineralogy that better explains carbonate mineralogical trends than the possible alternative controls of (1) variable Mg/Ca ratios in lake water and (2) degree of microbial activity in sediments. We also observe that cyclical change in carbonate mineralogy, believed to be induced by clay authigenesis, also causes isotopic covariation between δ13CPDB and δ18OPDB of bulk sediments because of differences in the equilibrium fractionation factors of dolomite and calcite (˜2‰ and ˜2.6%, respectively). This provides an alternative mechanism for the common pattern of isotopic covariation, which is typically attributed to the effect of simultaneous changes in water balance and biological activity on the carbon and oxygen isotopic composition of lake waters. These findings may help improve paleoenvironmental reconstructions based on lacustrine carbonate records by adding to the factors known to influence the mineralogical, compositional and stable isotopic signals recorded by lacustrine carbonates.

Montmorillonite-induced Bacteriophage φ6 Disassembly

NASA Astrophysics Data System (ADS)

Trusiak, A.; Gottlieb, P.; Katz, A.; Alimova, A.; Steiner, J. C.; Block, K. A.

2012-12-01

It is estimated that there are 1031 virus particles on Earth making viruses an order of magnitude more prevalent in number than prokaryotes with the vast majority of viruses being bacteriophages. Clays are a major component of soils and aquatic sediments and can react with RNA, proteins and bacterial biofilms. The clays in soils serve as an important moderator between phage and their host bacteria, helping to preserve the evolutionary balance. Studies on the effects of clays on viral infectivity have given somewhat contradictory results; possibly a consequence of clay-virus interactions being dependent on the unique structure of particular viruses. In this work, the interaction between montmorillonite and the bacteriophage φ6 is investigated. φ6 is a member of the cystovirus family that infects Pseudomonas syringe, a common plant pathogen. As a member of the cystovirus family with an enveloped structure, φ6 serves as a model for reoviruses, a human pathogen. Experiments were conducted with φ6 suspended in dilute, purified homoionic commercial-grade montmorillonite over a range of virus:clay ratios. At a 1:100000 virus:clay ratio, the clay reduced viral infectivity by 99%. The minimum clay to virus ratio which results in a measurable reduction of P. syringae infection is 1:1. Electron microscopy demonstrates that mixed suspensions of smectite and virus co-aggregate to form flocs encompassing virions within the smectite. Both free viral particles as well as those imbedded in the flocs are seen in the micrographs to be missing the envelope- leaving only the nucleocapsid (NC) intact; indicating that smectite inactivates the virus by envelope disassembly. These results have strong implications in the evolution of both the φ6 virus and its P. syringae host cells. TEM of aggregate showing several disassembled NCs.

Structures and mechanisms in clay nanopore trapping of structurally-different fluoroquinolone antimicrobials.

PubMed

Okaikue-Woodi, Fanny E K; Kelch, Sabrina E; Schmidt, Michael P; Enid Martinez, Carmen; Youngman, Randall E; Aristilde, Ludmilla

2018-03-01

Smectite clay nanoparticles are implicated in the retention of antimicrobials within soils and sediments; these clays are also inspected as drug carriers in physiological systems. Cation exchange is considered the primary adsorption mechanism of antimicrobials within smectite nanopores. However, a dual role of acid-base chemistry and adsorptive structures is speculated by recent studies. Using the prototypical smectite clay montmorillonite, we employed a combination of X-ray diffraction (XRD), nuclear magnetic resonance, attenuated total reflectance-Fourier transform infrared spectroscopy, and molecular dynamics simulations to investigate the interlayer nanopore trapping of two structurally-different fluoroquinolone (FQ) antimicrobials with similar acid-base chemistry: ciprofloxacin (a first-generation FQ) and moxifloxacin (a third-generation FQ). Greater sorption at pH 5.0 than at pH 7.0 for both FQs was consistent with cation-exchange of positively-charged species. However, the clay exhibited a near twofold higher sorption capacity for moxifloxacin than for ciprofloxacin. This difference was shown by the XRD data to be accompanied by enhanced trapping of moxifloxacin within the clay interlayers. Using the XRD-determined nanopore sizes, we performed molecular dynamics simulations of thermodynamically-favorable model adsorbates, which revealed that ciprofloxacin was adsorbed parallel to the clay surface but moxifloxacin adopted a tilted conformation across the nanopore. These conformations resulted in more slowly-exchanged than quickly-exchanged Na complexes with ciprofloxacin compared with moxifloxacin. These different Na populations were also captured by 23 Na nuclear magnetic resonance. Furthermore, the simulated adsorbates uncovered different complexation interactions that were corroborated by infrared spectroscopy. Therefore, beyond acid-base chemistry, our findings imply that distinct adsorbate structures control antimicrobial trapping within clay nanopores, which can promote persistence in environmental matrices and stable delivery in biological systems. Copyright © 2017 Elsevier Inc. All rights reserved.

Halloysite tubes as nanocontainers for anticorrosion coating with benzotriazole.

PubMed

Abdullayev, Elshad; Price, Ronald; Shchukin, Dmitry; Lvov, Yuri

2009-07-01

Halloysite clay nanotubes were investigated as a tubular container for the corrosion inhibitor benzotriazole. Halloysite is a naturally occurring cylindrical clay mineral with an internal diameter in the nanometer range and a length up to several micrometers, yielding a high-aspect-ratio hollow tube structure. Halloysite may be used as an additive in paints to produce a functional composite coating material. A maximum benzotriazole loading of 5% by weight was achieved for clay tubes of 50 nm external diameters and lumen of 15 nm. Variable release rates of the corrosion inhibitor were possible in a range between 5 and 100 h, as was demonstrated by formation of stoppers at tube openings. The anticorrosive performance of the sol-gel coating and paint loaded with 2-5% of halloysite-entrapped benzotriazole was tested on copper and on 2024-aluminum alloy by direct exposure of the metal plates to corrosive media. Kinetics of the corrosion spot formation at the coating defects was analyzed by the scanning vibrating electrode technique, and an essential damping of corrosion development was demonstrated for halloysite-loaded samples.

Clay with Desiccation Cracks is an Advection Dominated Environment

NASA Astrophysics Data System (ADS)

Baram, S.; Kurtzman, D.; Sher, Y.; Ronen, Z.; Dahan, O.

2012-04-01

Heavy clay sediments are regarded "safe" from the hydrological point of view due to their low hydraulic conductivities. However, the formation of desiccation cracks in dispersive clays may dramatically change their bulk hydraulic properties. The impact of desiccation cracks on water percolation, dissolved salts and contaminants transport and redox related reactions (microbial ammonium oxidation and denitrification) were investigated in 6 -12 m clay layer near a diary farm waste lagoon. The study implemented unique vadose-zone monitoring systems that enable in-situ measurements of the temporal variation of the sediment's water content along with frequent sampling of the sediment's pore water along the entire vadose zone (> 30 m). Results from four years of continuous measurements showed quick rises in sediment water content following rain events and temporal wastewater overflows. The percolation pattern indicated dominance of preferential flow through a desiccation-cracks network crossing the entire clay sediment layer. High water-propagation velocities (0.4 - 23.6 m h-1) were observed, indicating that the desiccation-crack network remains open and serves as a preferential flow pathway year-round, even at high sediment water content (~0.50 m3 m-3). The rapid percolation bypassed the most bio-geo-active parts of the soil, transporting even highly sorptive contaminants (testosterone and estrogen) in to the deep sections of the vadose zone, accelerating the underlying groundwater contamination. The ammonium and nitrate concentrations in the vadose zone and the high number of nitrifying and denitrifying bacteria (~108 gene copies gdry-sediemt-1, each) found in the sediment indicated that the entire vadose zone is aerated even at high water content conditions (~0.55 m3 m-3). The dissolved salts concentration in the pore-water and the δ2H-H2O and δ18O-H2O values of the pore-water substantially increased with depth (becoming less depleted) in the clay sediment, indicating deep soil evaporation. Daily fluctuation of the air temperature in the desiccation cracks supported thermally induced air convection within the cracks void and could explain the deep soil salinization process. Combination of all the abovementioned observations demonstrated that the formation of desiccation cracks network in dispersive clay sediments generates a bulk advection dominated environment for both air and water flow, and that the reference to clay sediments as "hydrologically safe" should to be reconsidered.

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

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

2013-08-01

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, 14 ,571) μg g⁻¹ and mean Fe concentration in the clay minerals was 2791 (±1782) μg g⁻¹. All specimens had Fe concentrations significantly higher (p ≤ 0.005) than the Fe concentration of WB (77 μg g⁻¹). 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.

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

Peptide formation in the prebiotic era - Thermal condensation of glycine in fluctuating clay environments

NASA Technical Reports Server (NTRS)

Lahav, N.; White, D.; Chang, S.

1978-01-01

As geologically relevant models of prebiotic environments, systems consisting of clay, water, and amino acids were subjected to cyclic variations in temperature and water content. Fluctuations of both variables produced longer oligopeptides in higher yields than were produced by temperature fluctuations alone. The results suggest that fluctuating environments provided a favorable geological setting in which the rate and extent of chemical evolution would have been determined by the number and frequency of cycles.

Evaluation of the predictive capability of coupled thermo-hydro-mechanical models for a heated bentonite/clay system (HE-E) in the Mont Terri Rock Laboratory

DOE PAGES

Garitte, B.; Shao, H.; Wang, X. R.; ...

2017-01-09

Process understanding and parameter identification using numerical methods based on experimental findings are a key aspect of the international cooperative project DECOVALEX. Comparing the predictions from numerical models against experimental results increases confidence in the site selection and site evaluation process for a radioactive waste repository in deep geological formations. In the present phase of the project, DECOVALEX-2015, eight research teams have developed and applied models for simulating an in-situ heater experiment HE-E in the Opalinus Clay in the Mont Terri Rock Laboratory in Switzerland. The modelling task was divided into two study stages, related to prediction and interpretation ofmore » the experiment. A blind prediction of the HE-E experiment was performed based on calibrated parameter values for both the Opalinus Clay, that were based on the modelling of another in-situ experiment (HE-D), and modelling of laboratory column experiments on MX80 granular bentonite and a sand/bentonite mixture .. After publication of the experimental data, additional coupling functions were analysed and considered in the different models. Moreover, parameter values were varied to interpret the measured temperature, relative humidity and pore pressure evolution. The analysis of the predictive and interpretative results reveals the current state of understanding and predictability of coupled THM behaviours associated with geologic nuclear waste disposal in clay formations.« less

Evaluation of the predictive capability of coupled thermo-hydro-mechanical models for a heated bentonite/clay system (HE-E) in the Mont Terri Rock Laboratory

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

Garitte, B.; Shao, H.; Wang, X. R.

Process understanding and parameter identification using numerical methods based on experimental findings are a key aspect of the international cooperative project DECOVALEX. Comparing the predictions from numerical models against experimental results increases confidence in the site selection and site evaluation process for a radioactive waste repository in deep geological formations. In the present phase of the project, DECOVALEX-2015, eight research teams have developed and applied models for simulating an in-situ heater experiment HE-E in the Opalinus Clay in the Mont Terri Rock Laboratory in Switzerland. The modelling task was divided into two study stages, related to prediction and interpretation ofmore » the experiment. A blind prediction of the HE-E experiment was performed based on calibrated parameter values for both the Opalinus Clay, that were based on the modelling of another in-situ experiment (HE-D), and modelling of laboratory column experiments on MX80 granular bentonite and a sand/bentonite mixture .. After publication of the experimental data, additional coupling functions were analysed and considered in the different models. Moreover, parameter values were varied to interpret the measured temperature, relative humidity and pore pressure evolution. The analysis of the predictive and interpretative results reveals the current state of understanding and predictability of coupled THM behaviours associated with geologic nuclear waste disposal in clay formations.« less

Biomineralization of endolithic microbes in rocks from the McMurdo Dry Valleys of Antarctica: implications for microbial fossil formation and their detection.

PubMed

Wierzchos, Jacek; Sancho, Leopoldo García; Ascaso, Carmen

2005-04-01

In some zones of Antarctica's cold and dry desert, the extinction of cryptoendolithic microorganisms leaves behind inorganic traces of microbial life. In this paper, we examine the transition from live microorganisms, through their decay, to microbial fossils using in situ microscopy (transmission electron microscopy, scanning electron microscopy in back-scattered electron mode) and microanalytical (energy dispersive X-ray spectroscopy) techniques. Our results demonstrate that, after their death, endolithic microorganisms inhabiting Commonwealth Glacier sandstone from the Antarctica McMurdo Dry Valleys become mineralized. In some cases, epicellular deposition of minerals and/or simply filling up of empty moulds by minerals leads to the formation of cell-shaped structures that may be considered biomarkers. The continuous deposition of allochthonous clay minerals and sulfate-rich salts fills the sandstone pores. This process can give rise to microbial fossils with distinguishable cell wall structures. Often, fossilized cell interiors were of a different chemical composition to the mineralized cell walls. We propose that the microbial fossil formation observed was induced by mineral precipitation resulting from inorganic processes occurring after the death of cryptoendolithic microorganisms. Nevertheless, it must have been the organic template that provoked the diffusion of mineral elements and gave rise to their characteristic distribution pattern inside the fossilized cells.

Interaction of Metal Oxides with Biomolecules: Implication in Astrobiology

NASA Astrophysics Data System (ADS)

Kamaluddin; Iqubal, Md. Asif

2014-08-01

Steps of chemical evolution have been designated as formation of biomonomers followed by their polymerization and then to modify in an organized structure leading to the formation of first living cell. Polymerization of biomonomers could have required some catalyst. In addition to clay, role of metal ions and metal complexes as prebiotic catalyst in the synthesis and polymerization of biomonomers cannot be ruled out. Metal oxides are important constituents of Earth crust and that of other planets. These oxides might have adsorbed organic molecules and catalyzed the condensation processes, which may have led to the formation of first living cell. Different studies were performed in order to investigate the role of metal oxides (especially oxides of iron and manganese) in chemical evolution. Iron oxides (goethite, akaganeite and hematite) as well as manganese oxides (MnO, Mn2O3, Mn3O4 and MnO2) were synthesized and their characterization was done using IR, powder XRD, FE-SEM and TEM. Role of above oxides was studied in the adsorption of ribose nucleotides, formation of nucleobases from formamide and oligomerization of amino acids. Above oxides of iron and manganese were found to have good adsorption affinity towards ribose nucleotides, high catalytic activity in the formation of several nucleobases from formamide and oligomerization of glycine and alanine. Characterization of products was performed using UV, IR, HPLC and ESI-MS techniques. Presence of hematite-water system on Mars has been suggested to be a positive indicator in the chemical evolution on Mars.

Ground-water resources of Liberty County, Texas, with a section on Stream runoff

USGS Publications Warehouse

Alexander, Walter H.; Breeding, S. D.

1950-01-01

Liberty County is in the Gulf Coastal Plain of southeastern Texas in the second tier of counties back from the Gulf. The geologic formations discussed in this report in upward sequence consist of the Oakville sandstone of Miocene age and the Lagarto clay of Miocene (?) age, the Willis sand of Pliocene (?) age, and the Lissie formation and Beaumont clay of Pleistocene age. The rocks of these formations crop out in belts roughly parallel to the Gulf shore and dip southeastward. As one travels across San Jacinto and Liberty Counties from northwest to southeast the belts of outcrop are traversed in the above order, beginning with the 0akville sandstone and Lagarto clay. The land surface slopes southeastward toward the Gulf at a rate less than the dip of the rocks; consequently artesian conditions exist in all parts of the county. The valley of the Trinity River is well known for its flowing weds, which range from 100 to 808 feet in depth. Most of the ground water used in the county is obtained from wells ranging in depth from 350 to about 1,000 feet and is drawn from the Lissie formation. Wells yielding 1,000 to 3,500 gallons a minute and ranging from 740 to 1,030 feet in depth have been developed for rice irrigation in the North Dayton area, in the southwestern part of the county. These wells draw water mostly from sands in the Lissie formation, but most of them are also screened in overlying thinner sands in the Beaumont clay. The municipal water supplies of Liberty, Cleveland, Dayton, and Diasetta are obtained from wells ranging from 350 to 833 feet in depth with reported yields of 300 to 350 gallons a minute. Most of the wells in the rural areas are less than 50 feet in depth and furnish small supplies of water for domestic use and for stock. Such supplies can be obtained almost anywhere in the county from shallow wells in the Lissie and Beaumont formations or in alluvial deposits. The average daily withdrawal of ground water for irrigation, public supply, and industrial use is estimated to have been about 7,500,000 gallons in 1944, distributed as follows: irrigation, 6,780,000 gallons; public supply, 325,000 gallons; and industrial use, 395,000 gallons.

Modelling Iron-Bentonite Interactions

NASA Astrophysics Data System (ADS)

Watson, C.; Savage, D.; Benbow, S.; Wilson, J.

2009-04-01

The presence of both iron canisters and bentonitic clay in some engineered barrier system (EBS) designs for the geological disposal of high-level radioactive wastes creates the potential for chemical interactions which may impact upon the long-term performance of the clay as a barrier to radionuclide migration. Flooding of potential radionuclide sorption sites on the clay by ferrous ions and conversion of clay to non-swelling sheet silicates (e.g. berthierine) are two possible outcomes deleterious to long-term performance. Laboratory experimental studies of the corrosion of iron in clay show that corrosion product layers are generally thin (< 1 µm) with magnetite, siderite, or ‘green rust' occurring depending upon temperature and ambient partial pressure of carbon dioxide. In theory, incorporation of iron into clay alteration products could act as a ‘pump' to accelerate corrosion. However, the results of laboratory experiments to characterise the products of iron-bentonite interaction are less than unequivocal. The type and amounts of solid products appear to be strong functions of time, temperature, water/clay ratio, and clay and pore fluid compositions. For example, the products of high temperature experiments (> 250 °C) are dominated by chlorite, whereas lower temperatures produce berthierine, odinite, cronstedtite, or Fe-rich smectite. Unfortunately, the inevitable short-term nature of laboratory experimental studies introduces issues of metastability and kinetics. The sequential formation in time of minerals in natural systems often produces the formation of phases not predicted by equilibrium thermodynamics. Evidence from analogous natural systems suggests that the sequence of alteration of clay by Fe-rich fluids will proceed via an Ostwald step sequence. The computer code, QPAC, has been modified to incorporate processes of nucleation, growth, precursor cannibalisation, and Ostwald ripening to address the issues of the slow growth of bentonite alteration products. This, together with inclusion of processes of iron corrosion and diffusion, has enabled investigation of a representative model of the alteration of bentonite in a typical EBS environment. Simulations with fixed mineral surface areas show that berthierine dominates the solid product assemblage, with siderite replacing it at simulation times greater than 10 000 years. Simulations with time-dependent mineral surface areas show a sequence of solid alteration products, described by: magnetite -> cronstedtite -> berthierine -> chlorite. Using plausible estimates of mineral-fluid interfacial free energies, chlorite growth is not achieved until 5 000 years of simulation time. The results of this modelling work suggest that greater emphasis should be placed upon methods to up-scale the results of laboratory experiments to timescales of relevance to performance assessment.

Hydrodynamic impacts on biogenic stabilisation and the fate of extracellular polymeric substances (EPS) in mixed sediment bedforms.

NASA Astrophysics Data System (ADS)

Hope, J. A.; Aspden, R.; Schindler, R.; Parsons, D. R.; Ye, L.; Baas, J.; Paterson, D. M.

2014-12-01

The stability and morphology of bedforms have traditionally been treated as a function of mean flow velocity/non-dimensional bed shear stress and sediment particle size, despite the known influence of key biological components such as extracellular polymeric substances (EPS). EPS is produced by microbial communities and can increase erosion thresholds by more than 300%. However, the mechanisms behind the influence of EPS on sediment transport and bedform dynamics is poorly understood, as is the fate of EPS and exchange of EPS between the sediment bed and water column during ripple formation. The exchange of EPS between the sediment bed and water column is dynamic, with important implications for a range of physical and geochemical processes, with the spatio-temporal variation in EPS content, from source to eventual fate, being extremely important for determining the behaviour and natural variability of sedimentary systems. This paper reports on a series of flume experiments where a tripartite mixture of sand, clay and model EPS (xanthan gum) was used to create a sediment substrate, which was subject to a unidirectional current (0.8 ms-1 for 10.5 hrs, n=6). For each run the spatio-temporal changes in concentration, distribution, and effect of EPS, on the evolving bed of mixed sediment was monitored throughout, with complete 3D bed morphology scans also acquired at ~360 s intervals. The various substrate mixtures produced bedforms varying from ripples to dunes and biochemical analysis of EPS concentration across the formed bedforms, suggest EPS is winnowed from the sediment - water interface, particularly at the bedform crests. The depth of winnowing in each run was found to be related to the bedform size, with variation in the stoss, crest and trough of the bedforms identified. The loss of EPS was also significantly correlated with the depth to which clay was winnowed, presumably due to a close association between the clay mineral and EPS fractions. The paper will discuss how sediment processes and flow are linked by migration of dissolved and particulate substances into and out of the bed and how this exchange is affected by the topography of the sediment bed and advective pore water transfers. Finally, the implications for natural systems and larger scale sediment-biota linkages will also be discussed.

Subsurface geology of the late Tertiary and Quaternary water-bearing deposits of the southern part of the San Joaquin Valley, California

USGS Publications Warehouse

Croft, M.G.

1972-01-01

The study area, which includes about 5,000 square miles of the southern part of the San Joaquin Valley, is a broad structural trough of mostly interior drainage. The Sierra Nevada on the east is composed of consolidated igneous and metamorphic rocks of pre-Tertiary age. The surface of these rocks slopes 4?-6? southwestward from the foothills and underlies the valley. The Coast Ranges on the west consist mostly of complexly folded and faulted consolidated marine and nonmarine sedimentary rocks of Jurassic, Cretaceous, and Tertiary age, which dip eastward and overlie the basement complex. Unconsolidated deposits, of late Pliocene to Holocene age, blanket the underlying consolidated rocks in the valley and are the source of most of the fresh ground water. The unconsolidated deposits, the subject of this report, are divided into informal stratigraphic units on the basis of source of sediment, environment of deposition, and texture. Flood-basin, lacustrine, and marsh deposits are fine grained and underlie the valley trough. They range in age from late Pliocene to Holocene. These deposits, consisting of nearly impermeable gypsiferous fine sand, silt, and clay, are more than 3,000 feet thick beneath parts of Tulare Lake bed. In other parts of the trough, flood-basin, lacustrine, and marsh deposits branch into clayey or silty clay tongues designated by the letter symbols A to F. Three of these tongues, the E, C, and A clays, lie beneath large areas of the southern part of the valley. The E clay includes the Corcoran Clay Member of the Tulare Formation, the most extensive hydrologic confining layer in the valley. The E clay underlies about 3,500 square miles of bottom land and western slopes. The beds generally are dark-greenish-gray mostly diatomaceous silty clay of Pleistocene age. Marginally, the unit bifurcates into an upper and a lower stratum that contains thin beds of moderately yellowish-brown silt and sand. The E clay is warped into broad, gentle northwesterly trending anticlines and synclines. The C clay, of Pleistocene age, is a fine-grained lacustrine or paludal deposit occurring 220-300 feet beneath Tulare Lake bed and parts of Fresno Slough. The beds consist of bluish-gray silty clay. Structural contours indicate that the C clay has been extensively warped and folded. The A clay of Pleistocene and Holocene (?) age is a fine-grained lacustrine or paludal deposit occurring 10-60 feet beneath Buena Vista, Kern, and Tulare Lake beds, and parts of Fresno Slough. The clay is mainly blue or dark greenish gray, plastic, and highly organic. In some areas the unit is separated into an upper and a lower stratum by several feet of sand. A radiocarbon date of 26,780 ? 600 years was obtained from wood cored 3 feet beneath the clay. Continental deposits are arkosic beds of late Pliocene and Pleistocene (?) age and were derived from the Sierra Nevada, Tehachapi, and San Emigdio Mountains. In places, a reduced-oxidized contact transgresses the deposits derived from the Sierra Nevada. The reduced deposits consist of moderately permeable bluish-green or bluish-gray fine to medium sand, silt, and clay. The oxidized deposits consist mainly of poorly permeable yellowish-brown silt and fine sand. Deposits derived from the Tehachapi and the San Emigdio Mountains consist of poorly to moderately permeable yellowish-brown sand and silt. Continental and alluvial deposits of Tertiary and Quaternary age that were derived from the Coast Ranges consist mainly of poorly to moderately permeable yellowish-brown gravel, sand, silt, and clay. They include the Tulare Formation and overlying alluvial deposits. Alluvium is composed of coarse arkosic deposits derived from the Sierra Nevada, Tehachapi, and San Emigdio Mountains. A reduced-oxidized contact also transgresses the alluvial deposits derived from the Sierra Nevada. The oxidized deposits consist of poorly to highly permeable yellowish-brown gravel, sand, silt, and clay. The reduc

Macro-scale deformation behavior and characterization of deformation mechanisms below µm-scale in experimentally deformed Boom Clay by using the combination of triaxial compression, X-ray µ-CT imaging, DIC, BIB cross sectioning, and SEM

NASA Astrophysics Data System (ADS)

Oelker, Anne; Desbois, Guillaume; Urai, Janos L.; Bésuelle, Pierre; Viggiani, Gioacchino; Levasseur, Séverine

2017-04-01

Boom Clay is one formation being studied in Belgium as a potential host rock for deep geological disposal of radioactive waste. This poorly indurated clay presents in its natural state favorable properties against the migration of radionuclides: low permeability, low solute diffusion rates, good retention and sorption capacity for many radionuclides and good self-sealing capacity. During construction of disposal galleries, stress redistribution will lead to perturbation of the clay and the formation around galleries of the so-called "Excavation disturbed Zone" (EdZ). The study of deformation mechanisms and evolution of Boom Clay properties at macro but also micro scale allows to assess in a more mechanistic way the evolution of Boom Clay properties in this EdZ. In this work, we show microstructural investigations of Boom Clay deformed in undrained triaxial compression by linking conventional stress/strain curves with Digital Image Correlation (DIC) and scanning electron microscopy (SEM) imaging of broad-ion-beam (BIB) milled cross-sections to deduce deformation mechanisms based on microstructures at sub-micron resolution. Two specimens, collected in Mol (Belgium) at the European Underground Laboratories (URL) on HADES level, were analyzed: The major principal stress σ1 was applied parallel as well as perpendicular to the bedding direction with an initial mean normal effective stress of 4.5 MPa and an initial pore water pressure of 2.3 MPa, which are equal to the in-situ values. Linking the resulting DIC-derived maps of incremental strains with the corresponding stress/strain curve give not only information about the moment of the shear band development, but also on the way strain evolves within the specimen throughout the rest. Incremental DIC analysis of X-ray tomographic scans performed during loading tests give a time evolution of the strain field, and subsequently allow to detect strain localization which appears close to the stress peak. Regions with a comparable high and low shear strain were chosen and prepared for BIB-SEM investigations. In this case, shear bands show typical characteristics of uncemented small-grained clay-rich materials deformed at high shear strains including anastomosing shears. At nano-scale, the preferential orientation of clay particles in the anastomosing shears are construed to be responsible for the shear weakness. In addition, the reorientation of clay particles during the deformation leads to the strong reduction of porosity in the shear band. Ductile deformation mechanisms represented by grain-rotation, grain-sliding, bending, and granular flow are strongly involved for the development of the shear band.

Sediment composition and texture of Pleistocene deep-sea turbidites in the eastern Nankai Trough gas hydrate field

NASA Astrophysics Data System (ADS)

Egawa, K.; Nishimura, O.; Izumi, S.; Ito, T.; Konno, Y.; Yoneda, J.; Jin, Y.; Kida, M.; Suzuki, K.; Nakatsuka, Y.; Nagao, J.

2013-12-01

In the 2012 JOGMEC/JAPEX pressure coring operation, we collected a totally 60-m-long core sample from the interval of gas hydrate concentration zone at the planned site of the world's first offshore production test of natural gas hydrates in the eastern Nankai Trough area. In this contribution, the cored sediments were sedimentologically, mineralogically, and paleontologically analyzed to know sediment composition and texture of reservoir formation, which are known to provide useful geological information to discuss sedimentation, diagenesis, and permeability. The targeted interval belongs to a Middle Pleistocene deep-sea turbidite sequence distributed around the Daini Atsumi Knoll, east of the Kumano forearc basin, and consists of the lower (thick sand-dominant), middle (thin-bedded sand-and-mud alteration), and upper (mud-dominant) formations in ascending order. X-ray powder diffraction analysis and scanning electron microscopic observation revealed that pore space in turbidite sands is commonly filled with clay fractions (mostly phyllosilicates) in the lower formation. Such a pore filling of clay fractions is reflected in particle size distribution showing high standard deviation and clay content, and thus is expected to have an impact on permeability. There is the older Pliocene to Early Pleistocene fossil coccolith record in the middle formation, indicating sediment reworking probably induced by submarine landslide. The coexistence of authigenic siderite and framboidal pyrite in the middle formation strongly suggests anoxic microbial activity under methane oxidation and sulfide reduction conditions at least before the hydrate cementation. This contribution was financially supported by the Research Consortium for Methane Hydrate Resources in Japan (MH21 Research Consortium) planned by the Ministry of Economy, Trade and Industry (METI).

Clay-Bacteria Systems and Biofilm Production

NASA Astrophysics Data System (ADS)

Steiner, J.; Alimova, A.; Katz, A.; Steiner, N.; Rudolph, E.; Gottlieb, P.

2007-12-01

Soil clots and the aerosol transport of bacteria and spores are promoted by the formation of biofilms (bacteria cells in an extracellular polymeric matrix). Biofilms protect microorganisms by promoting adhesion to both organic and inorganic surfaces. Time series experiments on bacteria-clay suspensions demonstrate that biofilm growth is catalyzed by the presence of hectorite in minimal growth media for the studied species: Gram negatives (Pseudomonas syringae and Escherichia coli,) and Gram positives (Staphylococcus aureus and Bacillus subtilis). Soil organisms (P. syringae, B. subtilis) and organisms found in the human population (E. coli, S. aureus) are both used to demonstrate the general applicability of clay involvement. Fluorescent images of the biofilms are acquired by staining with propidium iodide, a component of the BacLightTM Live/Dead bacterial viability staining kit (Molecular Probes, Eugene, OR). The evolving polysaccharide-rich biofilm reacts with the clay interlayer site causing a complex substitution of the two-water hectorite interlayer with polysaccharide. The result is often a three-peak composite of the (001) x-ray diffraction maxima resulting from polysaccharide-expanded clays and an organic-driven contraction of a subset of the clays in the reaction medium. X-ray diffractograms reveal that the expanded set creates a broad maximum with clay subsets at 1.84 nm and 1.41 nm interlayer spacings as approximated by a least squares double Lorentzian fit, and a smaller shoulder at larger 2q, deriving from a contraction of the interlayer spacing. Washing with chlorox removes organic material from the contracted clay and creates a 1-water hectorite single peak in place of the double peak. The clay response can be used as an indirect indicator of biofilm in an environmental system.

Heavy metal content and potential health risk of geophagic white clay from the Kumasi Metropolis in Ghana.

PubMed

Nkansah, Marian Asantewah; Korankye, Mavis; Darko, Godfred; Dodd, Matt

2016-01-01

Geophagia is the craving for non-food substances and commonly practiced among pregnant women and children. Consumption of geophagic clay samples can have serious implications on the health of the consumers as a result of the presence of toxic metals such as Pb, As, Hg and Cd. This study sought to determine the levels of heavy metals in the studied geophagic clay samples and to determine the potential risks of heavy metals as cumulative carcinogenic and non-carcinogenic risks to the health of the consumers via oral (ingestion) and dermal exposure routes. A total of thirty (30) white clay samples were analysed using Niton Thermo scientific XRF Analyser (Mobile Test S, NDTr-XL3t-86956, com 24). The clay samples were found to contain essential elements such as Ca, Fe, K and Zn as well as toxic metals such as As and Pb. There were isolated cases of the presence of Hg and all samples had Cd levels below detection. Health risk indices such as hazard quotient and cancer risk were calculated and the results indicated that consumers are likely to suffer from cancer through ingestion of geophagic clay. Bioaccessibility studies were done on zinc and it did not indicate any potential toxicity due to zincs essential nature. The levels of heavy metals in some of the geophagic clay consumed by some residents in the Kumasi were high compared to the Permitted Maximum Tolerable Daily Intake (PMTDI) by (WHO/FAO) and may pose potential health threat over time.

In vitro toxicological assessment of clays for their use in food packaging applications.

PubMed

Maisanaba, Sara; Puerto, María; Pichardo, Silvia; Jordá, María; Moreno, F Javier; Aucejo, Susana; Jos, Ángeles

2013-07-01

Montmorillonite based clays have a wide range of applications that are going to contribute to increase human exposure to these materials. One of the most promising uses of clays is the development of reinforced food contact materials that results in nanocomposites with improved barrier properties. Different organoclays have been developed introducing modifiers in the natural clay which is commercially available. However, the toxicological aspects of these materials have been scarcely studied so far. In the present study, the cytotoxic effects of a non-modified clay (Cloisite Na+) and an organoclay (Cloisite 30B) have been investigated in the hepatic cell line HepG2. Only Cloisite 30B showed cytotoxicity. In order to elucidate the toxic mechanisms underlying these effects, apoptosis, inflammation, oxidative stress and genotoxicity biomarkers were assayed. Moreover, a morphology study with light and electron microscopy was performed. Results showed genotoxic effects and glutathione decrease. The most relevant ultraestructural alterations observed were mitochondrial degeneration, dilated endomembrane systems, heterophagosomes formation, fat droplets appearance and presence of nuclear lipid inclusions. Cloisite 30B, therefore, induces toxic effects in HepG2 cells. Further research is needed to assess the risk of this clay on the human health. Copyright © 2013 Elsevier Ltd. All rights reserved.

VIS/NIR Spectroscopy to determine the spatial variation of the weathering degree in Paleogene clay soil - London Clay Formation

NASA Astrophysics Data System (ADS)

Nasser, Mohammed; Gibson, Andy, ,, Dr; Koor, Nick, ,, Dr; Gale, Professor Andy; Huggett, Jenny, ,, Dr; Branch, Steve

2017-04-01

The London Clay Formation (LCF) which underlies much of South-East England is hugely important as a construction medium. However, its geotechnical performance (shear strength, compressive strength, shrink-swell behaviour, etc. ) is greatly affected by its degree of weathering. Despite this importance, little attention has been focussed on a robust method to define and measure its degree of weathering. This is perhaps a result of a well-known colour change from bluish-grey to brown that accompanies 'weathering' and considered to be the result of oxidisation (Chandler and Apted 1988). Through wide experience, this definition is normally effective, but it is perhaps subjective and reliant on the experience of the investigator and the ability to observe samples or exposures. More objective investigation, typically using SEM is not normally economically feasible or expedient for construction works. We propose a simple, robust method to characterise the degree of weathering in the LCF using reflective or Visible-Near-InfraRed-Spectroscopy (VNIRS). 24 samples were extracted from 2 boreholes drilled in the Hampstead area of London to depths of 12 m within the uppermost Claygate Member of the LCF. VNIRS spectra (350-2500 nm) were measured from all samples and compared with XRD, XRF, SEM and PSD results on the same samples. Results show increased magnitude of absorption features related to clay mineralogy around 1400, 1900 and 2200 nm to a depth of 5 m beneath ground level. Beneath this depth, the absorption features show little variation. SEM analyses show corresponding changes in the degradation of pyrite crystals and individual clay (illite/smectite). These preliminary results show that there is a good potential for VNIRS spectroscopy to determine the variation of weathering in the LCF.

Widespread Surface Weathering on Early Mars: possible implication on the Past Climate

NASA Astrophysics Data System (ADS)

Loizeau, Damien; Carter, John; Mangold, Nicolas; Poulet, François; Rossi, Angelo P.; Allemand, Pascal; Lozac'h, Loïc; Quantin, Cathy; Bibring, Jean-Pierre

2015-04-01

The recent discovery of widespread hydrous clays on Mars with OMEGA/Mars Express and CRISM/MRO indicates that diverse and widespread aqueous environments existed on Mars, from the surface to kilometric depths [1, 2]. The study of the past habitability and past climates of the planet requires assessing the importance of sustained surface water vs. subsurface water in its aqueous history. Vertical sequences of Al-rich clays on top of Fe/Mg-rich clays in the top tens of meters of the surface are identified on Mars [3-6] (see figure 1) and interpreted as possible weathering profiles, similar to cases of pedogenesis on Earth (e.g. [7, 8]). A global study of these clay sequences has recently been published by Carter et al. [9]. This following work presents detailed geological analysis, performed for each identified candidate, in order to constrain their age and origin. With the increasing availability of CTX and HiRISE stereoimages, we investigate the thickness of the altered sequences, the age of the altered units and the different geological contexts to further understand the weathering process(es), and their possible implication on the past climate. The types of geologic settings where the interpreted weathering profiles are observed are much varied: from basin floor to plateaus, in apparent massive rocks to finely layered rocks. Besides, the number and variety of sequences is/was likely larger. However, in term of chronology, the alteration seems to have stopped in a relatively limited period of time for the studied cases, between 3.8 and 3.6 Ga. This would point to a formation due to a global process that enabled liquid water at the surface and pedogenesis in various regions, on various terrains, from late Noachian to early Hesperian. This global process would imply regular, widely distributed ice or precipitations in large regions of Mars at that time. If weathering occurred before that time, during the early or middle Noachian, the sequences may have been erased by the more intense erosion of that time. Also, it is difficult to date older terrains by crater counting on small surfaces. These observations make a strong constrain concerning the past habitability of Mars: liquid water has been widely available at the surface of the planet, in contact with different rocks, until the early Hesperian time. Acknowledgment: Some of the authors have received funding from the ERC (FP7/2007-2013)/ERC Grant agreement n° 280168. References: [1] Ehlmann B., et al. Nature, 479, 53-60 (2011). [2] Carter J., et al. JGR, 118, 831-858 (2013) [3] Gaudin A., et al. Icarus, 216(1), 257-268 (2011). [4] Loizeau D., et al. Icarus, 205, 396-418 (2010). [5] Noe Dobrea E., et al. JGR, 115, E00D19 (2010). [6] Le Deit L., et al. JGR, 117, E00J05 (2012). [7] Velde B., et al. Ed. Springer, Berlin, (1995). [8] Wilson M. Clay Minerals, 39, 233-266 (2004). [9] Carter J., et al. Icarus, 248, 373-382.

Development of eco-friendly porous fired clay bricks using pore-forming agents: a review.

PubMed

Bories, Cecile; Borredon, Marie-Elisabeth; Vedrenne, Emeline; Vilarem, Gerard

2014-10-01

Today, clay bricks are facing technological challenges and are uncompetitive compared to materials such as concrete. Their performance must be improved if they are to stand up to the competition. Increasing environmental concerns over the accumulation of unmanaged wastes from agricultural or industrial productions have made these good candidates for incorporation into building materials to improve their performance. This process leads to the formation of pores in the bricks, producing lightweight and sustainable building materials. This paper reviews the different pore-forming agents from renewable or mineral resources as described in the literature. It also presents the impact of pore-forming agents on the physical, mechanical and thermal properties of clay bricks. Copyright © 2014 Elsevier Ltd. All rights reserved.

Compositional characteristics of the Fire Clay coal bed in a portion of eastern Kentucky

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

Hower, J.C.; Andrews, W.M. Jr.; Rimmer, S.M.

The Fire Clay (Hazard No. 4) coal bed (Middle Pennsylvanian Breathitt Formation) is one of the most extensively mined coal in eastern Kentucky. The coal is used for metallurgical and steam end uses and, with its low sulfur content, should continue to be a prime steam coal. This study focuses on the petrology, mineralogy, ash geochemistry, and palynology of the coal in an eight 7.5-min quadrangle area of Leslie, Perry, Knott, and Letcher counties.

Mineralogical constraints on the paleoenvironments of the Ediacaran Doushantuo Formation

PubMed Central

Bristow, Thomas F.; Kennedy, Martin J.; Derkowski, Arkadiusz; Droser, Mary L.; Jiang, Ganqing; Creaser, Robert A.

2009-01-01

Assemblages of clay minerals are routinely used as proxies for paleoclimatic change and paleoenvironmental conditions in Phanerozoic rocks. However, this tool is rarely applied in older sedimentary units. In this paper, the clay mineralogy of the Doushantuo Formation in South China is documented, providing constraints on depositional conditions of the Ediacaran Yangtze platform that host the earliest animal fossils in the geological record. In multiple sections from the Yangtze Gorges area, trioctahedral smectite (saponite) and its diagenetic products (mixed-layer chlorite/smectite, corrensite, and chlorite) are the dominant clays through the lower 80 m of the formation and constitute up to 30 wt% of the bulk rock. Saponite is interpreted as an in situ early diagenetic phase that formed in alkaline conditions (pH ≥ 9). The absence of saponite in stratigraphically equivalent basin sections, 200–400 km to the south, indicates that alkaline conditions were localized in a nonmarine basin near the Yangtze Gorges region. This interpretation is consistent with crustal abundances of redox-sensitive trace elements in saponitic mudstones deposited under anoxic conditions, as well as a 10‰ difference in the carbon isotope record between Yangtze Gorges and basin sections. Our findings suggest that nonmarine environments may have been hospitable for the fauna preserved in the Yangtze Gorges, which includes the oldest examples of animal embryo fossils and acanthomorphic acritarchs. PMID:19666508

Radiometric ages of the Fire Clay tonstein [Pennsylvanian (Upper Carboniferous), Westphalian, Duckmantian]: A comparison of U-Pb zircon single-crystal ages and 40Ar/39Ar sanidine single-crystal plateau ages

USGS Publications Warehouse

Lyons, P.C.; Krogh, T.E.; Kwok, Y.Y.; Davis, D.W.; Outerbridge, W.F.; Evans, H.T.

2006-01-01

The Fire Clay tonstein [Pennsylvanian (Upper Carboniferous), Westphalian Series, Duckmantian Stage]-a kaolinized, volcanic-ash deposit occurring in Kentucky, West Virginia, Tennessee, and Virginia-is the most widespread bed in the Middle Pennsylvanian of the central Appalachian basin, USA. A concordant single-crystal U-Pb zircon datum for this tonstein gives a 206Pb/238U age of 314.6 ?? 0.9 Ma (2??). This age is in approximate agreement with a mean sanidine plateau age of 311.5 ?? 1.3 Ma (1??, n = 11) for the Fire Clay tonstein. The difference between the two ages may be due to bias between the 40K and 238U decay constants and other factors. The age of the Fire Clay tonstein has important implications for Duckmantian Stage (Westphalian Series) sedimentation rates, correlations with the Westphalian Series of Europe, Middle Pennsylvanian volcanic events, and the late Paleozoic time scale. ?? 2006 Elsevier B.V. All rights reserved.

Thermal and colloidal behavior of amine-treated clays: the role of amphiphilic organic cation concentration.

PubMed

Marras, S I; Tsimpliaraki, A; Zuburtikudis, I; Panayiotou, C

2007-11-15

The modification of sodium montmorillonite (NaMMT) through the insertion of amphiphilic hexadecylammonium cations into the clay's interlayer spaces has been studied. Alkylammonium concentrations equivalent to 0.15-3.00 times the cation exchange capacity of the clay were used. The conformation of the surfactant cations in the confined space of the silicate galleries was investigated by X-ray diffraction analysis and scanning electron microscopy, while the organoclay's thermal stability was examined by thermogravimetric analysis. The clay's surface properties induced by the ion-exchange process were followed by measurements of the mineral's zeta potential as a function of pH and surfactant concentration, while the coagulation rates of organoclay suspensions in water and in chloroform were examined using dynamic light scattering. All the results are consistent with showing that the overall characteristics and thus the behavior of the modified MMT particles strongly depend on the alkylammonium surfactant concentration used in the modification process. This, however, has very important implications for any attempt to incorporate the organomodified MMT particles into different media for various applications such as polymer nanocomposite preparation.

Crystal structure control of aluminized clay minerals on the mobility of caesium in contaminated soil environments

NASA Astrophysics Data System (ADS)

Dzene, Liva; Ferrage, Eric; Viennet, Jean-Christophe; Tertre, Emmanuel; Hubert, Fabien

2017-02-01

Radioactive caesium pollution resulting from Fukushima Dai-ichi and Chernobyl nuclear plant accidents involves strong interactions between Cs+ and clays, especially vermiculite-type minerals. In acidic soil environments, such as in Fukushima area, vermiculite is subjected to weathering processes, resulting in aluminization. The crystal structure of aluminized clays and its implications for Cs+ mobility in soils remain poorly understood due to the mixture of these minerals with other clays and organic matter. We performed acidic weathering of a vermiculite to mimic the aluminization process in soils. Combination of structure analysis and Cs+ extractability measurements show that the increase of aluminization is accompanied by an increase in Cs+ mobility. Crystal structure model for aluminized vermiculite is based on the interstratification of unaltered vermiculite layers and aluminized layers within the same particle. Cs+ in vermiculite layers is poorly mobile, while the extractability of Cs+ is greatly enhanced in aluminized layers. The overall reactivity of the weathered clay (cation exchange capacity, Cs+ mobility) is then governed by the relative abundance of the two types of layers. The proposed layer model for aluminized vermiculite with two coexisting populations of caesium is of prime importance for predicting the fate of caesium in contaminated soil environments.

Clay illuviation provides a long-term sink for C sequestration in subsoils

NASA Astrophysics Data System (ADS)

Torres-Sallan, Gemma; Schulte, Rogier P. O.; Lanigan, Gary J.; Byrne, Kenneth A.; Reidy, Brian; Simó, Iolanda; Six, Johan; Creamer, Rachel E.

2017-04-01

Soil plays a key role in the global carbon (C) cycle. Most current assessments of SOC stocks and the guidelines given by Intergovernmental Panel on Climate Change (IPCC) focus on the top 30 cm of soil. Our research shows that, when considering only total quantities, most of the SOC stocks are found in this top layer. However, not all forms of SOC are equally valuable as long-term stable stores of carbon: the majority of SOC is available for mineralisation and can potentially be re-emitted to the atmosphere. SOC associated with micro-aggregates and silt plus clay fractions is more stable and therefore represents a long-term carbon store. Our research shows that most of this stable carbon is located at depths below 30 cm (42% of subsoil SOC is located in microaggregates and silt and clay, compared to 16% in the topsoil), specifically in soils that are subject to clay illuviation. This has implications for land management decisions in temperate grassland regions, defining the trade-offs between primary productivity and C emissions in clay-illuviated soils, as a result of drainage. Therefore, climate smart land management should consider the balance between SOC stabilisation in topsoils for productivity versus sequestration in subsoils for climate mitigation.

Nonlinear Propagation of Sound in Recently Settled Flocculated Sediments

NASA Astrophysics Data System (ADS)

Reed, A. H.; Sanders, W. M.

2016-12-01

Cohesive sediments undergo changes in a whirlwind. Dumped out of the river and into the estuary, they get bathed in salty water and subject to turbulent motion. During this sequence of events, the clay particles form clay aggregates of larger size with higher settling rates than the clay particles. Once the flocs have settled, cohesive sediments may form a sediment deposit of mud. Our interest is in the factors that control the development of soundspeed within these muds. This paper addresses organic matter influences on floc aggregation and settling rates. In laboratory studies, organic matter type differed in mixtures with either bentonite or kaolinite clays. The organic matter types used were guar gum, a net positive biopolymer, and xanthan gum, a net negative biopolymer derived from bacterial exudates, similar to those commonly found in estuaries. These biopolymers were dissolved into low salinity water (0-10 ppt). The biopolymer mixture was degassed and during the degassing process, either bentonite or kaolinite clay was added to the vessel. Surprisingly, different settling rates occurred in the clay-biopolymer mixtures. The settling rates of the clay-guar mixtures was more rapid (1-2 days) than the settling rate for the clay-xanthan mixtures. While clay-guar consolidated further, clay-xanthan maintained consistency for more than 2 weeks with density slowly increasing during that period. Compressional soundspeed (Vp) measurements were made with depth through the vessel using 0.5 mHz piezoelectric transducers. It was found that Vp in water was similar to that of the clay-xanthan. Vp was the same in the upper 6 cm of mud as it was in the overlying water and Vp decreased to become slower with increasing depth. Compressional wave velocity (Vp) also changed slightly with the guar complexes below the sediment water interface to the depth of the vessel. Vp was slightly slower in the mud than in the water column. Vp of the water was 1480-1495 m/s whereas Vp within the clay-biopolymer was below the minimum Vp in the water column. This slight decrease in Vp with depth is consistent for that of naturally occurring surficial mud deposits. This work suggests that organic matter type can play a critical role in the rate of consolidation within a mud deposit, which has implications for mud strength development and transport potential.

Pyromorphite Formation And Stability After Quick Lime Neutralisation In The Presence Of Soil And Clay Sorbents

EPA Science Inventory

Soluble Pb is immobilised in pure systems as pyromorphite by adding sources of P, but doubts remain about the efectiveness of this approach in natural soil systems, particularly given the ability of soil humic substances to interfere with Pb-mineral formation. In addition, recen...

The Collins Creek and Pleasant Creek Formations: Two new upper cretaceous subsurface units in the Carolina/Georgia Coastal Plain

USGS Publications Warehouse

,; Prowell, D.C.; Christopher, R.A.

2004-01-01

This paper formally defines two new Upper Cretaceous subsurface units in the southern Atlantic Coastal Plain of North Carolina, South Carolina and Georgia: the Collins Creek Formation and the Pleasant Creek Formation. These units are confined to the subsurface of the outer Coastal Plain, and their type sections are established in corehole CHN-820 from Charleston County, S.C. The Collins Creek Formation consists of greenish-gray lignitic sand and dark-greenish-gray sandy clay and is documented in cores from Allendale, Beaufort, Berkeley, Dorchester, Jasper and Marion Counties, South Carolina, and from Screven County, Georgia. Previously, Collins Creek strata had been incorrectly assigned to the Middendorf Formation. These sediments occupy a stratigraphic position between the Turonian/Coniacian Cape Fear Formation (?) below and the proposed upper Coniacian to middle Santonian Pleasant Creek Formation above. The Collins Creek Formation is middle and late Coniacian in age on the basis of calcareous nannofossil and palynomorph analyses. The Pleasant Creek Formation consists of olive-gray sand and dark-greenish-gray silty to sandy clay and is documented in cores from New Hanover County, North Carolina, and Berkeley, Charleston, Dorchester, Horry and Marion Counties, South Carolina. The strata of this unit previously were assigned incorrectly to the Middendorf Formation and (or) the Cape Fear Formation. These sediments occupy a stratigraphic position between the proposed Collins Creek Formation below and the Shepherd Grove Formation above. The Pleasant Creek Formation is late Coniacian and middle Santonian in age, on the basis of its calcareous nannofossil and palynomorph assemblages.

Microbial reduction of structural iron in interstratified illite-smectite minerals by a sulfate-reducing bacterium

USGS Publications Warehouse

Liu, D.; Dong, H.; Bishop, M.E.; Zhang, Jiahua; Wang, Hongfang; Xie, S.; Wang, Shaoming; Huang, L.; Eberl, D.D.

2012-01-01

Clay minerals are ubiquitous in soils, sediments, and sedimentary rocks and could coexist with sulfate-reducing bacteria (SRB) in anoxic environments, however, the interactions of clay minerals and SRB are not well understood. The objective of this study was to understand the reduction rate and capacity of structural Fe(III) in dioctahedral clay minerals by a mesophilic SRB, Desulfovibrio vulgaris and the potential role in catalyzing smectite illitization. Bioreduction experiments were performed in batch systems, where four different clay minerals (nontronite NAu-2, mixed-layer illite-smectite RAr-1 and ISCz-1, and illite IMt-1) were exposed to D. vulgaris in a non-growth medium with and without anthraquinone-2,6-disulfonate (AQDS) and sulfate. Our results demonstrated that D. vulgaris was able to reduce structural Fe(III) in these clay minerals, and AQDS enhanced the reduction rate and extent. In the presence of AQDS, sulfate had little effect on Fe(III) bioreduction. In the absence of AQDS, sulfate increased the reduction rate and capacity, suggesting that sulfide produced during sulfate reduction reacted with the phyllosilicate Fe(III). The extent of bioreduction of structural Fe(III) in the clay minerals was positively correlated with the percentage of smectite and mineral surface area of these minerals. X-ray diffraction, and scanning and transmission electron microscopy results confirmed formation of illite after bioreduction. These data collectively showed that D. vulgaris could promote smectite illitization through reduction of structural Fe(III) in clay minerals. ?? 2011 Blackwell Publishing Ltd.

Micro-fabric damages in Boom Clay inferred from cryo-BIB-SEM experiment: recent results

NASA Astrophysics Data System (ADS)

Desbois, Guillaume; Schmatz, Joyce; Klaver, Jop; Urai, Janos L.

2017-04-01

The Boom Clay is considered as a potential host rock in Belgium for nuclear waste disposal in a deep geological formation. One of the keys to understand the long-term performance of such a host rock is the fundamental understanding of coupling between microstructural evolution, poromechanical behaviour and the state of hydration of the system. At in situ conditions, Boom Clay is a nearly water-saturated (>94%) clay-rich geomaterial. Subsequently, for measurement of mechanical and transport properties in laboratory, cores of Boom Clay are vacuum-packed in Al-coated-poly-ethylene barrier foil to be best preserved at original hydric state. Because clay microstructures are very sensitive to dehydration, the validity of investigations done on such preserved or/and dried samples is often questionable. Desbois et al. (2009, 2013, 2014) showed the possibility to image fluid-filled porosity in Boom Clay, by using the FIB-cryo-SEM (FIB: Focussed Ion Beam) and FIB-cryo-SEM (BIB: Broad Ion Beam) techniques. However, surprisingly in Desbois et al. (2014), BIB-cryo-SEM experiments on Boom Clay, shown that the majority of the pores were fluid-free, contrasting with result in Desbois et al. (2009). In Desbois et al. (2014), several reasons were discussed to explain such discrepancies. The likely ones are the sealing efficiency of the Al-barrier foil at long term and the volume expansion due to the release of in-situ stress after core extraction, contributing both to dehydration and microfabric damage. This contribution presents the newest results based on cryo-BIB-SEM. Small pieces (30 mm3) of Boom Clay were preserved in liquid nitrogen after the core extraction at the MOL/Dessel Underground Research Laboratory in Belgium. A maximum of ten minutes time span was achieved between opening the core, the sub-sample extraction and the quenching of sub-samples in liquid nitrogen. First results show that all pores visible at cryo-SEM resolution are water saturated. However, water-filled micro-cracks are also present and they are interpreted to result from the releasing of in-situ stress after the core extraction. Moreover, the comparison of the clay micro-fabrics in the same preserved and dried sample suggests collapsing of the clay aggregates' pores in dried sample. These newest results are still preliminary and they need to be analysed in more details. However, if they are confirmed they may be important input to discuss about the validity of measurement of mechanical and transport properties done in laboratory. Desbois G., Urai J.L. and Kukla P.A. (2009). Morphology of the pore space in claystones - evidence from BIB/FIB ion beam sectioning and cryo-SEM observations. E-Earth, 4 :15-22. Desbois G., J.L. Urai, F. Pérez-Willard, Z. Radi, S. van Offern, I. Burkart, P.A. Kukla, U. Wollenberg (2013). Argon broad ion beam tomography in a cryogenic scanning electron microscope: a novel tool for the investigation of representative microstructures in sedimentary rocks containing pore fluid. Journal of Microscopy, 249(3): 215-235. Desbois G., Urai J.L., Hemes S., Brassinnes S., De Craen M., Sillen X. (2014). Nanometer-scale pore fluid distribution and drying damage in preserved clay cores from Belgian clay formations inferred by BIB-cryo-SEM. Engineering Geology, 170:117-131.

The use of expanded clay dust in paint manufacturing

NASA Astrophysics Data System (ADS)

Sverguzova, S. V.; Sapronova, Zh A.; Starostina, Yu L.; Belovodskiy, E. A.

2018-01-01

Production increase of useful products is accompanied by the formation and the accumulation of the vast amounts of industrial wastes, the bulk of which is not involved in the recycling processes. An example of such wastes is dust bag filters of ceramsite production. At the large enterprises, the volume of its formation can reach 7-8 tons of dust per day, which is 10-15% of feedstock mass. The studies on the use of ceramsite production dust as filler pigment in the composition of organic mixed primer of red-brown color are carried out in this work. For comparison, red iron oxide pigment (Pg FGM) was used. The results showed that, primer with the use of expanded clay dust is characterized by the short drying time and meets all regulatory requirements.

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.

Rheological behavior of water-in-oil emulsions stabilized by hydrophobic bentonite particles.

PubMed

Binks, Bernard P; Clint, John H; Whitby, Catherine P

2005-06-07

A study of the rheological behavior of water-in-oil emulsions stabilized by hydrophobic bentonite particles is described. Concentrated emulsions were prepared and diluted at constant particle concentration to investigate the effect of drop volume fraction on the viscosity and viscoelastic response of the emulsions. The influence of the structure of the hydrophobic clay particles in the oil has also been studied by using oils in which the clay swells to very different extents. Emulsions prepared from isopropyl myristate, in which the particles do not swell, are increasingly flocculated as the drop volume fraction increases and the viscosity of the emulsions increases accordingly. The concentrated emulsions are viscoelastic and the elastic storage and viscous loss moduli also increase with increasing drop volume fraction. Emulsions prepared from toluene, in which the clay particles swell to form tactoids, are highly structured due to the formation of an integrated network of clay tactoids and drops, and the moduli of the emulsions are significantly larger than those of the emulsions prepared from isopropyl myristate.

Influence of clay particles on microfluidic-based preparation of hydrogel composite microsphere

NASA Astrophysics Data System (ADS)

Hong, Joung Sook

2016-05-01

For the successful fabrication of a hydrogel composite microsphere, this study aimed to investigate the influence of clay particles on microsphere formation in a microfluidic device which has flow focusing and a 4.5:1 contraction channel. A poly alginic acid solution (2.0 wt.%) with clay particles was used as the dispersed phase to generate drops in an oil medium, which then merged with drops of a CaCl2 solution for gelation. Drop generations were observed with different flow rates and particles types. When the flow rate increased, drop generation was enhanced and drop size decreased by the build-up of more favorable hydrodynamic flow conditions to detach the droplets. The addition of a small amount of particles insignificantly changed the drop generation behavior even though it reduced interfacial tension and increased the viscosity of the solution. Instead, clays particles significantly affected hydro-gelation depending on the hydrophobicity of particles, which produced further heterogeneity in the shape and size of microsphere.

Interaction between ATP, metal ions, glycine, and several minerals

NASA Technical Reports Server (NTRS)

Rishpon, J.; Ohara, P. J.; Lawless, J. G.; Lahav, N.

1982-01-01

Interactions between ATP, glycine and montmorillonite and kaolinite clay minerals in the presence of various metal cations are investigated. The adsorption of adenine nucleotides on clays and Al(OH)3 was measured as a function of pH, and glycine condensation was followed in the presence of ATP, ZnCl2, MgCl2 and either kaolinite or montmorillonite. The amounts of ATP and ADP adsorbed are found to decrease with increasing Ph, and to be considerably enhanced in experiments with Mg(2+)- and Zn(2+)-montmorillonite with respect to Na(+)-montmorillonite. The effects of divalent cations are less marked in kaolinite. Results for Al(OH)3 show the importance of adsorption at clay platelet edges at high pH. The decomposition of ATP during drying at high temperature is observed to be inhibited by small amounts of clay, vacuum, or Mg(2+) or Zn(2+) ions, and to be accompanied by peptide formation in the presence of glycine. Results suggest the importance of Zn(2+) and Mg(2+) in chemical evolution.

Mineralogy and provenance of clays in miarolitic cavities of the Pikes Peak Batholith, Colorado

USGS Publications Warehouse

Kile, D.E.

2005-01-01

Clay samples from 105 cavities within miarolitic granitic pegmatites throughout the Pikes Peak batholith, in Colorado, were analyzed by powder X-ray diffraction (XRD). Smectite (beidellite), illite, and kaolinite were found within the cavities. Calculation of crystallite-thickness distribution (CTD), mean thickness of the crystallites, and variance in crystallite thickness, as deduced from XRD patterns, allowed a determination of provenance and mode of formation for illite and smectite. Authigenic miarolitic-cavity illite and smectite show lognormal CTDs and larger mean thicknesses of crystallites than do their soil-derived counterparts; non-lognormal illite in a cavity results from mixing of cavity and soil illite. Analysis of mean thickness and thickness variance shows that crystal growth of illite is initiated by a nucleation event of short duration, followed by surface-controlled kinetics. Crystallization of the miarolitic cavity clays is presumed to occur by neoformation from hydrothermal fluids. The assessment of provenance allows a determination of regional and local distributions of clay minerals in miarolitic cavities within the Pikes Peak batholith.

Integrated palynology and sequence stratigraphy of the upper Cretaceous (Maastrichtian) strata, Rio Grande Embayment, Texas, using well, outcrop, and seismic data

NASA Astrophysics Data System (ADS)

Mahmoud, Salah El-Din Ragab

Numerous nomenclature problems surround the Campanian and Maastrichtian strata of the Rio Grande Embayment. Sellards et al. (1932) and Stephenson et al. (1942) placed the Upson Clay and San Miguel Formation in the Taylor Group (Campanian). These workers assigned the overlying Olmos Coal and the Escondido Formation to the Navarro Group (Maastrichtian). Pessagno (1969, p. 90--91) tentatively included the Upson Clay, the San Miguel Formation, the Olmos Coal, and the Escondido Formation in the Navarro Group, but noted that these strata are lithologically dissimilar to those of the type Navarro Group in Navarro County (northeast Texas). He (ibid, p. 91) suggested that "---Future workers should consider the possibility of excluding the entire sequence from the Navarro Group. It is perhaps more closely related to the Difunta Group of Mexico or deserves a group name of its own." Pessagno (1967; 1969, p. 91--92) utilized planktonic foraminiferal biostratigraphic data to determine (1) that the Upson Clay and San Miguel Formation are assignable to the lower Maastrichtian and (2) that the Escondido Formation is assignable to the upper Maastrichtian. The present investigation attempts to build on the chronostratigraphic framework established by Pessagno (1967, 1969). Palynology is used for the first time in this report to generate biostratigraphic, chronostratigraphic, and paleoecological data for the Maastrichtian strata in the study area. New palynological data, integrated with existing planktonic foraminifera and megafossils, indicate that San Miguel Formation and Olmos Coal are of Maastrichtian age. Tying results with seismic data results in dating interpreted sequence boundaries to be within the time interval of 83 and 63 MA. Five seismic facies are delineated and a rate of sediment supply higher than the rate of subsidence during a prolonged progradational episode is suggested in the study area. Three-dimensional seismic data are interpreted in terms of the structure and hydrocarbon potential. Analysis of structural elements indicates northwest-southeast compressional forces resulting from sediment loading. Parasequence-level mapping was carried out and paleogeographic and depositional history was inferred and used in interpreting systems tracts. The study on San Miguel Formation by Weise (1980) was revisited using sequence stratigraphic techniques.

Influence of Alkali Resistant (Ar) Fibreglass in Porcelain Clay for Manufacturing Vitrified Clay Pipes

NASA Astrophysics Data System (ADS)

Ikhmal Hanapi, Muhammad; Ahmad, Sufizar; Taib, Hariati; Ismail, Al Emran; Nasrull Abdol Rahman, Mohd; Salleh, Salihatun Md; Sadikin, Azmahani; Mahzan, Shahruddin

2017-10-01

The aim of this work is to determine the characteristics of porcelain ceramic with influence of milled Alkali Resistant (AR) fiberglass for manufacturing vitrified clay pipes. In this study, raw materials consist of porcelain clay and AR fiberglass were refined into powders less than 90μm. Subsequently, these samples were compacted into cylindrical pellet for chemical analysis using X-Ray Fluorescence (XRF). The ceramic sample was produced by mixing different weight percentage of AR glass to porcelain ceramic with 3 wt%, 6 wt%, 9 wt% and 12 wt%. Subsequently, the sample was compacted with 3 ton of pressure load and sintered at 900 °C, 1000 °C, 1100 °C and 1200 °C. The phase identification by using X-Ray Diffraction (XRD) and microstructural analysis were performed for the sintered sample. Chemical analysis revealed that the significant element for all raw material are SiO2, Al2O3, Na2O and K2O. Phase identification analysis shown that sample sintered at 1000 °C produces quartz (SiO2), berlinite (AlPO4), albite (NaAlSi3O8) and calcium-magnesium-aluminum-silicate (CaMgAlSiO). The formation of primary mullite was observed in sample sintered at 1100 °C. The image of microstructural morphology denoted that the formation of glassy phase with decreasing amount of void when sintering temperature and addition of AR glass were increased, which correspond well to phase identification analysis.

Contrasting frictional behaviour of fault gouges containing Mg-rich phyllosilicates

NASA Astrophysics Data System (ADS)

Sanchez Roa, C.; Faulkner, D.; Jimenez Millan, J.; Nieto, F.

2015-12-01

The clay mineralogy of fault gouges has important implications on frictional properties and stability of fault planes. We studied the specific case of the Galera fault zone where fault gouges containing Mg-rich phyllosilicates appear as hydrothermal deposits related to high salinity fluids enriched in Mg2+. These deposits are dominated by sepiolite and palygorskite, both fibrous clay minerals with similar composition to Mg-smectite. The frictional strengths of sepiolite and palygorskite have not yet been determined, however, as they are part of the clay mineral group, it has been assumed that their frictional behaviour would be in line with platy clay minerals. We performed frictional sliding experiments on powdered pure standards and fault rocks in order to establish the frictional behaviour of sepiolite and palygorskite using a triaxial deformation apparatus with a servo-controlled axial loading system and fluid pressure pump. Friction coefficients for palygorskite and sepiolite as monomineralic samples were found to be 0.65 to 0.7 for dry experiments, and 0.45 to 0.5 for water-saturated experiments. Although these fibrous minerals are part of the phyllosilicates group, they show higher friction coefficients and their mechanical behaviour is less stable than platy clay minerals. This difference is a consequence of their stronger structural framework and the discontinuity of water layers. Our results present a contrast in mechanical behaviour between Mg-rich fibrous and platy clay minerals in fault gouges, where smectite is known to considerably reduce friction coefficients and to increase the stability of the fault plane leading to creeping processes. Transformations between saponite and sepiolite have been previously observed and could modify the deformation regime of a fault zone. Constraining the stability conditions and possible mineral reactions or transformations in fault gouges could help us understand the general role of clay minerals in fault stability.

The Effects Of Physical And Biological Cohesion On Bedforms

NASA Astrophysics Data System (ADS)

Parsons, D. R.; Schindler, R.; Baas, J.; Hope, J. A.; Malarkey, J.; Paterson, D. M.; Peakall, J.; Manning, A. J.; Ye, L.; Aspden, R.; Alan, D.; Bass, S. J.

2014-12-01

Most coastal sediments consist of complex mixtures of cohesionless sands, physically-cohesive clays and extra cellular polymeric substances (EPS) that impart biological cohesion. Yet, our ability to predict bedform dimensions in these substrates is reliant on predictions based exclusively on cohesionless sand. We present findings from the COHBED project - which explicitly examines how bedform dynamics are modified by natural cohesion. Our experimental results show that for ripples, height and length are inversely proportional to initial clay content and bedforms take longer to appear, with no ripples when clay content exceeds 18%. When clay is replaced by EPS the development time and time of first appearance of ripples both increase by two orders of magnitude, with no bedforms above 0.125% EPS. For dunes, height and length are also inversely proportional to initial substrate clay content, resulting in a transition from dunes to ripples normally associated with velocity decreases. Addition of low EPS concentrations into the substrate results in yet smaller bedforms at the same clay contents and at high EPS concentrations, biological cohesion supersedes all electrostatic bonding, and bedform size is no longer related to mud content. The contrast in physical and biological cohesion effects on bedform development result from the disparity between inter-particle electrostatic bonding of clay particles and EPS grain coating and strands that physically link sediments together, which effects winnowing rates as bedforms evolve. These findings have wide ranging implications for bedform predictions in both modern and ancient environments. Coupling of biological and morphological processes not only requires an understanding of how bedform dimensions influence biota and habitat, but also how benthic species can modify bedform dimensions. Consideration of both aspects provides a means in which fluid dynamics, sediment transport and ecosystem energetics can be linked to yield improved predictions of morphological and habitat adjustment.

Effects of clay on toxin binding capacity, ruminal fermentation, diet digestibility, and growth of steers fed high-concentrate diets.

PubMed

Antonelo, D S; Lancaster, N A; Melnichenko, S; Muegge, C R; Schoonmaker, J P

2017-10-01

Three experiments were conducted to determine the effect of increasing concentrations of a smectite clay on toxin binding capacity, ruminal fermentation, diet digestibility, and growth of feedlot cattle. In Exp. 1, 72 Angus × Simmental steers were blocked by BW (395 ± 9.9 kg) and randomly allotted to 3 treatments (4 pens/treatment and 6 steers/pen) to determine the effects of increasing amounts of clay (0, 1, or 2%) on performance. The clay was top-dressed on an 80% concentrate diet at a rate of 0, 113, or 226 g/steer daily to achieve the 0, 1, and 2% treatments, respectively. Steers were slaughtered at a target BW of 606 kg. In Exp. 2, 6 steers (596 ± 22.2 kg initial BW) were randomly allotted to the same 3 treatments in a replicated 3 × 3 Latin square design (21-d periods) to determine the effects of increasing amounts of clay on ruminal pH, VFA, and nutrient digestibility. In Exp. 3, 150 mg of clay was incubated in 10 mL of rumen fluid with 3 incremental concentrations (6 replicates per concentration) of aflatoxin B (AFB) or ergotamine tartate (ET) to determine binding capacity. During the first 33-d period, there was a quadratic effect of clay on ADG ( < 0.01) and G:F ( < 0.01), increasing from 0 to 1% clay and then decreasing from 1 to 2% clay. However, during the second 30-d period, clay linearly decreased ADG and G:F ( ≤ 0.03) and overall ADG, DMI, and G:F were not impacted ( ≥ 0.46). Clay linearly decreased marbling score ( = 0.05). Hepatic enzyme activity did not differ among treatments on d 0 or at slaughter ( ≥ 0.15). Clay linearly decreased ruminal lactate and propionate, linearly increased formate and the acetate:propionate ratio ( ≤ 0.04), and tended ( = 0.07) to linearly increase butyrate. Clay tended to linearly increase ( = 0.06) OM and CP apparent digestibility. Ruminal pH, urine pH, and other digestibility measures did not differ among treatments ( ≥ 0.15). Clay was able to effectively bind AFB and ET at concentrations above the normal physiological range (52 and 520 μg/mL), but proportional adsorption was decreased to 35.5 and 91.1% at 5,200 μg/mL ( < 0.01) for AFB and ET, respectively. In conclusion, clay effectively binds ruminal toxins, decreases ruminal lactate, and improves performance only during adaptation to a high-concentrate feedlot diet.

Fundamental investigations of clay/polymer nanocomposites and applications in co-extruded microlayered systems

NASA Astrophysics Data System (ADS)

Decker, Jeremy John

The second and fourth generations of hydroxylated dendritic polyesters (HBP2, HBP4) were combined with unmodified sodium montmorillonite clay (Na +MMT) in water to generate a broad range of polymer clay nanocomposites from 0 to 100% wt/wt Na+MMT. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to investigate intercalation states of the clay galleries. It was shown that interlayer spacings were independent of generation number and changed over the composition range from 0.5 nm to 3.5 nm in 0.5 nm increments that corresponded to a flattened HBP conformation within the clay tactoids. The HBP4/Na+MMT systems were investigated to study the vitrified Rigid Amorphous Fraction (RAF) induced by the clay surfaces. Differential Scanning Calorimetry (DSC) showed changes in heat capacity, Delta Cp, at Tg, that decreased with clay content, until completely suppressed at 80 wt% Na+MMT due to confinement. RAF was quantified from these changes in heat capacity and verified by the analysis of orthopositronium lifetime temperature scans utilizing positron annihilation lifetime spectroscopy (PALS): verifying the glassy nature of the RAF at elevated temperatures. Mathematical relationships allowed for correlation of the interlayer spacings with DeltaC p. RAF formation correlated to intercalated HBP4, and external surfaces of the clay tactoids. The interdiffusion of a polymer pair in microlayers was exploited to increase the concentration of nanoclay particles. When microlayers of a nanocomposite composed of organically modified montmorillonite (M2(HT)2 ) inside maleic anhydride grafted linear low-density polyethylene (LLDPE-g-MA) and low-density polyethylene (LDPE) were taken into the melt, the greater mobility of the linear LLDPE-g-MA chains compared to the branched LDPE chains caused shrinkage of the nanocomposite microlayers, concentrating the M 2(HT)2 contained within. Analysis of the clay morphology within these layers demonstrated an increase in clay particle lengths and aspect ratios, which was attributed to the growth of skewed aggregates during concentration. The melt induced clay concentration and increased clay particle dimensions caused significant decreases in the permeability of the nanocomposite microlayers and reduced the overall permeability of the multilayered films. Morphology and transport behavior of these microlayered films were compared to a series of bulk nanocomposites using a second LLDPE-g-MA containing M 2(HT)2 with varying clay content.

The effect of clay on the dissolution of nuclear waste glass

NASA Astrophysics Data System (ADS)

Lemmens, K.

2001-09-01

In a nuclear waste repository, the waste glass can interact with metals, backfill materials (if present) and natural host rock. Of the various host rocks considered, clays are often reported to delay the onset of the apparent glass saturation, where the glass dissolution rate becomes very small. This effect is ascribed to the sorption of silica or other glass components on the clay. This can have two consequences: (1) the decrease of the silica concentration in solution increases the driving force for further dissolution of glass silica, and (2) the transfer of relatively insoluble glass components (mainly silica) from the glass surface to the clay makes the alteration layer less protective. In recent literature, the latter explanation has gained credibility. The impact of the environmental materials on the glass surface layers is however not well understood. Although the glass dissolution can initially be enhanced by clay, there are arguments to assume that it will decrease to very low values after a long time. Whether this will indeed be the case, depends on the fate of the released glass components in the clay. If they are sorbed on specific sites, it is likely that saturation of the clay will occur. If however the released glass components are removed by precipitation (growth of pre-existing or new secondary phases), saturation of the clay is less likely, and the process can continue until exhaustion of one of the system components. There are indications that the latter mechanism can occur for varying glass compositions in Boom Clay and FoCa clay. If sorption or precipitation prevents the formation of protective surface layers, the glass dissolution can in principle proceed at a high rate. High silica concentrations are assumed to decrease the dissolution rate (by a solution saturation effect or by the impact on the properties of the glass alteration layer). In glass corrosion tests at high clay concentrations, silica concentrations are, however, often higher than the silica concentrations in equilibrium with the glass surface ( C ∗Si, saturation) that are found in absence of clay. Nevertheless, the glass dissolution proceeds at relatively high rate. C ∗Si, saturation seems to be increased by the presence of clay. To understand this, more knowledge is necessary concerning the fate of the released silica and the silica speciation in solution.

Numerical investigation of the seismic detectability of carbonate thin beds in the Boom Clay formation

NASA Astrophysics Data System (ADS)

Carcione, José M.; Gei, Davide

2016-07-01

The present study evaluates the capacity of the Boom Clay as a host rock for disposal purposes, more precisely its seismic characterization, which may assess its long-term performance to store radioactive wastes. Although the formation is relatively uniform and homogeneous, there are embedded thin layers of septaria (carbonates) that may affect the integrity of the Boom Clay. Therefore, it is essential to locate these geobodies. The seismic data to characterize the Boom Clay has been acquired at the Kruibeke test site. The inversion, which allowed us to obtain the anisotropy parameters and seismic velocities of the clay, is complemented with further information such as log and laboratory data. The attenuation properties have been estimated from equivalent formations (having similar composition and seismic velocities). The inversion yields quite consistent results although the symmetry of the medium is unusual but physically possible, since the anisotropy parameter ɛ is negative. According to a time-domain calculation of the energy velocity at four frequency bands up to 900 Hz, velocity increases with frequency, a behaviour described by the Zener model. Then, we use this model to describe anisotropy and anelasticity that are implemented into the equation of motion to compute synthetic seismograms in the space-time domain. The technique is based on memory variables and the Fourier pseudospectral method. We have computed reflection coefficients of the septaria thin layer. At normal incidence, the P-wave coefficient vanishes at specific thicknesses of the layer and there is no conversion to the S wave. For example, calculations at 600 Hz show that for thicknesses of 1 m the septarium can be detected more easily since the amplitudes are higher (nearly 0.8). Converted PS waves have a high amplitude at large offsets (between 30° and 80°) and can be useful to identify the target on this basis. Moreover, we have investigated the effect of septaria embedded in the Boom Clay with several simulations, by considering a lateral partial continuity of the calcareous thin inclusions. The simulations with layers of calcareous material show continuity of the reflections even when the percentage of carbonate within the layer is very small (5-15 per cent), while for low content of the calcareous material, isolated septaria boulders generate diffraction events. We have also simulated the stacked seismic section obtained from processing of the field data. The matching between the field and synthetic sections is acceptable.

Fe(II) sorption on pyrophyllite: Effect of structural Fe(III) (impurity) in pyrophyllite on nature of layered double hydroxide (LDH) secondary mineral formation

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

Starcher, Autumn N.; Li, Wei; Kukkadapu, Ravi K.

Fe(II)-Al(III)-LDH (layered double hydroxide) phases have been shown to form from reactions of aqueous Fe(II) with Fe-free Al-bearing minerals (phyllosilicate/clays and Al-oxides). To our knowledge, the effect of small amounts of structural Fe(III) impurities in “neutral” clays on such reactions, however, were not studied. In this study to understand the role of structural Fe(III) impurity in clays, laboratory batch studies with pyrophyllite (10 g/L), an Al-bearing phyllosilicate, containing small amounts of structural Fe(III) impurities and 0.8 mM and 3 mM Fe(II) (both natural and enriched in 57Fe) were carried out at pH 7.5 under anaerobic conditions (4% H2 – 96%more » N2 atmosphere). Samples were taken up to 4 weeks for analysis by Fe-X-ray absorption spectroscopy and 57Fe Mössbauer spectroscopy. In addition to the precipitation of Fe(II)-Al(III)-LDH phases as observed in earlier studies with pure minerals (no Fe(III) impurities in the minerals), the analyses indicated formation of small amounts of Fe(III) containing solid(s), most probably hybrid a Fe(II)-Al(III)/Fe(III)-LDH phase. The mechanism of Fe(II) oxidation was not apparent but most likely was due to interfacial electron transfer from the sorbed Fe(II) to the structural Fe(III) and/or surface-sorption-induced electron-transfer from the sorbed Fe(II) to the clay lattice. Increase in the Fe(II)/Al ratio of the LDH with reaction time further indicated the complex nature of the samples. This research provides evidence for the formation of both Fe(II)-Al(III)-LDH and Fe(II)-Fe(III)/Al(III)-LDH-like phases during reactions of Fe(II) in systems that mimic the natural environments. Better understanding Fe phase formation in complex laboratory studies will improve models of natural redox systems.« less

Application of Spectral Gamma Ray for Lithofacies and Paleo-environmental Interpretation: A Case Study from the Late Ordovician Glaciogenic Deposits, Saudi Arabia

NASA Astrophysics Data System (ADS)

Alqubalee, Abdullah; Abdullatif, Osman; Babalola, Lamidi

2017-04-01

This study is an integral part of multidisciplinary research being carried out on the Late Ordovician Sarah Formation in the Rub' Al-Khali Basin, Saudi Arabia. Sarah Formation proved to be important target for tight gas reservoir in Saudi Arabia. This study integrates lithofacies characteristics and spectral Gamma Ray of core samples so as to identify and differentiate among different depositional environments. Thorium (Th, ppm) and potassium (K, %) are acquired with approximately a reading point per inch using high-resolution Spectral Core Gamma. The cores description and analysis from six exploratory wells revealed four depositional environments ranging from the glaciofluvial, glaciolacustrine delta, subglacial to the nearshore environments. Based on lithofacies and geochemical analysis of the core samples, four groups of lithofacies including sandstone (G1), claystone and/or argillaceous sandstone (G2), calcareous and/or evaporitic sandstone (G3), and diamictites (G4) were recognized in each well. The bivariate plots of Th and K were used to delineate the minerals contents in each core and environment. The results showed that the G1 facies of the nearshore and glaciofluvial environments are characterized by similar distribution patterns of these elements exhibiting lower clay minerals variations than that in the other groups of lithofacies. These patterns consist of two mineral groups, the first one includes illite and montmorillonite clay minerals while the second one includes mica, glauconite, and feldspar. By contrast, G1 and G2 lithofacies of the glaciolacustrine delta environment are characterized by a range of clay minerals. However, G3 of this environment exhibits similar pattern of the nearshore and the glaciofluvial environments This is because the grains of G3 are cemented by anhydrite rather than by clays. Based on the lithological characteristic, matrix-supported and clast-supported diamictites were identified in the subglacial environment. The differences between these two lithofacies were clearly detected using Th/K plot. Both diamictites are characterized by a range of minerals including illite, mixed layer clays, glauconite, and feldspar. The matrix-supported diamictites contain higher proportions of these minerals. This study indicates that the relationship between Th and K can be used to predict the types of lithofacies and clay contents in different glaciogenic depositional environments. In addition, it can be used to predict the relative amounts of the clay minerals in each lithofacies. In turn, identifying the types and the amounts of clay minerals in lithofacies facilitate the prediction of reservoir quality and eventually lead to enhancement of their development and productivity.

CO 2 Sorption to Subsingle Hydration Layer Montmorillonite Clay Studied by Excess Sorption and Neutron Diffraction Measurements

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

Rother, Gernot; Ilton, Eugene S.; Wallacher, Dirk

2013-01-02

Geologic storage of CO 2 requires that the caprock sealing the storage rock is highly impermeable to CO 2. Swelling clays, which are important components of caprocks, may interact with CO 2 leading to volume change and potentially impacting the seal quality. The interactions of supercritical (sc) CO 2 with Na saturated montmorillonite clay containing a subsingle layer of water in the interlayer region have been studied by sorption and neutron diffraction techniques. The excess sorption isotherms show maxima at bulk CO2 densities of ≈0.15 g/cm 3, followed by an approximately linear decrease of excess sorption to zero and negativemore » values with increasing CO 2 bulk density. Neutron diffraction experiments on the same clay sample measured interlayer spacing and composition. The results show that limited amounts of CO 2 are sorbed into the interlayer region, leading to depression of the interlayer peak intensity and an increase of the d(001) spacing by ca. 0.5 Å. The density of CO 2 in the clay pores is relatively stable over a wide range of CO 2 pressures at a given temperature, indicating the formation of a clay-CO 2 phase. Finally, at the excess sorption maximum, increasing CO 2 sorption with decreasing temperature is observed while the high-pressure sorption properties exhibit weak temperature dependence.« less

Nature of Reduced Carbon in Martian Meteorites

NASA Technical Reports Server (NTRS)

Gibson, Everett K., Jr.; McKay, D. S.; Thomas-Keprta, K. L.; Clemett, S. J.; White, L. M.

2012-01-01

Martian meteorites provide important information on the nature of reduced carbon components present on Mars throughout its history. The first in situ analyses for carbon on the surface of Mars by the Viking landers yielded disappointing results. With the recognition of Martian meteorites on Earth, investigations have shown carbon-bearing phases exist on Mars. Studies have yielded presence of reduced carbon, carbonates and inferred graphitic carbon phases. Samples ranging in age from the first approximately 4 Ga of Mars history [e.g. ALH84001] to nakhlites with a crystallization age of 1.3 Ga [e.g. Nakhla] with aqueous alteration processes occurring 0.5-0.7 Ga after crystallizaton. Shergottites demonstrate formation ages around 165-500 Ma with younger aqueous alterations events. Only a limited number of the Martian meteorites do not show evidence of significance terrestrial alterations. Selected areas within ALH84001, Nakhla, Yamato 000593 and possibly Tissint are suitable for study of their indigenous reduced carbon bearing phases. Nakhla possesses discrete, well-defined carbonaceous phases present within iddingsite alteration zones. Based upon both isotopic measurements and analysis of Nakhla's organic phases the presence of pre-terrestrial organics is now recognized. The reduced carbon-bearing phases appear to have been deposited during preterrestrial aqueous alteration events that produced clays. In addition, the microcrystalline layers of Nakhla's iddingsite have discrete units of salt crystals suggestive of evaporation processes. While we can only speculate on the origin of these unique carbonaceous structures, we note that the significance of such observations is that it may allow us to understand the role of Martian carbon as seen in the Martian meteorites with obvious implications for astrobiology and the pre-biotic evolution of Mars. In any case, our observations strongly suggest that reduced organic carbon exists as micrometer- size, discrete structures on Mars associated with clay and salt minerals. The Mars Science Laboratory s investigators should be aware of reduced organic carbon components within clay-bearing phases.

Rheology of polyaniline-dinonylnaphthalene disulfonic acid (DNNDSA) montmorillonite clay nanocomposites in the sol state: shear thinning versus pseudo-solid behavior.

PubMed

Garai, Ashesh; Nandi, Arun K

2008-04-01

The melt rheology of polyaniline (PANI)-dinonylnaphthalenedisulfonic acid (DNNDSA) gel nanocomposites (GNCs) with organically modified (modified with cetyl trimethylammonium bromide)-montmorillonite (om-MMT) clay has been studied for three different clay concentrations at the temperature range 120-160 degrees C. Field emission scanning electron microscopy (FE-SEM), wide angle X-ray scattering (WAXS), differential scanning calorimetry (DSC) and dc-conductivity data (approximately 10(-3) S/cm) indicate that the PANI-DNNDSA melt is in sol state and it is not de-doped at that condition. The WAXS data indicate that in GNC-1 sol clay tactoids are in exfoliated state but in the other sols they are in intercalated state. The zero shear viscosity (eta0), storage modulus (G') and loss modulus (G") increase than that of pure gel in the GNCs. The pure sol and the sols of gel nanocomposites (GNCs) exhibit Newtonian behavior for low shear rate (< 6 x 10(-3) s(-1)) and power law variation for the higher shear rate region. The characteristic time (A) increase with increasing clay concentration and the power law index (n) decreases with increase in clay concentration in the GNCs indicating increased shear thinning for the clay addition. Thus the sols of om-clay nanocomposites of PANI-DNNDSA system are easily processible. The storage modulus (G') of GNC sols are higher than that of pure PANI-DNNDSA sol, GNC1 sol shows a maximum of 733% increase in storage modulus and the percent increase decreases with increase in temperature. Exfoliated nature of clay tactoids has been attributed for the above dramatic increase of G'. The PANI-DNNDSA sol nanocomposites behave as a pseudo-solid at higher frequency where G' and loss modulus (G") show a crossover point in the frequency sweep experiment at a fixed temperature. The crossover frequency decreases with increase in clay concentration and it increases with increase in temperature for GNC sols. The pseudo-solid behavior has been explained from jamming or network formation of clay tactoids under shear. A probable explanation of the two apparently contradictory phenomena of shear thinning versus pseudo-solid behavior of the nanocomposite sols is discussed.

Prediction of gas production using well logs, Cretaceous of north-central Montana

USGS Publications Warehouse

Hester, T.C.

1999-01-01

Cretaceous gas sands underlie much of east-central Alberta and southern Saskatchewan, eastern Montana, western North Dakota, and parts of South Dakota and Wyoming. Estimates of recoverable biogenic methane from these rocks in the United States are as high as 91 TCF. In northern Montana, current production is localized around a few major structural features, while vast areas in between these structures are not being exploited. Although the potential for production exists, the lack of commercial development is due to three major factors: 1) the lack of pipeline infrastructure; 2) the lack of predictable and reliable rates of production; and 3) the difficulty in recognizing and selecting potentially productive gas-charged intervals. Unconventional (tight), continuous-type reservoirs, such as those in the Cretaceous of the northern Great Plains, are not well suited for conventional methods of formation evaluation. Pay zones frequently consist only of thinly laminated intervals of sandstone, silt, shale stringers, and disseminated clay. Potential producing intervals are commonly unrecognizable on well logs, and thus are overlooked. To aid in the identification and selection of potential producing intervals, a calibration system is developed here that empirically links the 'gas effect' to gas production. The calibration system combines the effects of porosity, water saturation, and clay content into a single 'gas-production index' (GPI) that relates the in-situ rock with production potential. The fundamental method for isolating the gas effect for calibration is a crossplot of neutron porosity minus density porosity vs gamma-ray intensity. Well-log and gas-production data used for this study consist of 242 perforated intervals from 53 gas-producing wells. Interval depths range from about 250 to 2400 ft. Gas volumes in the peak calendar year of production range from about 4 to 136 MMCF. Nine producing formations are represented. Producing-interval data show that porosity and gas production are closely linked to clay volume. Highest porosities and maximum gas production occur together at an intermediate clay content of about 12% (60 API). As clay volume exceeds 35% (130 API), minimum porosity required for production increases rapidly, and the number of potential producing intervals declines. Gas production from intervals where clay volume exceeds 50% is rare. Effective porosities of less than about 8% are probably inadequate for commercial gas production in these rocks regardless of clay content.

Integrated stratigraphy of a shallow marine Paleocene-Eocene boundary section, MCBR cores, Maryland (USA)

NASA Astrophysics Data System (ADS)

Self-Trail, J. M.; Robinson, M. M.; Edwards, L. E.; Powars, D. S.; Wandless, G. A.; Willard, D. A.

2013-12-01

An exceptional Paleocene-Eocene boundary section occurs in a cluster of six short (<15m) coreholes (MCBR 1 through 6) drilled near Mattawoman Creek in western Charles County, Maryland. The sediments consist of glauconite-rich sand of the upper Paleocene Aquia Formation and silty clay of the lower Eocene Marlboro Clay. Sediment samples were analyzed for carbon and oxygen isotopes, percent calcium carbonate, calcareous nannofossils, planktic and benthic foraminifera, dinoflagellates, pollen, and lithology. A well-defined carbon isotope excursion (CIE) documents a gradual negative shift in δ13C values that starts below the lithologic break between the Aquia Formation and the Marlboro Clay. A benthic foraminifer extinction event, reduction of calcareous nannofossil assemblages, and change in core color from gray to alternating gray and pink also occurs within the CIE transition. These alternating changes in color coincide with cyclic peaks in the carbon isotope and percent calcium carbonate curves, where gray color corresponds to a positive shift in carbon isotope values and to a corresponding increase in percent benthic and planktic foraminifera. The upper third of the Marlboro Clay is barren of all calcareous microfossil material, although the presence of foraminiferal molds and linings proves that deposition occurred in a marine environment. Co-occurrence of the dinoflagellates Apectodinium augustum and Phthanoperidinium crenulatum at the top of the Marlboro Clay suggests that the Marlboro Clay at Mattawoman Creek is truncated. This is corroborated by the absence in the Marlboro of specimens of the calcareous nannofossil Rhomboaster-Discoaster assemblage, which is restricted to early Eocene Zone NP9b. Based on planktic/benthic foraminifera ratios, deposition of sediments at Mattawoman Creek occurred predominantly in an inner neritic environment, at water depths between 25-50 m. Occasional deepening to approximately 75m (middle neritic environment) occurred in the early Eocene, as represented by the basal Marlboro Clay. The planktic/benthic ratio, however, could also be affected by surface productivity and/or river runoff. The gradual shift up-section in core color from gray to alternating gray and red, to dark red, coupled with dissolution of calcareous microfossil assemblages, is possibly secondary and may represent lysocline shoaling in a nearshore environment. This would suggest that lysocline shoaling continued after the CIE and well into the early Eocene.

Ectomycorrhizal formation in herbicide-treated soils of differing clay and organic matter content

Treesearch

Matt D. Busse; Gary O. p Fiddler; Alice W. Ratcliff

2004-01-01

Herbicides are commonly used on private timberlands in the western United States for site preparation and control of competing vegetation. How non-target soil biota respond to herbicide applications, however, is not thoroughly understood. We tested the effects of triclorpyr, imazapyr, and sulfometuron methyl on ectomycorrhizal formation in a greenhouse study. Ponderosa...

NMR imaging and cryoporometry of swelling clays

NASA Astrophysics Data System (ADS)

Dvinskikh, Sergey V.; Szutkowski, Kosma; Petrov, Oleg V.; Furó, István.

2010-05-01

Compacted bentonite clay is currently attracting attention as a promising "self-sealing" buffer material to build in-ground barriers for the encapsulation of radioactive waste. It is expected to fill up the space between waste canister and surrounding ground by swelling and thus delay flow and migration from the host rock to the canister. In environmental sciences, evaluation and understanding of the swelling properties of pre-compacted clay are of uttermost importance for designing such buffers. Major goal of present study was to provide, in a non-invasive manner, a quantitative measure of bentonite distribution in extended samples during different physical processes in an aqueous environment such as swelling, dissolution, and sedimentation on the time scale from minutes to years. The propagation of the swelling front during clay expansion depending on the geometry of the confining space was also studied. Magnetic resonance imaging and nuclear magnetic resonance spectroscopy were adapted and used as main experimental techniques. With this approach, spatially resolved movement of the clay/water interface as well as clay particle distributions in gel phase can be monitored [1]. Bulk samples with swelling in a vertical tube and in a horizontal channel were investigated and clay content distribution profiles in the concentration range over five orders of magnitude and with sub-millimetre spatial resolution were obtained. Expansion rates for bulk swelling and swelling in narrow slits were compared. For sodium-exchanged montmorillonite in contact with de-ionised water, we observed a remarkable acceleration of expansion as compared to that obtained in the bulk. To characterize the porosity of the clay a cryoporometric study [2] has been performed. Our results have important implications to waste repository designs and for the assessment of its long-term performance. Further research exploring clay-water interaction over a wide variety of clay composition and water ionic strength as well as investigating the effect of the confining geometry and material surface properties seem to be worth to pursue. Acknowledgements: This work has been supported by the Swedish Nuclear Fuel and Waste Management Co (SKB) and the Swedish Research Council VR. References: [1] Dvinskikh S. V., Szutkowski K., Furó I. MRI profiles over a very wide concentration ranges: application to swelling of a bentonite clay. J. Magn. Reson. 198, 146 (2009). [2] Petrov O. V., Furó I. NMR cryoporometry: Principles, applications and potential. Prog. Nucl. Magn. Reson. Spec. 54, 97 (2009).

Wave-induced ripple development in mixed clay-sand substrates

NASA Astrophysics Data System (ADS)

Wu, Xuxu; Parsons, Daniel; Baas, Jaco H.; Mouazé, Dominique; McLelland, Stuart; Amoudry, Laurent; Eggenhuisen, Jorris; Cartigny, Matthieu; Ruessink, Gerben

2016-04-01

This paper reports on a series of experiments that aim to provide a fuller understanding of ripple development within clay-sand mixture substrates under oscillatory flow conditions. The work was conducted in the Total Environment Simulator at the University of Hull and constituted 6 separate runs, in which 5 runs were conducted under identical sets of regular waves (an additional run was conducted under irregular waves, but is not discussed in present paper). The bed content was systematically varied in its composition ranging from a pure sand bed through to a bed comprising 7.4% clay. A series of state-of-the-art measurements were employed to quantify interactions of near-bed hydrodynamics, sediment transport, and turbulence over rippled beds formed by wave action, during and after, each run. The experimental results demonstrate the significant influence of the amount of cohesive clay materials in the substrate on ripple evolution under waves. Most importantly, addition of clay in the bed dramatically slowed down the rate of ripple development and evolution. The equilibrium time of each run increased exponentially from 30 minutes under the control conditions of a pure sand bed, rising to ~350 minutes for the bed with the highest fraction of clay. The paper discusses the slower ripple growth rates with higher cohesive fractions, via an influence on critical shear, but highlights that the end equilibrium size of ripples is found to be independent of increasing substrate clay fraction. The suspended particles mass (SPM) concentration indicates that clay particles were suspended and winnowed by wave action. Additionally, laser granulometry of the final substrates verified that ripple crests were composed of pure sand layers that were absent at ripple troughs, reflecting a relatively higher winnowing efficiency at wave ripples crest. The winnowing process and its efficiency is inexorably linked to wave ripple development and evolution. The implications of the results for sediment dynamics in mixed-bed substrates are highlighted and discussed.

Searching for Ancient Lakebeds in Ladon Basin, Mars and Implications for Future Exploration

NASA Astrophysics Data System (ADS)

Colón, A. M.; Miranda, C.; Milliken, R.

2017-12-01

It is well known from terrestrial studies that clay-rich rocks, and lacustrine mudstones in particular, are efficient at trapping, binding, and preserving organic matter through geologic time. This has also been demonstrated on Mars, where the Curiosity rover has detected organics in ancient mudstones in Gale crater. A number of other potential ancient lake sites have been proposed as landing sties for the Mars 2020 rover, including regions within the Ladon Basin and Valles system. In this study we map of the distribution of clay deposits in the Uzboi-Morava-Ladon (ULM) System, a system thought to have been a series of lakes interconnected by channels, and assess how these hydrous minerals relate to topography, adjacent fluvial networks, and the overall stratigraphy of basin deposits. We use CTX images and near-IR spectral reflectance data from the Mars Reconnaissance Orbiter CRISM instrument to independently map morphological and mineralogical features within Ladon. We find a number of occurrences of stratified, light-toned outcrops within the basin, but individual outcrops are small even at the scale of CTX images and are concentrated in several locations in the basin. Some light-toned outcrops are associated with clay minerals, but in general the light-toned appearance appears to be a poor proxy for clay distribution. CRISM data reveal that some clay-bearing regions are visually indistinct from adjacent clay-poor terrains. Some of the best examples of stratified, clay-bearing rocks are found in Ladon Valles, where they occur in terraces. In general, the stratigraphic, topographic, and morphologic evidence do not preclude a lacustrine origin, but there is no diagnostic evidence to support this interpretation either. The clay-bearing and light-toned deposits within Ladon basin may instead reflect deposition in an alluvial/fluvial system that post-dates the peak period of inferred lacustrine activity in the ULM system.

X-Ray Fingerprinting Techniques for Recognizing A Hydrological Role in the Formation of Minerals on the Surface of Mars

NASA Technical Reports Server (NTRS)

Metzger, Ellen P.; John, R.

1999-01-01

Previous work has demonstrated the ability of a miniaturized XRD-XRF instrument to perform in-situ analyses without sample preparation or acquisition. Deployment of this instrument on a Martian rover will allow a large number of rapid qualitative analyses, which will maximize the diversity of samples studied and selected for possible return. As a first step in designing a decision tree for recognizing minerals in complex mixtures, d spacings were plotted against intensity for several mineral groups comprising rock and soil types inferred for the surface of Mars (weathered basalt, playa and hydrothermal deposits, clay-rich soils). In all groups, d spacings cluster in a range from about 1-4 angstroms, which can under certain circumstances obscure patterns for individual phases. However, within the silicate family, minerals containing either bound OH- or molecules of H20 (clays, micas, amphiboles, zeolites) are characterized by a shift of peaks to higher d spacings. Large d spacings (greater than about 7 angstroms) thus act as a first-order filter for distinguishing hydrous from anhydrous silicates. The ability to quickly verify the presence of silicates that have interacted with water has important implications for using mineral chemistry and structure to help decipher the hydrologic and atmospheric history of Mars. This represents a beginning for developing more sophisticated methods of pattern recognition. These will combine XRD and XRF analyses with optical data to rapidly7 discern environmentally diagnostic assemblages without the necessity of identifying every peak individual mineral phase.

Generalized thickness of the confining bed overlying the Floridan Aquifer, Southwest Florida Water Management District

USGS Publications Warehouse

Buono, Anthony; Spechler, R.M.; Barr, G.L.; Wolansky, R.M.

1979-01-01

This map presents the thickness of the confining bed overlying the Floridan aquifer in the Southwest Florida Water Management District and adjacent areas. The bed separates the surficial aquifer from the underlying Floridan aquifer. Lithologic logs and information from quarries were used in conjunction with an unpublished map to compile this map at 1:250,000 scale. Units included in the confining bed are: clay, sandy clay and marl, undifferentiated with respect to age, the Hawthorn Formation, and the unconsolidated sections of the Tampa Limestone. (Kosco-USGS)

Enhanced Preliminary Assessment Report: Croom Army Housing Units, Croom, Maryland

DTIC Science & Technology

1989-10-01

aquifer from recharge (via rain) or leakage (via confining beds and other aquifers). The Patuxent, Patapsco, and Magothy formations contain aquifers that...is generally low in chlorides and total dissolved solids. The Magothy formation is one of the most extensive water-bearing aquifers in the Coastal...the base of the formation, and clays increase toward its top. A potential problem in the Magothy aquifer is the possible intrusion of brackish water

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.

1968-01-01

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.

Microbial reduction of structural iron in interstratified illite-smectite minerals by a sulfate-reducing bacterium.

PubMed

Liu, D; Dong, H; Bishop, M E; Zhang, J; Wang, H; Xie, S; Wang, S; Huang, L; Eberl, D D

2012-03-01

Clay minerals are ubiquitous in soils, sediments, and sedimentary rocks and could coexist with sulfate-reducing bacteria (SRB) in anoxic environments, however, the interactions of clay minerals and SRB are not well understood. The objective of this study was to understand the reduction rate and capacity of structural Fe(III) in dioctahedral clay minerals by a mesophilic SRB, Desulfovibrio vulgaris and the potential role in catalyzing smectite illitization. Bioreduction experiments were performed in batch systems, where four different clay minerals (nontronite NAu-2, mixed-layer illite-smectite RAr-1 and ISCz-1, and illite IMt-1) were exposed to D. vulgaris in a non-growth medium with and without anthraquinone-2,6-disulfonate (AQDS) and sulfate. Our results demonstrated that D. vulgaris was able to reduce structural Fe(III) in these clay minerals, and AQDS enhanced the reduction rate and extent. In the presence of AQDS, sulfate had little effect on Fe(III) bioreduction. In the absence of AQDS, sulfate increased the reduction rate and capacity, suggesting that sulfide produced during sulfate reduction reacted with the phyllosilicate Fe(III). The extent of bioreduction of structural Fe(III) in the clay minerals was positively correlated with the percentage of smectite and mineral surface area of these minerals. X-ray diffraction, and scanning and transmission electron microscopy results confirmed formation of illite after bioreduction. These data collectively showed that D. vulgaris could promote smectite illitization through reduction of structural Fe(III) in clay minerals. © 2011 Blackwell Publishing Ltd.

Dynamics of confined reactive water in smectite clay-zeolite composites.

PubMed

Pitman, Michael C; van Duin, Adri C T

2012-02-15

The dynamics of water confined to mesoporous regions in minerals such as swelling clays and zeolites is fundamental to a wide range of resource management issues impacting many processes on a global scale, including radioactive waste containment, desalination, and enhanced oil recovery. Large-scale atomic models of freely diffusing multilayer smectite particles at low hydration confined in a silicalite cage are used to investigate water dynamics in the composite environment with the ReaxFF reactive force field over a temperature range of 300-647 K. The reactive capability of the force field enabled a range of relevant surface chemistry to emerge, including acid/base equilibria in the interlayer calcium hydrates and silanol formation on the edges of the clay and inner surface of the zeolite housing. After annealing, the resulting clay models exhibit both mono- and bilayer hydration structures. Clay surface hydration redistributed markedly and yielded to silicalite water loading. We find that the absolute rates and temperature dependence of water dynamics compare well to neutron scattering data and pulse field gradient measures from relevant samples of Ca-montmorillonite and silicalite, respectively. Within an atomistic, reactive context, our results distinguish water dynamics in the interlayer Ca(OH)(2)·nH(2)O environment from water flowing over the clay surface, and from water diffusing within silicalite. We find that the diffusion of water when complexed to Ca hydrates is considerably slower than freely diffusing water over the clay surface, and the reduced mobility is well described by a difference in the Arrhenius pre-exponential factor rather than a change in activation energy.

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

Effect of organic matters on CO2 hydrate phase equilibrium conditions in Na-montmorillonite clay

NASA Astrophysics Data System (ADS)

Park, T.; Kyung, D.; Lee, W.

2013-12-01

Formation of gas hydrates provides an attractive idea for storing greenhouse gases in a long-term stable geological formation. Since the phase equilibrium conditions of gas hydrates indicate the stability of hydrates, estimation of the phase equilibrium conditions of gas hydrates in marine geological conditions is necessary. In this study, we have identified the effects of organic matters (glycine, glucose, and urea) and solid surface (montmorillonite (MMT)) on the three-phase (liquid-hydrate-vapor) equilibrium conditions of CO2 hydrate. CO2 phase equilibrium experiments were conducted using 0.5mol% organic matter solutions with and without 10g soil mineral were experimentally conducted. Addition of organic matters shifted the phase equilibrium conditions of CO2 hydrate to the higher pressure or lower pressure region because of higher competition of water molecules due to the dissolved organic matters. Presence of MMT also leaded to the higher equilibrium pressure due to the interaction of cations with water molecules. By addition of organic matters to the clay suspension, the hydrate phase equilibrium conditions were less inhibited compared to those of MMT and organic matters independently. The diminished magnitudes by addition of organic matters to the clay suspension (MMT > MMT+urea > MMT+glycine > MMT+glucose > DIW) were different to the order of inhibition degree without MMT (Glucose > glycine > urea > DIW). X-ray diffraction (XRD), scanning electron microscope (SEM), and ion chromatography (IC) analysis were conducted to support the hypothesis that the organic matters interact with cations in MMT interlayer space, and leads to the less inhibition of phase equilibrium conditions. The present study provides basic information for the formation and dissociation of CO2 hydrates in the geological formation when sequestering CO2 as a form of CO2 hydrate.

Phosphates in some Missouri refractory clays

USGS Publications Warehouse

Halley, Robert B.; Foord, Eugene E.; Keller, David J.; Keller, Walter 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 diaspore, 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.

Advanced clay nanocomposites based on in situ photopolymerization utilizing novel polymerizable organoclays

NASA Astrophysics Data System (ADS)

Kim, Soon Ki

Polymer nanocomposite technology has had significant impact on material design. With the environmental advantages of photopolymerization, a research has recently focused on producing nanocomposites utilizing inexpensive clay particles based on in situ photopolymerization. In this research, novel polymerizable organoclays and thiol-ene photopolymerization have been utilized to develop advanced photopolymer clay nanocomposites and to overcome several limitations in conventional free radical photopolymers. To this end, factors important in nanocomposite processes such as monomer composition, clay dispersion, and photopolymerization behavior in combination with the evolution of ultimate nanocomposite properties have been investigated. For monomer-organoclay compositions, higher chemical compatibility of components induces enhanced clay exfoliation, resulting in photopolymerization rate increases due to an amplified clay template effect. Additionally, by affecting the stoichiometric ratio between thiol and acrylate double bond in the clay gallery, thiolated organoclays enhance thiol-ene copolymerization with increased final thiol conversion while acrylated organoclays encourage acrylate homopolymerization. In accordance with the reaction behavior, incorporation of thiolated organoclays makes polymer chains more flexible with decreased glass transition temperature due to higher formation of thio-ether linkages while adding acrylated organoclays significantly increases the modulus. Photopolymer nanocomposites also help overcome two major drawbacks in conventional free radical photopolymerization, namely severe polymerization shrinkage and oxygen inhibition during polymerization. With addition of a low level of thiol monomers, the oxygen inhibition in various acrylate systems can be overcome by addition of only 5wt% thiolated organoclay. The same amount of polymerizable organoclay also induces up to 90% decreases in the shrinkage stress for acrylate or thiol-acrylate systems. However, nonreactive clays do not reduce the stress substantially and even decreases the polymerization rate in air. Additionally, the clay morphology and polymerization behavior are closely related with evolution of ultimate nanocomposite performance. Use of polymerizable organoclay significantly improves overall toughness of nanocomposites by increasing either modulus or elongation at break based on the type of polymerizable organoclay, which demonstrates the promise of this technology as a modulation and/or optimization tool for nanocomposite properties.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

The mineralogical composition of agrogray, dark gray, and agro-dark gray soils (Luvic Greyzemic Retic Phaeozems); agro-dark gray residual-calcareous soils (Calcaric Cambic Phaeozems); clay-illuvial agrochernozems (Luvic Chernic Phaeozems); and agrochernozems with migrational-mycelial carbonates (Haplic Chernozems) developed in the forest-steppe of Central Siberia within the Irkutsk Depression has been studied. The clay (<1 μm) fraction separated from these soils consists of mixed-layer minerals with alternating layers of hydromica, smectite, vermiculite, and chlorite; the proportions between them change within the soil profiles. The clay fraction also contains hydromicas, kaolinite, chlorite, and some admixture of the fine-dispersed quartz. Each type of the soils is characterized by its own distribution pattern of clay material with specific alternation of layers in the mixed-layer formations. Mixed-layer minerals of the chlorite-vermiculite type predominate in the upper horizons of texture-differentiated soils. Down the soil profile, the content of mixed-layer mica-smectitic minerals increases. In the clay fraction of arable dark gray-humus soils with residual carbonates, the distribution of the clay fraction and major mineral phases in the soil profile is relatively even. An increased content of well-crystallized kaolinite is typical of these soils. The parent material of agrochernozems has a layered character: the upper horizons are generally depleted of clay, and the middle-profile and lower horizons are characterized by the considerable kaolinite content. In general, the clay material of soils of the Tulun-Irkutsk forest-steppe differs considerably from the clay material of foreststeppe soils developed from loesslike and mantle loams in the European part of Russia. In particular, this difference is seen in the proportions between major mineral phases and between biotitic and muscovitic components, as well as in the degree of crystallinity and behavior of kaolinite and chlorite.

Diffusional Transport of Organic Solutes in Subsurface Clay Lenses and Layers

NASA Astrophysics Data System (ADS)

Demond, A. H.; Ayral, D.; Goltz, M. N.

2009-12-01

The storage of organic solvents in clay lenses and layers in the subsurface creates long-term contaminant sources. Because of the low hydraulic conductivities of clay, it is thought that organic movement into clay lenses occurs through the process of diffusion. The ratio of the effective diffusion coefficient in the porous medium and the diffusion coefficient in bulk water is usually given by the tortuosity factor which accounts for the reduced area and the increased path length in the porous medium. However, there is field evidence which suggests that the concentrations in these lenses exceed that which can be accounted for by simple diffusion. There are reports, for example, of tortuosity factors greater than 1.0, which theoretically is not possible. Clays such as montmorillonite or bentonite shrink and swell depending on water content, and similar behavior can occur in the presence of organic solvents. In fact, research has shown that the basal spacing of bentonite can decrease by 50% when permeated with heptane. Such contraction of the clay structure can lead to the formation of cracks and macropores, with a concomitant alteration of the diffusional pathways that solutes follow. Models formulated for diffusional transport in soil are available to calculate the tortuosity factor as a function of water content. In addition, models are available to simulate phenomena in which the diffusion coefficient is concentration dependent. However, calculations of diffusional transport using such models show that they may not adequately reflect the impact of the alteration of the clay structure. However, modeling the transport of organic solutes in clay as a dual-domain system with some minimal advective transport in macropores can yield tortuosity factors greater than 1.0. Thus, it appears the cracking of clay in contact with organic solvents and a resultant advective component to transport of the solute may be an explanation of field observations.

Description of Arundel Clay ornithomimosaur material and a reinterpretation of Nedcolbertia justinhofmanni as an "Ostrich Dinosaur": biogeographic implications.

PubMed

Brownstein, Chase Doran

2017-01-01

The fossil record of dinosaurs from the Early Cretaceous of Eastern North America is scant, especially since a few stratigraphic units from the east are fossiliferous. Among these stratigraphic units, the Arundel Clay of the eastern seaboard has produced the best-characterized dinosaur faunas known from the Early Cretaceous of Eastern North America. The diverse dinosaur fauna of the Arundel Clay has been thoroughly discussed previously, but a few of the dinosaur species originally described from the Arundel Clay are still regarded as valid genera. Much of the Arundel material is in need of review and redescription. Among the fossils of dinosaurs from this stratigraphic unit are those referred to ornithomimosaurs. Here, the researcher describes ornithomimosaur remains from the Arundel Clay of Prince George's County, Maryland which may be from two distinct ornithomimosaur taxa. These remains provide key information on the theropods of the Early Cretaceous of Eastern North America. Recent discoveries of small theropod material from the Arundel Clay possibly belonging to ornithomimosaurs are also reviewed and described for the first time. The description of the Arundel material herein along with recent discoveries of basal ornithomimosaurs in the past 15 years has allowed for comparisons with the coelurosaur Nedcolbertia justinhofmanni , suggesting the latter animal was a basal ornithomimosaur rather than a "generalized" coelurosaur as it was originally described. Comparisons between the Arundel ornithomimosaur material and similar Asian and European specimens suggest that both extremely basal ornithomimosaurs and more intermediate or derived forms may have coexisted throughout the northern hemisphere during the Early Cretaceous.

Microstructures and deformation mechanisms in Opalinus Clay: insights from scaly clay from the Main Fault in the Mont Terri Rock Laboratory (CH)

NASA Astrophysics Data System (ADS)

Laurich, Ben; Urai, Janos L.; Nussbaum, Christophe

2017-01-01

The Main Fault in the shaly facies of Opalinus Clay is a small reverse fault formed in slightly overconsolidated claystone at around 1 km depth. The fault zone is up to 6 m wide, with micron-thick shear zones, calcite and celestite veins, scaly clay and clay gouge. Scaly clay occurs in up to 1.5 m wide lenses, providing hand specimens for this study. We mapped the scaly clay fabric at 1 m-10 nm scale, examining scaly clay for the first time using broad-ion beam polishing combined with scanning electron microscopy (BIB-SEM). Results show a network of thin shear zones and microveins, separating angular to lensoid microlithons between 10 cm and 10 µm in diameter, with slickensided surfaces. Our results show that microlithons are only weakly deformed and that strain is accumulated by fragmentation of microlithons by newly formed shear zones, by shearing in the micron-thick zones and by rearrangement of the microlithons.The scaly clay aggregates can be easily disintegrated into individual microlithons because of the very low tensile strength of the thin shear zones. Analyses of the microlithon size by sieving indicate a power-law distribution model with exponents just above 2. From this, we estimate that only 1 vol % of the scaly clay aggregate is in the shear zones.After a literature review of the hypotheses for scaly clay generation, we present a new model to explain the progressive formation of a self-similar network of anastomosing thin shear zones in a fault relay. The relay provides the necessary boundary conditions for macroscopically continuous deformation. Localization of strain in thin shear zones which are locally dilatant, and precipitation of calcite veins in dilatant shear fractures, evolve into complex microscale re-partitioning of shear, forming new shear zones while the microlithons remain much less deformed internally and the volume proportion of the µm-thick shear zones slowly increases. Grain-scale deformation mechanisms are microfracturing, boudinage and rotation of mica grains, pressure solution of carbonate fossils and pore collapse during ductile flow of the clay matrix. This study provides a microphysical basis to relate microstructures to macroscopic observations of strength and permeability of the Main Fault, and extrapolating fault properties in long-term deformation.

Validating Experimental Bedform Dynamics on Cohesive Sand-Mud Beds in the Dee Estuary

NASA Astrophysics Data System (ADS)

Baas, Jaco H.; Baker, Megan; Hope, Julie; Malarkey, Jonathan; Rocha, Renata

2014-05-01

Recent laboratory experiments and field measurements have shown that small quantities of cohesive clay, and in particular 'sticky' biological polymers, within a sandy substrate dramatically reduce the development rate of sedimentary bedforms, with major implications for sediment transport rate calculations and process interpretations from the sedimentary record. FURTHER INFORMATION Flow and sediment transport predictions from sedimentary structures found in modern estuaries and within estuarine geological systems are impeded by an almost complete lack of process-based knowledge of the behaviour of natural sediments that consist of mixtures of cohesionless sand and biologically-active cohesive mud. Indeed, existing predictive models are largely based on non-organic cohesionless sands, despite the fact that mud, in pure form or mixed with sand, is the most common sediment on Earth and also the most biologically active interface across a range of Earth-surface environments, including rivers and shallow seas. The multidisciplinary COHBED project uses state-of-the-art laboratory and field technologies to measure the erosional properties of mixed cohesive sediment beds and the formation and stability of sedimentary bedforms on these beds, integrating the key physical and biological processes that govern bed evolution. The development of current ripples on cohesive mixed sediment beds was investigated as a function of physical control on bed cohesion versus biological control on bed cohesion. These investigations included laboratory flume experiments in the Hydrodynamics Laboratory (Bangor University) and field experiments in the Dee estuary (at West Kirby near Liverpool). The flume experiments showed that winnowing of fine-grained cohesive sediment, including biological stabilisers, is an important process affecting the development rate, size and shape of the cohesive bedforms. The ripples developed progressively slower as the kaolin clay fraction in the sandy substrate bed was increased. The same result was obtained for xanthan gum, which is a proxy for biological polymers produced by microphytobenthos. Yet, the xanthan gum was several orders more effective in slowing down ripple development than kaolin clay, suggesting that the cohesive forces for biological polymers are much higher than for clay minerals, and that sedimentological process models should refocus on biostabilisation processes. The first results of the field experiments show that the winnowing of fines from developing ripples and the slowing down of current ripple development in mixed cohesive sediment is mimicked on intertidal flats in the Dee estuary. In particular, these field data revealed that current ripples in cohesive sediment are smaller with more two-dimensional crestlines than in non-cohesive sand. The wider implications of these findings will be discussed. COHBED Project Team (NERC): Alan Davies (Bangor University); Daniel Parsons, Leiping Ye (University of Hull); Jeffrey Peakall (University of Leeds); Dougal Lichtman, Louise O'Boyle, Peter Thorne (NOC Liverpool); Sarah Bass, Andrew Manning, Robert Schindler (University of Plymouth); Rebecca Aspden, Emma Defew, Julie Hope, David Paterson (University of St Andrews)

OIL WELL REMEDIATION IN CLAY AND WAYNE COUNTIES, IL

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

Peter L. Dakuras; Larry Stieber; Dick Young

2003-02-01

This is the first technical progress report of the remediation of two wells and a water injection well in Clay County, Illinois. The location is identified as the Routt lease and the wells will be identified as the Routt No.3 and Routt No.4 respectively throughout this report. The Clay County portion of this project has met all legal, financial, and environmental requirements to drill and /or pump oil at this lease. We have also obtained all available information about this site and have taken the necessary steps to improve access roads, dig the necessary pits and build the necessary firewalls.more » Both wells have been drilled to the Salem formation. Gas gun technology was used to stimulate the reservoir of the Routt No.3. This report will address the technical aspects of the remediation.« less

Formation of metal clusters in halloysite clay nanotubes

NASA Astrophysics Data System (ADS)

Vinokurov, Vladimir A.; Stavitskaya, Anna V.; Chudakov, Yaroslav A.; Ivanov, Evgenii V.; Shrestha, Lok Kumar; Ariga, Katsuhiko; Darrat, Yusuf A.; Lvov, Yuri M.

2017-12-01

We developed ceramic core-shell materials based on abundant halloysite clay nanotubes with enhanced heavy metal ions loading through Schiff base binding. These clay tubes are formed by rolling alumosilicate sheets and have diameter of c.50 nm, a lumen of 15 nm and length 1 μm. This allowed for synthesis of metal nanoparticles at the selected position: (1) on the outer surface seeding 3-5 nm metal particles on the tubes; (2) inside the tube's central lumen resulting in 10-12 nm diameter metal cores shelled with ceramic wall; and (3) smaller metal nanoparticles intercalated in the tube's wall allowing up to 9 wt% of Ru, and Ag loading. These composite materials have high surface area providing a good support for catalytic nanoparticles, and can also be used for sorption of metal ions from aqueous solutions.

Formation of metal clusters in halloysite clay nanotubes.

PubMed

Vinokurov, Vladimir A; Stavitskaya, Anna V; Chudakov, Yaroslav A; Ivanov, Evgenii V; Shrestha, Lok Kumar; Ariga, Katsuhiko; Darrat, Yusuf A; Lvov, Yuri M

2017-01-01

We developed ceramic core-shell materials based on abundant halloysite clay nanotubes with enhanced heavy metal ions loading through Schiff base binding. These clay tubes are formed by rolling alumosilicate sheets and have diameter of c .50 nm, a lumen of 15 nm and length ~1 μm. This allowed for synthesis of metal nanoparticles at the selected position: (1) on the outer surface seeding 3-5 nm metal particles on the tubes; (2) inside the tube's central lumen resulting in 10-12 nm diameter metal cores shelled with ceramic wall; and (3) smaller metal nanoparticles intercalated in the tube's wall allowing up to 9 wt% of Ru, and Ag loading. These composite materials have high surface area providing a good support for catalytic nanoparticles, and can also be used for sorption of metal ions from aqueous solutions.

Aqueous geochemistry on Mars: Possible clues from salts and clays in SNC meteorites

NASA Technical Reports Server (NTRS)

Gooding, James L.

1992-01-01

All subgroups of the shergottite, nakhlite, and chassignite (SNC) meteorites contain traces of water precipitated minerals that include various combinations of carbonates, sulfates, halides, ferric oxides, and aluminosilicate clays of preterrestrial origin. Oxygen three-isotope analysis of thermally extracted bulk water has confirmed that at least some of the water in SNC's is, indeed, extraterrestrial. A mixture of aqueous precipitates found in the SNC's, comprising smectite, illite, and gypsum (with minor halite +/- calcite and hematite), provides a self-consistent, though not unique, model for the bulk elemental composition of surface sediments at the Viking Lander sites. Therefore, if the salts and clays in SNC's are truly linked to aqueous alteration and soil formation on Mars, then the suite of SNC secondary minerals might provide the best currently available insight into near-surface martian chemistry.

Environmental Inventory: Little South Fork Cumberland River.

DTIC Science & Technology

1981-11-01

coal and clay shale. The contact between the Mississippian strata (Pennington Formation ) and...these formations include the Barren Fork coal bed and the Stearns coal zone. In addition to these there are several unnamed coal beds. Number and...Cindy Cliff, Coal Cliff, Sand Cliff and Balls Cliff are being mined by the Greenwood Land and Mining Company of Somerset and Parkers Lake, Kentucky

Excavation Induced Hydraulic Response of Opalinus Clay - Investigations of the FE-Experiment at the Mont Terri URL in Switzerland

NASA Astrophysics Data System (ADS)

Vogt, T.; Müller, H. R.; Garitte, B.; Sakaki, T.; Vietor, T.

2013-12-01

The Full-Scale Emplacement (FE) Experiment at the Mont Terri underground research laboratory in Switzerland is a full-scale heater test in a clay-rich formation (Opalinus Clay). Based on the Swiss disposal concept it simulates the construction, emplacement, backfilling, and post-closure thermo-hydro-mechanical (THM) evolution of a spent fuel / vitrified high-level waste (SF / HLW) repository tunnel in a realistic manner. The main aim of this experiment is to investigate SF / HLW repository-induced THM coupled effects mainly in the host rock but also in the engineered barrier system (EBS), which consists of bentonite pellets and blocks. A further aim is to gather experience with full-scale tunnel construction and associated hydro-mechanical (HM) processes in the host rock. The entire experiment implementation (in a 50 m long gallery with approx. 3 m diameter) as well as the post-closure THM evolution will be monitored using a network of several hundred sensors (state-of-the-art sensors and measurement systems as well as fiber-optic sensors). The sensors are distributed in the host rock's near- and far-field, the tunnel lining, the EBS, and on the heaters. The heater emplacement and backfilling has not started yet, therefore only the host rock instrumentation is installed at the moment and is currently generating data. We will present the instrumentation concept and rationale as well as the first monitoring results of the excavation and ventilation phase. In particular, we investigated the excavation induced hydraulic response of the host rock. Therefore, the spatiotemporal evolution of porewater-pressure time series was analyzed to get a better understanding of HM coupled processes during and after the excavation phase as well as the impact of anisotropic geomechanic and hydraulic properties of the clay-rich formation on its hydraulic behavior. Excavation related investigations were completed by means of inclinometer data to characterize the non-elastic and time-dependent deformations. In addition, we evaluated the effect of drainage and suction processes during the ventilation phase on the pressure distribution in the host rock. Based on our results the conceptual models of HM processes and hydraulic behavior of clay rich formations during excavation and ventilation phases could be improved.

Chronology of magmatism and mineralization in the Kassandra mining area, Greece: The potentials and limitations of dating hydrothermal illites

NASA Astrophysics Data System (ADS)

Gilg, H. Albert; Frei, Robert

1994-05-01

Various geochronological methods ( U/Pb, Rb/Sr, and K/Ar) have been applied to constrain the timing of magmatism and polymetallic mineralization in the Kassandra mining district, northern Greece. These data provide the first geochronological evidence that porphyry copper mineralization, proximal copper skarns, and distal high-temperature carbonate-hosted Pb-Zn-Ag-Au replacement ores formed contemporaneously and probably within less than 2 million years. Polymetallic mineralization is temporally related to the emplacement of granodioritic to quartz dioritic porphyries (24-25 Ma) that postdate the largest post-tectonic intrusion of the area, the Stratoni granodiorite (27.9 ± 1.2 Ma). Andesite porphyry dikes, which crosscut the Pb-Zn-Ag-Au ores and associated alterations, represent the last magmatic phase in the area (19.1 ± 0.6 Ma) and did not contribute to metal concentration. The combination of K/Ar, Rb/Sr, and oxygen isotope studies of hydrothermal illite-rich clays and careful granulometric analysis constrains the reliability of these geochronological methods and emphasizes the importance of characterizing the post-formational history of the sample. We identify various processes which partly disturbed the K/Ar and Rb/Sr system of some clays, such as retrograde alteration by heated meteoric waters, superimposed supergene illitization, and resetting of both isotopic systems due to a hydrothermal overprint related to the intrusion of the andesite porphyry. Our data, however, suggest that diffusive Ar loss from the finest clay fractions (< 0.6 μm) during cooling of the hydrothermal system probably played the most important role in the disturbance of the K/Ar system. Conventional K/Ar ages of < 2 μm fractions from high-temperature illites (> 200°C), therefore, do not give reliable formation ages. The loss of Ar may be used to model the cooling history of the hydrothermal system applying the concept of closure temperatures ( DODSON, 1973). 40K- 40Ar rad isochrons of natural, coarser grained (> 0.6 μm) size fractions of illites from single samples, even when slightly contaminated with feldspars, may yield meaningful ages either of the formation or of a reheating event. The Rb/Sr dating of hydrothermal clays is sensitive to contamination by adsorbed strontium, which may not be cogenetic with the clay, as well as feldspars, which may not have been homogenized isotopically by the illitization process.

Adsorption of organic ligands on low surface charge clay minerals: the composition in the aqueous interface region.

PubMed

Jelavić, S; Stipp, S L S; Bovet, N

2018-06-27

An understanding of the mechanisms that control the adsorption of organic molecules on clay minerals is of interest in several branches of science and industry. Oil production using low salinity injection fluids can increase yields by as much as 40% over standard injection with seawater or formation water. The mechanism responsible for the low salinity response is still debated, but one hypothesis is a change in pore surface wettability. Organic contamination in soil and drinking water aquifers is a challenge for municipal water suppliers and for agriculture. A better understanding is needed for how mineral species, solution composition and pH affect the desorption of low molecular weight organic ligands from clay minerals and consequently their wettability. We used X-ray photoelectron spectroscopy under cryogenic conditions to investigate the in situ composition in the mineral-solution interface region in a series of experiments with a range of pH and ion concentrations. We demonstrate that both chlorite and kaolinite release organic molecules under conditions relevant for low salinity water flooding. This release increases with a higher solution pH but is only slightly affected by the character of the organic ligand. This is consistent with the observation that low salinity enhanced oil recovery correlates with the presence of chlorite and kaolinite. Our results indicate that the pore surface charge and salinity of formation water and injection fluids are key parameters in determining the low salinity response. In general, our results imply that clay mineral surface charge influences the composition in the interface through an affinity for organic molecules.

Generalized thickness and configuration of the top of the intermediate aquifer, West-Central Florida

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

Corral, M.A. Jr.; Wolansky, R.M.

1984-01-01

The water-bearing units of the intermediate aquifer consist of discontinuous sand, gravel, shell, and limestone and dolomite beds in the Tamiami Formation of late Miocene age and the Hawthorn Formation of middle Miocene age. Within parts of Polk, Manatee, Hardee, De Soto, Sarasota, and Charlotte Counties, sand and clay beds within the Tampa Limestone that are hydraulically connected to the Hawthorn Formation are also included in the intermediate aquifer. 15 refs.

Is it efficient to co-compost and co-vermicompost green waste with biochar and/or clay to reduce CO2 emissions? A short-term laboratory experiment on (vermi)composts with additives.

NASA Astrophysics Data System (ADS)

Barthod, Justine; Rumpel, Cornélia; Paradelo, Remigio; Dignac, Marie-France

2016-04-01

Intensive farming practices can lead to a depletion of soil organic matter, negatively impacting important soil properties such as structural stability, fertility and C storage. The addition of organic amendments such as compost and vermicompost, rich in carbon, helps maintaining soil organic matter levels or restoring degraded soils. Composting and vermicomposting are based on stabilization of organic matter through the mineralization of easily decomposable organic matter compounds, therefore releasing greenhouse gases, including CO2. The aim of this study was to evaluate the global potential reduction of such emissions by the use of additives (2:1 clay and/or biochar): during (vermi)composting processes and after use of the final products as soil amendments. We hypothesized that the interactions between the additives and organic matter may lead to carbon stabilization and that such interactions may be enhanced by the presence of worms (Eisenia). We added in different proportions clay (25% or 50%), biochar (10%) and a mixture of biochar (10%) with clay (25%) to pre-composted green waste. The CO2 emissions of the composting and vermicomposting processes were measured during 21 days. After that, the amendments were added to a loamy cambisol soil and the CO2 emissions were monitored during 30 days of a laboratory experiment. The most efficient treatments in terms of reducing global CO2 emissions were the co-vermicomposting process with 25% clay followed by co-composting with 50% clay and with 10% biochar plus 25% clay. In this treatment (vermicompost with 25% clay), the carbon emissions were decreased by up to 44% compared to regular compost. Addition of biochar reduced CO2 emissions only during composting. Co-composting with biochar could be a promising avenue to limit global CO2 emissions whereas in presence of worms clay additions are better suited. These findings suggest that the presence of worms increased the formation of organo-mineral associations and thus C protection up to a certain clay/organic matter ratio. This strategy could be used to enhance the stability of organic amendments and increase soil carbon sequestration.

Report on International Collaboration Involving the FE Heater and HG-A Tests at Mont Terri

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

Houseworth, Jim; Rutqvist, Jonny; Asahina, Daisuke

Nuclear waste programs outside of the US have focused on different host rock types for geological disposal of high-level radioactive waste. Several countries, including France, Switzerland, Belgium, and Japan are exploring the possibility of waste disposal in shale and other clay-rich rock that fall within the general classification of argillaceous rock. This rock type is also of interest for the US program because the US has extensive sedimentary basins containing large deposits of argillaceous rock. LBNL, as part of the DOE-NE Used Fuel Disposition Campaign, is collaborating on some of the underground research laboratory (URL) activities at the Mont Terrimore » URL near Saint-Ursanne, Switzerland. The Mont Terri project, which began in 1995, has developed a URL at a depth of about 300 m in a stiff clay formation called the Opalinus Clay. Our current collaboration efforts include two test modeling activities for the FE heater test and the HG-A leak-off test. This report documents results concerning our current modeling of these field tests. The overall objectives of these activities include an improved understanding of and advanced relevant modeling capabilities for EDZ evolution in clay repositories and the associated coupled processes, and to develop a technical basis for the maximum allowable temperature for a clay repository.« less

Study of Adsorption and Flocculation Properties of Natural Clays to Remove Prorocentrum lima

PubMed Central

Louzao, Maria Carmen; Abal, Paula; Fernández, Diego A.; Vieytes, Mercedes R.; Legido, José Luis; Gómez, Carmen P.; Pais, Jesus; Botana, Luis M.

2015-01-01

High accumulations of phytoplankton species that produce toxins are referred to as harmful algal blooms (HABs). HABs represent one of the most important sources of contamination in marine environments, as well as a serious threat to public health, fisheries, aquaculture-based industries, and tourism. Therefore, methods effectively controlling HABs with minimal impact on marine ecology are required. Marine dinoflagellates of the genera Dinophysis and Prorocentrum are representative producers of okadaic acid (OA) and dinophysistoxins responsible for the diarrhetic shellfish poisoning (DSP) which is a human intoxication caused by the consumption of shellfish that bioaccumulate those toxins. In this work we explore the use of natural clay for removing Prorocentrum lima. We evaluate the adsorption properties of clays in seawater containing the dinoflagellates. The experimental results confirmed the cell removal through the flocculation of algal and mineral particles leading to the formation of aggregates, which rapidly settle and further entrain cells during their descent. Moreover, the microscopy images of the samples enable one to observe the clays in aggregates of two or more cells where the mineral particles were bound to the outer membranes of the dinoflagellates. Therefore, this preliminary data offers promising results to use these clays for the mitigation of HABs. PMID:26426051

Preliminary report on the White Canyon area, San Juan county, Utah

USGS Publications Warehouse

Benson, William E.; Trites, Albert F.; Beroni, Ernest P.; Feeger, John A.

1952-01-01

The White Canyon area, in the central part of San Juan County, Utah, consists of approximately two 15-minute quadrangles. Approximately 75 square miles have been mapped by the Geological Survey on a scale of 1 inch equals 1 mile, using a combined aerial photography-plane table method. Structure contours were drawn on top of the Organ Rock member of the Cutler formation. Parts of the Gonway and North Point claims, 1/4 mile east of the Happy Jack mine, were mapped in detail. The principal objectives of the investigations were: (1) to establish ore guides; (2) to select areas favorable for exploration; and (3) to map the general geology and to determine the regional relationships of the uranium deposits. The White Canyon area is comprised of sedimentary rocks of Carboniferous to Jurassic age, more than 2,000 feet thick, having a regional dip of 1° to 2° SW. The nearest igneous rocks are in the Henry Mountains about 7 miles west of the northern part of the area; The Shinarump conglomerate of the late Triassic age, the principal ore horizon in the White Canyon area, consists of lenticular beds of sandstone, conglomeratic sandstone, conglomerate, clay, and siltstone. The Shinarump conglomerate, absent in places, is as much as 75 feet thick. The sandstones locally contain molds of logs and fragments of altered volcanic ash. Some of the logs have been replaced by copper and uranium minerals and iron oxides. The clay and siltstone underlie and are interbedded with the sandstone, and are most common in channels that cut into the underlying Moenkopi formation. The Shinarump conglomerate contains reworked Moenkopi siltstone fragments, clay balls, carbonized wood, and pebbles of quarts, quartzite, and chert. Jointing is prominent in the Western part of the mapped area. The three most prominent joint trends are due east, N. 65°-75° W., and N. 65°-75° E. All joints have vertical dips. The red beds are bleached along some joints, especially those that trend N. 65°-75° W. All uranium ore produced has been from the lower part of the Shinarump conglomerate, where it commonly occurs with copper as disseminations and fracture coatings in sandstone. Uranium and copper minerals also occur in low-grade disseminated deposits in the lower Chinle and in the Moenkopi formation and in veins cutting these formations. Although some uranium deposits occur in Chinarump channels and scours, copper and uranium minerals along fractures suggest that channel control may be secondary. Logs and clay balls apparently have exerted some chemical influences for deposition. The uranium occurs as the oxide in some deposits, and as secondary hydrous sulfates, phosphates, oxides, and silicates in these and several other deposits. Charcoal, iron and manganese oxides, and veinlets of hydrocarbon are abnormally radioactive in most of the deposits. Base-metal sulfides are commonly found inside the oxidized zone. Secondary copper minerals include the hydrous sulfates and carbonate. Gangue minerals include quarts, clay minerals, and manganese oxides, dickite (?), calcite, gypsum, pyrite, and chalcedony (?). Principal wall-rock alteration appears to have been silicification, clay alteration, and bleaching. Most of the shipped ore has contained more than 0.3 percent uranium. The ore also contains copper, commonly in grades lower than 1.0 percent. Criteria believed to be most useful for prospecting for concealed uranium deposits are (1) visible uranium minerals; (2) sulfide minerals; (3) secondary copper minerals; (4) dickite (?); (5) hydrocarbons; and (6) bleaching and alteration of the Moenkopi formation.

Geochemical and mineralogical constraints on the distribution and enrichment of the rare earth elements during pedogenesis and tropical weathering

NASA Astrophysics Data System (ADS)

Hardy, Liam; Smith, Martin; Moles, Norman; Marsellos, Antonios

2015-04-01

Current European manufacturing relies heavily on imports from the USA & China for unprocessed rare earth elements (REEs) and rare earth oxides (REOs). It has been suggested that the EU holds viable reserves of REEs that, with adequate research, could satisfy 10% of EU industrial demand, by the recycling of mine waste from bauxite production (red muds) alone (Deady, E. (BGS), 2014). Focus has been turned to the potential for Mount Weld type laterite deposits being exploited in the EU, but limited exploration and understanding of EU laterite (& paleo laterite) formations currently makes them unattractive to investment. Although previously researched, the full range of factors influencing the transition of rare earth (primarily lanthanide series, Y & Sc) elements between mineral and clay phases in allochthonous soils, saprolites and laterites is not fully understood, especially in present and Paleo-European environments (Herrington, Boni, Skarpelis, & Large, 2007) (Deady, E. (BGS), 2014) but several deposits globally are suggested to have formed at economically viable concentrations due to this secondary remobilisation & transition from mineral to clay phase and subsequent seasonal leaching and evaporation system, to form depositional buffer zones other than the soil base. (Hoatson, Jaireth, & Miezitis, 2011) (Berger, Janots, Gnos, Frei, & Bernier, 2014). This project intends to use new techniques in sequential extractions, ICP-MS, Quantitative XRD & SEM analysis to expand current knowledge around lateritic & allochtonous ore forming, & weathering processes. Heavy REE content and mineralogical variations in clays will be examined, with examples from a selection of profiles across Southern Europe (and potentially paleo soils from Scandinavia) to define the main influencing factors on REE concentration. Are the specific sites enriched simply by the nature of their source rock (protolith), by the soil formation (pedogenesis), or by biogenic & meteorological factors? These results will then be applied in targeted, environmentally focused exploration projects, and perhaps enhance techniques used industrially for the extraction of HREEs, for less environmentally damaging production in sensitive areas (with current research sites within national parks in Italy and Portugal; and in areas where it is believed more attention should be paid to environmental preservation, including Central Turkey and Southern China). It is hypothesised that: HREE content in tropical laterite formations is due primarily to the source rock's mineralogy, although it's distribution is a result of slower genesis and leaching as opposed to more common biogenetic pedogenesis. It is suggested this distribution initially forms banded horizontal enrichment zones according to protolith, but eventual separation of heavy and light REEs is controlled by clay-surface (the protolith's weathering style), solvent type, fluctuation and availability. It may be found, as in Fe-Ni laterite resources globally (Herrington, Boni, Skarpelis, & Large, 2007) (Eliopoulos, 2000), that high initial bedrock concentrations of REEs are not necessarily required if prolonged weathering continues to concentrate these elements/minerals over longer periods (although this has been found inversely in certain Turkish bauxites (Karadag˘, Peli, Ary, & Ayhan, 2008)). Regardless of eventual concentrations, identifying the argillic phase and the time scales required for clay REE hosting clay formation may broaden the European search for supergene enrichments to REE hosting marine shales, mineral sands and other sedimentary formations that have been long-term- weathered without major displacement.

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

DOE PAGES

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

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

Natural versus anthropogenic genesis of mardels (closed depressions) on the Gutland plateau (Luxembourg); archaeometrical and palynological evidence of Roman clay excavation from mardels.

NASA Astrophysics Data System (ADS)

van Mourik, Jan; Braekmans, Dennis; Doorenbosch, Marieke; Kuijper, Wim; van der Plicht, Hans

2016-04-01

Mardels, small closed depressions, are distinctive landforms on the Luxembourger Gutland plateau. In the present landscape most mardels are shallow fens, filled with colluvial sediments. The genesis of mardels has been studied intensively, inside and outside Luxembourg. Some researchers suggested a natural development and consider mardels as subsidence basins due to subsurface solution of gypsum veins, other researchers suggested cultural causes and consider mardels as prehistorical quarries. In the Gutland, mardels occur on various substrates. Mardels on the Strassen marls (li3) are abandoned quarries, related to clay excavation in Roman Time. Mardels on the Luxembourger sandstone (li2) are sinkholes, related to joint patterns in the sandstone formation. Mardels on the Keuper marls (km1,3) are originally subsidence basins, related to subsurface dissolutions of gypsum lenses and veins, filled with colluvial clay. The results of pollen analysis and archaeometrical tests demonstrate Roman extraction of clay for the production of ancient ceramics. So, the natural depressions have been enlarged to the present mardels. After excavation, the sedimentation of colluvium restarted in the abandoned quarries.

Safety-relevant hydrogeological properties of the claystone barrier of a Swiss radioactive waste repository: An evaluation using multiple lines of evidence

NASA Astrophysics Data System (ADS)

Gautschi, Andreas

2017-09-01

In Switzerland, the Opalinus Clay - a Jurassic (Aalenian) claystone formation - has been proposed as the first-priority host rock for a deep geological repository for both low- and intermediate-level and high-level radioactive wastes. An extensive site and host rock investigation programme has been carried out during the past 30 years in Northern Switzerland, comprising extensive 2D and 3D seismic surveys, a series of deep boreholes within and around potential geological siting regions, experiments in the international Mont Terri Rock Laboratory, compilations of data from Opalinus Clay in railway and motorway tunnels and comparisons with similar rocks. The hydrogeological properties of the Opalinus Clay that are relevant from the viewpoint of long-term safety are described and illustrated. The main conclusions are supported by multiple lines of evidence, demonstrating consistency of conclusions based on hydraulic properties, porewater chemistry, distribution of natural tracers across the Opalinus Clay as well as small- and large-scale diffusion models and the derived conceptual understanding of solute transport.

Preparation of alpha-alumina-supported mesoporous bentonite membranes for reverse osmosis desalination of aqueous solutions.

PubMed

Li, Liangxiong; Dong, Junhang; Lee, Robert

2004-05-15

In this study, mesoporous bentonite clay membranes approximately 2 microm thick were prepared on porous alpha-alumina substrates by a sol-gel method. Nanosized clay particles were obtained from commercial Na-bentonite powders (Wyoming) by a process of sedimentation, washing, and freeze-drying. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption-desorption were employed for membrane characterization. It was found that the content of solids, concentration of polymer binder, and pH value of the clay colloidal suspension had critical influences on membrane formation during the dip-coating process. The membranes were tested for reverse osmosis separation of a 0.1 M NaCl solution. Both water permeability and Na(+) rejection rate of the supported membranes were comparable to those of the compacted thick membranes reported in the literature. However, due to the drastically reduced membrane thickness, water permeance and flux of the supported membranes were significantly higher than those of the compacted thick membranes. It was also observed that the calcination temperature played a critical role in determining structural stability in water and desalination performance of the clay membrane.

Atomistic Structure of Mineral Nano-aggregates from Simulated Compaction and Dewatering.

PubMed

Ho, Tuan Anh; Greathouse, Jeffery A; Wang, Yifeng; Criscenti, Louise J

2017-11-10

The porosity of clay aggregates is an important property governing chemical reactions and fluid flow in low-permeability geologic formations and clay-based engineered barrier systems. Pore spaces in clays include interlayer and interparticle pores. Under compaction and dewatering, the size and geometry of such pore spaces may vary significantly (sub-nanometer to microns) depending on ambient physical and chemical conditions. Here we report a molecular dynamics simulation method to construct a complex and realistic clay-like nanoparticle aggregate with interparticle pores and grain boundaries. The model structure is then used to investigate the effect of dewatering and water content on micro-porosity of the aggregates. The results suggest that slow dewatering would create more compact aggregates compared to fast dewatering. Furthermore, the amount of water present in the aggregates strongly affects the particle-particle interactions and hence the aggregate structure. Detailed analyses of particle-particle and water-particle interactions provide a molecular-scale view of porosity and texture development of the aggregates. The simulation method developed here may also aid in modeling the synthesis of nanostructured materials through self-assembly of nanoparticles.

Atomistic Structure of Mineral Nano-aggregates from Simulated Compaction and Dewatering

DOE PAGES

Ho, Tuan Anh; Greathouse, Jeffery A.; Wang, Yifeng; ...

2017-11-10

The porosity of clay aggregates is an important property governing chemical reactions and fluid flow in low-permeability geologic formations and clay-based engineered barrier systems. Pore spaces in clays include interlayer and interparticle pores. Under compaction and dewatering, the size and geometry of such pore spaces may vary significantly (sub-nanometer to microns) depending on ambient physical and chemical conditions. Here we report a molecular dynamics simulation method to construct a complex and realistic clay-like nanoparticle aggregate with interparticle pores and grain boundaries. The model structure is then used to investigate the effect of dewatering and water content on micro-porosity of themore » aggregates. The results suggest that slow dewatering would create more compact aggregates compared to fast dewatering. Furthermore, the amount of water present in the aggregates strongly affects the particle-particle interactions and hence the aggregate structure. Detailed analyses of particle-particle and water-particle interactions provide a molecular-scale view of porosity and texture development of the aggregates. The simulation method developed here may also aid in modeling the synthesis of nanostructured materials through self-assembly of nanoparticles.« less

Origin, distribution, and rapid removal of hydrothermally formed clay at Mount Baker, Washington

USGS Publications Warehouse

Frank, David

1983-01-01

Clay minerals are locally abundant in two hydrothermal areas at Mount Baker-Sherman Crater and the Dorr Fumarole Field. The silt- and clay-size fractions of volcanic debris that is undergoing alteration at and near the ground surface around areas of current fumarolic activity in Sherman Crater are largely dominated by alunite and a silica phase, either opal or cristobalite, but contain some kaolinite and smectite. Correspondingly, the chemistry of solutions at the surface of the crater, as represented by the crater lake, favors the formation of alunite over kaolinite. In contrast, vent-filling debris that was ejected to the surface from fumaroles in 1975 contains more than 20 percent clay-size material in which kaolinite and smectite are dominant. The youngest eruptive deposit (probably 19th century) on the crater rim was also altered prior to ejection and contains as much as 27 percent clay-size material in which kaolinite, smectite, pyrophyllite, and mixed-layer illitesmectite are abundant. The hydrothermal products, kaolinite and alunite, are present in significant amounts in five large Holocene mudflows that originated at the upper cone of Mount Baker. The distribution of kaolinite in crater and valley deposits indicates that, with the passage of time, increasingly greater amounts of this clay mineral have been incorporated into large mass movements from the upper cone. Either erosion has cut into more kaolinitic parts of the core of Sherman Crater, or the amount of kaolinite has increased through time in Sherman Crater.

Origin of PCDDs in ball clay assessed with compound-specific chlorine isotope analysis and radiocarbon dating.

PubMed

Holmstrand, Henry; Gadomski, Damien; Mandalakis, Manolis; Tysklind, Mats; Irvine, Robert; Andersson, Per; Gustafsson, Orjan

2006-06-15

Polychlorinated dibenzo-p-dioxins (PCDDs) of high concentrations in a ball clay deposit from the Mississippi Embayment were found to be consistent with a natural abiotic and non-pyrogenic origin by investigation with bulk radiocarbon analysis, compound-specific chlorine isotope analysis (CSIA-delta37Cl) of octachlorodibenzo-p-dioxin (OCDD), and black carbon (BC) analysis. The conventional radiocarbon date of total organic carbon from a depth of approximately 10 m in three parallel cores ranged from 14 700 years to >48 000 years, indicating that the strata with elevated levels of PCDDs have remained isolated from recent anthropogenic input in these >40 Ma old clay sediments. The CSIA-delta37Cl of OCDD yielded a delta37Cl of -0.2 per thousandth, which is significantly higher than the postulated range for biotic chlorination by chloroperoxidase enzymes, -11 to -10 per thousandth, and falls within the known range for abiotic organochlorines, -6 to +3 per thousandth. The absence of correlations between concentrations of PCDDs and corresponding pyrogenic black carbon (BC), together with estimations of BC sorptive loadings and the absence of polychlorinated dibenzofurans (PCDFs), suggest that vegetation fires did not form these ball-clay PCDDs. Results from this study indicate that the high levels of the toxic and carcinogenic PCDDs found in kaolinite-bearing clays may result from natural abiotic formation via in situ surface-promoted reactions on the clay mineral, including a so-far unknown organic precursor, rather than being the result of anthropogenic contamination.

Surface geology of the Jeptha Knob cryptoexplosion structure, Shelby County, Kentucky

USGS Publications Warehouse

Cressman, Earle Rupert

1981-01-01

The Jeptha Knob crytoexplosion structure, described by Bucher in 1925, was remapped in 1973 as part of the U.S. Geological Survey and the Kentucky Geological Survey cooperative mapping program. The knob is in the western part of the Blue Grass region. Hilltops in the rolling farmland adjacent to the knob are underlain by the nearly flat-lying Grant Lake and Callaway Creek Limestones of middle Late Ordovician age, and the valleys are cut in interbedded limestone and shale of the Clays Ferry Formation of late Middle and early Late Ordovician age. Precambrian basement is estimated to be 4,000 ft below the surface. The mapped area is 50 miles west of the crest of the Cincinnati arch; the regional dip is westward 16 ft per mile. The 38th parallel lineament is 50 miles to the south. The structure, about 14,000 ft in diameter, consists of a central area 6,300 ft in diameter of uplifted Clays Ferry Formation surrounded by a belt of annular faults that are divided into segments by radial faults. The grass structure of the Clays Ferry Formation is that of a broad dame, but same evidence indicates that, in detail, the beds are complexly folded. The limestone of the Clays Ferry is brecciated and infiltrated by limonite. The brecciation is confined to single beds, and there is no mixing of fragments from different beds. A small plug of the Logana Member of the Lexington Limestone (Middle Ordovician) has been upfaulted at least 700 ft and emplaced within the Clays Ferry. The central uplift is separated by high-angle and, in places, reverse faults from the belt of annular faulting. The concentric faults in the zone of annular faults are extensional, and the general aspect is of collapse and inward movement. Lenses of breccia are present along many of the concentric faults, but not along the radial faults. At least same of the breccia was injected from below. The youngest beds involved in the faulting are in the Bardstown Member of the Drakes Formation of late Late Ordovician age. The faulted and brecciated beds are overlain by nearly horizontal dolomite and shale of Early and Middle Silurian age. The basal 5 ft of the oldest Silurian unit, the Brassfield Formation, contains calcarenite and calcirudite composed, in large part, of locally derived fragments from the Upper Ordovician formations. The Jeptha Knob structure was formed in latest Late Ordovician or earliest Early Silurian time. At the time of formation, the area was either very slightly above or very slightly below sea level; the sediments were already largely indurated. At the onset of Silurian deposition, the area of the central uplift was probably a broad shallow depression not more than about 15 ft deep, possibly surrounded by a rim of Upper Ordovician rocks or rock fragments. The origin of the Jeptha Knob structure cannot be determined from the available data. Shatter cones and coesite, considered by many to be definitive criteria far origin by impact, have not been found. On the other hand, geophysical studies indicate that there is no coincident uplift of the basement, and there is no certain relation of Jeptha Knob to any obvious structural trend.

Genesis of petroduric and petrocalcic horizons in Latinamerica volcanic soils

NASA Astrophysics Data System (ADS)

Quantin, Paul

2010-05-01

Introduction. In Latinamerica, from Mexico to Chile, there are indurated volcanic soils horizons, named 'tepetate' in Mexico or cangahua in the Andes Mountains. Apart from original volcanic tuffs, these horizons were produced by pedogenesis: either through a former weathering of volcanic ash layers into fragic and later to petrocalcic horizons; or after a former soil formation through a second process of transformation from clayey volcanic soils to silicified petroduric horizons. This oral presentation will briefly deal with the formation of petroduric horizons in Mexico and petrocalcic horizon in Ecuador. Petroduric horizon genesis in Mexico. A soil climato-toposequence, near to Veracruz (Rossignol & Quantin, 1997), shows downwards an evolution from a ferralic Nitisol to a petroduric Durisol. A Durisol profile comports these successive horizons: at the top A and Eg, then columnar Btg-sim, laminar Bt-sim , prismatic Bsim, plinthite Cg, over andesite lava flow. Among its main features are especially recorded: clay mineralogy, microscopy and HRTEM. These data show: an increase in cristobalite at the expenses of 0.7 nm halloysite in Egsiltans, laminar Bt-sim, around or inside the columns or prisms of Btg-sim and Bsimhorizons. HRTEM (Elsass & al 2000) on ultra thin sections reveals an 'epigenesis' of clay sheets by amorphous silica, to form successively A-opal, Ct-opal and microcrystalline cristobalite. From these data and some groundwater chemical analyses, a scenario of duripan formation from a past clayey Nitisol is inferred: clay eluviation-illuviation process? alternate redoximorphy? clay degradation, Al leaching and Si accumulation, to form successively A-opal, Ct-opal and cristobalite. Petrocalcic horizon genesis in Ecuador. A soil climato-toposequence on pyroclastic flows, near to Bolivar in Ecuador (Quantin & Zebrowski, 1997), shows downwards the evolution from fragic-eutric-vitric Cambisols to petrocalcic-vitric Phaeozems, at the piedmont under semi-arid climate. A complex soil profile of petrocalcic Phaeozem, derived from 4 pyroclastic layers, shows among its successive horizons: in layer 3 the 'upper cangahua' with petrocalcic features and in layer 4 the 'lower cangahua' with hard fragipan properties. The features of the petrocalcic cangahua differ from a Mexican fragipan (Hidalgo & al 1997) by: a hard calcrete, higher alkalinity, stability in water after HCl and NaOH treatment, 2-4% of 'free silica'. The macro and micro-morphology shows: the laminar calcite crust, at the top of cangahua, with alternate micrite-sparite layers; downwards, microcalcite infillings in the voids of a prismatic structure, invading the groundmass by epigenesis of clay sheets, together whith microcrystalline opal. From these data this scenario is inferred: after a former weathering of volcanic glass to form a clayey matrix, as well amorphous silica and microcalcite coatings and infillings, then a second process, perhaps due to drier climate, produced the laminar crust formation, by invasion of microcalcite in the matrix. Conclusion. The petrocalcic horizon in Ecuador was produced by two processes: from a former phase of weathering giving a fragic horizon to a second producing the accumulation of calcite and some opal over and inside the matrix, due to climate change. The petroduric horizon in Mexico, is the product of a very complex soil transformation, from a former clayey Nitisol, through four successive processes: clay eluviation-illuviation, alternate redoximorphy, clay degradation, finally a progressive silicification over and inside the groundmass, probably due to pedoclimate change. References F. Elsass, D. Dubroeucq & M. Thiry. 2000. Clay Minerals, 35, 477-489. C. Hidalgo, P. Quantin & F. Elsass. 1997. Memorias del III Simposio Internacional sobre Suelos volcanicos endurecidos (Quito 1996), p. 65-72. - P. Quantin & C. Zebrowski. 1997. idem, p. 29-47.- J.P. Rossignol & P. Quantin. 1997. idem, p. 73-82.

Pedogenesis of a catena of the Farmdale-Sangamon Geosol complex in the north central United States

USGS Publications Warehouse

Jacobs, P.M.; Konen, M.E.; Curry, B. Brandon

2009-01-01

The Farmdale-Sangamon Geosol pedocomplex consists of the Sangamon Geosol and the overlying Farmdale Geosol, which form the most extensive terrestrial record of the last interglacial to glacial transition in the Midwest United States. The geosol complex formed for upwards of 100??ka, extending from the end of MIS 6 through 4 for the Sangamon Geosol, then the Farmdale Geosol for during a brief episode at the end of MIS 3 following slow accumulation and pedogenic modification of eolian silt deposited on top of the Sangamon Geosol. Our study site consists of a buried paleo-hillslope transect that forms a catena, enabling evaluation of slope effects on interglacial-scale soil formation. The Sangamon Geosol is formed in calcareous and illitic glaciogenic sediment. Along the catena the Sangamon Geosol profiles display some morphological changes, namely in terms of colors that we interpret as indicators of differences in drainage. Most thickness and horizonation characteristics are similar all along the transect, with intact upper sola horizons (AE and E horizons) that overlie clay-enriched Bt horizons. The Bt horizons contain abundant clay that exists as illuvial clay coatings, matrix infills, and as mosaic-speckled domains. The clay originated both by in situ weathering and through illuviation from the clay depleted upper sola. Slope does not appear to affect Bt characteristics beyond redder hues of the matrix and clay coatings in the upper slope position. With depth, effects of carbonate leaching and infilling of clay in the matrix decrease and clay coatings are restricted to walls of voids adjacent to aggregates. Clay mineralogy shows illite depletion, but no interstratified kaolinite-expandable minerals, indicating the degree of weathering is not as great as is typical of Sangamon Geosol profiles formed in loess or in glaciogenic sediment of the central Illinois type area. Clay mineralogy is also stratified with depth, coincident with particle size, which probably indicates sorting of layers of illitic dolomite and shale. Variation of horizon and profile characteristics appears to largely be a function of particle size variability and stratification than topographic position in the catena. The influence of hillslope position on soil redistribution during formation of the Sangamon Geosol appears negligible given the uniformity of upper solum horizon thickness and sandy particle size characteristics, so we conclude that a bioturbation and rainwash origin of the upper solum and the texture contrast in these profiles is not the best process model explanation. We suggest that the base-rich nature of these soils led to ecosystem characteristics that discouraged erosion and encouraged infiltration and a lessivage-type origin of the texture contrast. No convincing evidence of MIS 6 through MIS 4 loess occurs at this site. The Farmdale Geosol formed in the Robein Silt, which is Roxana Silt (MIS 3 loess) that was redistributed downslope. The Robein Silt is thicker and finer in the topographic low and indicates the cooler and forested environmental conditions during MIS 3 were conducive to downslope movement of soil and also produced greater differences in drainage-induced soil morphological changes in the Farmdale Geosol. ?? 2009 Elsevier B.V. All rights reserved.

Pyronin Y (basic xanthene dye)-bentonite composite: A spectroscopic study

NASA Astrophysics Data System (ADS)

Tabak, A.; Kaya, M.; Yilmaz, N.; Meral, K.; Onganer, Y.; Caglar, B.; Sungur, O.

2014-02-01

The expansion by 1.43 Angstrom of basal spacing and the shift to higher frequencies of in-plane ring vibrations of the Pyronin Y molecule at 1603 and 1527 cm-1 on the formation of Pyronin Y-bentonite composite exhibited that the dye cations might be oriented as a monolayer form in the interlamellar spacing with aromatic rings parallel to clay layers. Thermal analysis results of this composite compared to those of raw bentonite signified the different outer sphere water entities associated with the replacement of inorganic cations with organic dye cations and the gradual decomposition of the organic molecule in the interlamellar spacing. Thermo-Infrared spectra of Pyronin Y-bentonite sample up to high temperatures showed the thermal stability of the dye-clay composite as a result of the presence of π interactions. The pore structure characteristics of Pyronin Y-bentonite composite exhibited the increase in the number of mesopores during formation of the composite.

Evaluation of the ability of calcite, bentonite and barite to enhance oil dispersion under arctic conditions.

PubMed

Jézéquel, Ronan; Receveur, Justine; Nedwed, Tim; Le Floch, Stéphane

2018-02-01

A test program was conducted at laboratory and pilot scale to assess the ability of clays used in drilling mud (calcite, bentonite and barite) to create oil-mineral aggregates and disperse crude oil under arctic conditions. Laboratory tests were performed in order to determine the most efficient conditions (type of clay, MOR (Mineral/Oil Ratio), mixing energy) for OMA (Oil Mineral Aggregate) formation. The dispersion rates of four crude oils were assessed at two salinities. Dispersion was characterized in terms of oil concentration in the water column and median OMA size. Calcite appeared to be the best candidate at a MOR of 2:5. High mixing energy was required to initiate OMA formation and low energy was then necessary to prevent the OMAs from resurfacing. Oil dispersion using Corexit 9500 was compared with oil dispersion using mineral fines. Copyright © 2017 Elsevier Ltd. All rights reserved.

Acid composition and use thereof in treating fluid-bearing geologic formations

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

Kucera, C.H.

1972-04-04

A composition useful as a fluid-loss control additive consists of a mixture of the following ingredients in the amount of between 7% and 30% by wt of each, to make a total of 100%: (1) an aqueous dispersion for binding clay selected from the class consisting of resins, rubber, rosin acids, and natural gums; (2) a thickening agent selected from the class consisting of fatty acids having from 10 to 24 carbon atoms, rosin acids, and metal soaps thereof; (3) an anionic or nonionic surfactant; and (4) a colloid-forming material which is either clay or asbestos cement. Another optional ingredientmore » is a low- viscosity oil, which is added in amount of up to 75% by wt of the sum of ingredients (1) to (4). The present composition prevents or greatly retards the excessive loss of fluids through the connecting pores of a geologic formation. (7 claims)« less

Self-healing coatings based on halloysite clay polymer composites for protection of copper alloys.

PubMed

Abdullayev, Elshad; Abbasov, Vagif; Tursunbayeva, Asel; Portnov, Vasiliy; Ibrahimov, Hikmat; Mukhtarova, Gulbaniz; Lvov, Yuri

2013-05-22

Halloysite clay nanotubes loaded with corrosion inhibitors benzotriazole (BTA), 2-mercaptobenzimidazole (MBI), and 2-mercaptobenzothiazole (MBT) were used as additives in self-healing composite paint coating of copper. These inhibitors form protective films on the metal surface and mitigate corrosion. Mechanisms involved in the film formation have been studied with optical and electron microscopy, UV-vis spectrometry, and adhesivity tests. Efficiency of the halloysite lumen loading ascended in the order of BTA < MBT < MBI; consequently, MBI and MBT halloysite formulations have shown the best protection. Inhibitors were kept in the tubes buried in polymeric paint layer for a long time and release was enhanced in the coating defects exposed to humid media with 20-50 h, sufficient for formation of protective layer. Anticorrosive performance of the halloysite-based composite acrylic and polyurethane coatings have been demonstrated for 110-copper alloy strips exposed to 0.5 M aqueous NaCl for 6 months.

Heterogeneous nucleation of nitric acid trihydrate on clay minerals: relevance to type ia polar stratospheric clouds.

PubMed

Hatch, Courtney D; Gough, Raina V; Toon, Owen B; Tolbert, Margaret A

2008-01-17

Although critical to atmospheric modeling of stratospheric ozone depletion, selective heterogeneous nuclei that promote the formation of Type Ia polar stratospheric clouds (PSCs) are largely unknown. While mineral particles are known to be good ice nuclei, it is currently not clear whether they are also good nuclei for PSCs. In the present study, a high-vacuum chamber equipped with transmission Fourier transform infrared spectroscopy and a quadrupole mass spectrometer was used to study heterogeneous nucleation of nitric acid trihydrate (NAT) on two clay minerals-Na-montmorillonite and kaolinite-as analogs of atmospheric terrestrial and extraterrestrial minerals. The minerals are first coated with a 3:1 supercooled H2O/HNO3 solution prior to the observed nucleation of crystalline NAT. At 220 K, NAT formation was observed at low SNAT values of 12 and 7 on kaolinite and montmorillonite clays, respectively. These are the lowest SNAT values reported in the literature on any substrate. However, NAT nucleation exhibited significant temperature dependence. At lower temperatures, representative of typical polar stratospheric conditions, much higher supersaturations were required before nucleation was observed. Our results suggest that NAT nucleation on mineral particles, not previously treated with sulfuric acid, may not be an important nucleation platform for Type Ia PSCs under normal polar stratospheric conditions.

Valorisation of different types of boron-containing wastes for the production of lightweight aggregates.

PubMed

Kavas, T; Christogerou, A; Pontikes, Y; Angelopoulos, G N

2011-01-30

Four boron-containing wastes (BW), named as Sieve (SBW), Dewatering (DBW), Thickener (TBW) and Mixture (MBW) waste, from Kirka Boron plant in west Turkey were investigated for the formation of artificial lightweight aggregates (LWA). The characterisation involved chemical, mineralogical and thermal analyses as well as testing of their bloating behaviour by means of heating microscopy. It was found that SBW and DBW present bloating behaviour whereas TBW and MBW do not. Following the above results two mixtures M1 and M2 were prepared with (in wt.%): 20 clay mixture, 40 SBW, 40 DBW and 20 clay mixture, 35 SBW, 35 DBW, 10 quartz sand, respectively. Two different firing modes were applied: (a) from room temperature till 760 °C and (b) abrupt heating at 760 °C. The obtained bulk density for M1 and M2 pellets is 1.2g/cm(3) and 0.9 g/cm(3), respectively. The analysis of microstructure with electron microscopy revealed a glassy phase matrix and an extended formation of both interconnected and isolated, closed pores. The results indicate that SBW and DBW boron-containing wastes combined with a clay mixture and quartz sand can be valorised for the manufacturing of lightweight aggregates. Copyright © 2010 Elsevier B.V. All rights reserved.

The PETM in the mid-Atlantic Coastal Plain: A widespread record of unique climate signatures in shallow-shelf Marlboro Clay

NASA Astrophysics Data System (ADS)

Powars, D. S.; Edwards, L. E.; Kopp, R. E.; Self-Trail, J.; Schultz, A.

2009-12-01

Abrupt sedimentary changes mark the Paleocene-Eocene Thermal Maximum (PETM) in the mid-Atlantic Coastal Plain. Across the tectonic downwarp known as the Salisbury Embayment (southeastern Virginia to central New Jersey), kaolinite-rich clay (the Marlboro Clay) abruptly replaces glauconite-rich quartz sand, silt, and illite-smectite clay of the late Paleocene. Dozens of cored boreholes obtained by the USGS and other Federal and State agencies, together with geophysical logs from more than 100 boreholes, allow us to document the widespread distribution and depositional, biostratigraphic, paleoecologic, taphonomic, and tectonic characteristics of the Marlboro Clay. In Maryland and Virginia, the Marlboro Clay is a silvery-gray to pale-red plastic clay and locally includes thin laminations and thicker beds of silt, concretions, pyrite nodules, and rare shell fragments (in downdip cores). The clay is unconformity bounded with highly burrowed contacts. The lower contact is locally so bioturbated that it has been reported as gradational. The upper contact in Virginia has glauconite-rich, sand-filled burrows from the overlying Nanjemoy Formation (lower Eocene) that penetrate as much as 8.5 m down into the Marlboro Clay (total thickness only 9 m). Biostratigraphically, the Marlboro Clay is placed in calcareous nannofossil Zone NP9 (and NP10 in downdip cores) and includes the PETM marker dinocyst species Apectodinium augustum (in downdip cores). In New Jersey, a similar clay deposit is described from the subsurface; and based on consistency in lithology, biostratigraphy, stratigraphic position, isotopic composition and its magnetic properties, we apply the name Marlboro Clay to this unique clay unit throughout the Salisbury Embayment. Structure-contour and isopach maps of the present configuration of the Marlboro Clay reveal a widespread deposit with localized truncation or thinning. Tectonic folding and faulting along the inner Coastal Plain and along the James River structural zone produced syn- and post-depositional erosional thinning on uplifted sides of faults and thickening in downdropped areas. The Chesapeake Bay Impact Structure (CBIS) removed the Marlboro Clay across a large area of southeastern Virginia. Faults and folds associated with the CBIS appear to deform the clay in an outer-fracture-zone that extends up to 25-km outside the crater’s outer rim. The Marlboro Clay thickens and is slightly finer-grained in the deeper part of the Marlboro basin in where structure contours on the top-of-basement generally mimic the tectonic downwarp. The apparent deepest (>200 m below sea level) and thickest (>14 m) part of the Marlboro depositional basin appears to extend from just south of the mouth of the Potomac River northward to the lower Choptank River valley, Maryland, then turns sharply northeastward to beneath the central part of Delaware Bay. The Marlboro Clay of the mid-Atlantic United States thus provides a widespread deposit that in its regional and tectonic setting records, in its unusual sedimentary properties, the severe regional environmental changes associated with global climate change during the PETM.

Continental weathering as a driver of Late Cretaceous cooling: new insights from clay mineralogy of Campanian sediments from the southern Tethyan margin to the Boreal realm

NASA Astrophysics Data System (ADS)

Chenot, Elise; Deconinck, Jean-François; Pucéat, Emmanuelle; Pellenard, Pierre; Guiraud, Michel; Jaubert, Maxime; Jarvis, Ian; Thibault, Nicolas; Cocquerez, Théophile; Bruneau, Ludovic; Razmjooei, Mohammad J.; Boussaha, Myriam; Richard, James; Sizun, Jean-Pierre; Stemmerik, Lars

2018-03-01

New clay mineralogical analyses have been performed on Campanian sediments from the Tethyan and Boreal realms along a palaeolatitudinal transect from 45° to 20°N (Danish Basin, North Sea, Paris Basin, Mons Basin, Aquitaine Basin, Umbria-Marche Basin and Tunisian Atlas). Significant terrigenous inputs are evidenced by increasing proportions of detrital clay minerals such as illite, kaolinite and chlorite at various levels in the mid- to upper Campanian, while smectitic minerals predominate and represented the background of the Late Cretaceous clay sedimentation. Our new results highlight a distinct latitudinal distribution of clay minerals, with the occurrence of kaolinite in southern sections and an almost total absence of this mineral in northern areas. This latitudinal trend points to an at least partial climatic control on clay mineral sedimentation, with a humid zone developed between 20° and 35°N. The association and co-evolution of illite, chlorite and kaolinite in most sections suggest a reworking of these minerals from basement rocks weathered by hydrolysis, which we link to the formation of relief around the Tethys due to compression associated with incipient Tethyan closure. Diachronism in the occurrence of detrital minerals between sections, with detrital input starting earlier during the Santonian in the south than in the north, highlights the northward progression of the deformation related to the anticlockwise rotation of Africa. Increasing continental weathering and erosion, evidenced by our clay mineralogical data through the Campanian, may have resulted in enhanced CO2 consumption by silicate weathering, thereby contributing to Late Cretaceous climatic cooling.

Geochemical and technological characterization of clays of Corumbataí Formation, Paraná Basin, in the state of São Paulo, Brazil for the application in the ceramic industry.

NASA Astrophysics Data System (ADS)

Christofoletti, Sergio Ricardo; Torres Moreno, Maria Margarita; Batezelli, Alessandro; Zanardo, Antenor

2014-05-01

The Corumbataí Formation is a geological unit of the Paraná Basin comprises a range of predominantly argillaceous facies. These clays are important from an economic point of view, because they represent important mineral deposits suppliers of raw materials for the ceramic industry in the production of ceramic tiles.The study presents preliminary results of a research that aims to study the clays municipalities Tambaú, Ferreira and Santa Rosa of Viterbo in the State of São Paulo for their application and diversification of ceramic products. The methodology used was based on a detailed description of facies using the methodology in principles of analysis of Basin Miall (1984), followed by mineralogical identification by X-ray Diffraction, chemical analysis of major elements by X-ray Fluorescence and technological tests ceramic. According to the geological surveys of mines studied through columnar sections were identified the following lithofacies from base to top: Massive, Laminated, Intercalated and Altered. The mineralogy present on these lithofacies is composed by minerals: quartz, microclineo, albite, calcite, dolomite and hematite and by clay minerals illite, kaolinite and montmorillonite. The quartz represents the mineral more present in diffraction and occurs with d001 of 3.33Å in all lithofacies studied. The illite clay mineral represents the most frequent in studied samples presenting d 001 10Å in three conditions (natural, heated and treated with ethylene glycol) in which the blade was subjected to the analysis of X-ray diffraction, the presence of kaolinite or montmorillonite occurs or not in samples. It was observed a increased frequency of some minerals in the lithofacies studied, carbonates (calcite and dolomite), hematite and feldspar occurring in the intermediate portions of the profile with a predominance in lithofacies Intercalated. The illita clay mineral occurs throughout the profile, but with greater frequency in the lithofacies Massive and Laminated. The clay minerals kaolinite and montmorillonite occur in portions intermediate and top of the profiles studied in the intercalated and altered lithofacies. The chemical results of major elements by X-ray fluorescence confirmed the mineralogical results, with average values of 63.74 % of SiO2, 12.50 of Al2O3, 4.35% of of K2O, 0.45% of Na2O, 2,72% of CaO and 1,87 of MgO. The results chemical and mineralogical subsidized testing and ceramic formulations due to be executed later so defining the main applications of these clays in the production of ceramic products. The authors acknowledge the finantial support of Fundação de Amparo à Pesquisa do Estado de São Paulo-FAPESP, (Process, number 2012/24219-9).

The effect of mineral composition on the sorption of cesium ions on geological formations.

PubMed

Kónya, József; Nagy, Noémi M; Nemes, Zoltán

2005-10-15

The sorption of cesium-137 on rock samples, mainly on clay rocks, is determined as a function of the mineral composition of the rocks. A relation between the mineral groups (tectosilicates, phyllosilicates, clay minerals, carbonates) and their cesium sorption properties is shown. A linear model is constructed by which the distribution coefficients of the different minerals can be calculated from the mineral composition and the net distribution coefficient of the rock. On the basis of the distribution coefficients of the minerals the cesium sorption properties of other rocks can be predicted.

Carbon isotopic compositions of organic matter across continental Cretaceous-Tertiary (K-T) boundary sections: Implications for paleoenvironment after the K-T impact event

USGS Publications Warehouse

Maruoka, T.; Koeberl, C.; Bohor, B.F.

2007-01-01

To assess the environmental perturbation induced by the impact event that marks the Cretaceous-Tertiary (K-T) boundary, concentrations and isotopic compositions of bulk organic carbon were determined in sedimentary rocks that span the terrestrial K-T boundary at Dogie Creek, Montana, and Brownie Butte, Wyoming in the Western Interior of the United States. The boundary clays at both sites are not bounded by coals. Although coals consist mainly of organic matter derived from plant tissue, siliceous sedimentary rocks, such as shale and clay, may contain organic matter derived from microbiota as well as plants. Coals record ??13C values of plant-derived organic matter, reflecting the ??13C value of atmospheric CO2, whereas siliceous sedimentary rocks record the ??13C values of organic matter derived from plants and microbiota. The microbiota ??13C value reflects not only the ??13C value of atmospheric CO2, but also biological productivity. Therefore, the siliceous rocks from these sites yields information that differs from that obtained previously from coal beds. Across the freshwater K-T boundary at Brownie Butte, the ??13C values decrease by 2.6??? (from - 26.15??? below the boundary clay to - 28.78??? above the boundary clay), similar to the trend in carbonate at marine K-T sites. This means that the organic ??13C values reflect the variation of ??13C of atmospheric CO2, which is in equilibrium with carbon isotopes at the ocean surface. Although a decrease in ??13C values is observed across the K-T boundary at Dogie Creek (from - 25.32??? below the boundary clay to - 26.11??? above the boundary clay), the degree of ??13C-decrease at Dogie Creek is smaller than that at Brownie Butte and that for marine carbonate. About 2??? decrease in ??13C of atmospheric CO2 was expected from the ??13C variation of marine carbonate at the K-T boundary. This ??13C-decrease of atmospheric CO2 should affect the ??13C values of organic matter derived from plant tissue. As such a decrease in ??13C value was not observed at Dogie Creek, a process that compensates the ??13C-decrease of atmospheric CO2 should be involved. For example, the enhanced contribution of 13C-enriched organic matter derived from algae in a high-productivity environment could be responsible. The ??13C values of algal organic matter become higher than, and thus distinguishable from, those of plant organic matter in situations with high productivity, where dissolved HCO3- becomes an important carbon source, as well as dissolved CO2. As the ??13C-decrease of atmospheric CO2 reflected a reduction of marine productivity, the compensation of the ??13C decrease by the enhanced activity of the terrestrial microbiota means that the microbiota at freshwater environment recovered more rapidly than those in the marine environment. A distinct positive ??13C excursion of 2??? in the K-T boundary clays is superimposed on the overall decreasing trend at Dogie Creek; this coincides with an increase in the content of organic carbon. We conclude that the K-T boundary clays include 13C-enriched organic matter derived from highly productive algae. Such a high biological productivity was induced by phenomena resulting from the K-T impact, such as nitrogen fertilization and/or eutrophication induced by enhanced sulfide formation. The high productivity recorded in the K-T boundary clays means that the freshwater environments (in contrast to marine environments) recovered rapidly enough to almost immediately (within 10??yr) respond to the impact-related environmental perturbations. ?? 2006 Elsevier B.V. All rights reserved.

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.

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;

Genesis analysis of high-gamma ray sandstone reservoir and its log evaluation techniques: a case study from the Junggar basin, northwest China.

PubMed

Wang, Liang; Mao, Zhiqiang; Sun, Zhongchun; Luo, Xingping; Song, Yong; Liu, Zhen

2013-01-01

In the Junggar basin, northwest China, many high gamma-ray (GR) sandstone reservoirs are found and routinely interpreted as mudstone non-reservoirs, with negative implications for the exploration and exploitation of oil and gas. Then, the high GR sandstone reservoirs' recognition principles, genesis, and log evaluation techniques are systematically studied. Studies show that the sandstone reservoirs with apparent shale content greater than 50% and GR value higher than 110API can be regarded as high GR sandstone reservoir. The high GR sandstone reservoir is mainly and directly caused by abnormally high uranium enrichment, but not the tuff, feldspar or clay mineral. Affected by formation's high water sensitivity and poor borehole quality, the conventional logs can not recognize reservoir and evaluate the physical property of reservoirs. Then, the nuclear magnetic resonance (NMR) logs is proposed and proved to be useful in reservoir recognition and physical property evaluation.

Genesis Analysis of High-Gamma Ray Sandstone Reservoir and Its Log Evaluation Techniques: A Case Study from the Junggar Basin, Northwest China

PubMed Central

Wang, Liang; Mao, Zhiqiang; Sun, Zhongchun; Luo, Xingping; Song, Yong; Liu, Zhen

2013-01-01

In the Junggar basin, northwest China, many high gamma-ray (GR) sandstone reservoirs are found and routinely interpreted as mudstone non-reservoirs, with negative implications for the exploration and exploitation of oil and gas. Then, the high GR sandstone reservoirs' recognition principles, genesis, and log evaluation techniques are systematically studied. Studies show that the sandstone reservoirs with apparent shale content greater than 50% and GR value higher than 110API can be regarded as high GR sandstone reservoir. The high GR sandstone reservoir is mainly and directly caused by abnormally high uranium enrichment, but not the tuff, feldspar or clay mineral. Affected by formation's high water sensitivity and poor borehole quality, the conventional logs can not recognize reservoir and evaluate the physical property of reservoirs. Then, the nuclear magnetic resonance (NMR) logs is proposed and proved to be useful in reservoir recognition and physical property evaluation. PMID:24078797

Natural Arsenic in the Miocene Hawthorn Group, Florida: Wide Ranging Implications for ASR, Phosphate Mining, Private Well

NASA Astrophysics Data System (ADS)

Lazareva, O. V.; Pichler, T.

2004-12-01

In order to understand the mineralogical association and distribution of arsenic (As) in the Hawthorn Group we examined in detail the chemical and mineralogical composition of 370 samples that were collected from 16 cores in central Florida. In our study area the Hawthorn group consists primarily of a basal carbonate unit (the Arcadia Formation) and an upper siliciclastic unit (The Peace River Formation). The Peace River Formation contains appreciable amounts of phosphate and is currently being exploited for phosphate ore. Samples were taken for each Formation at intervals of 25ft. In addition to the interval samples we also took samples that contained visible pyrite crystals, iron oxides, green clays, phosphatic and organic material. These additional samples were collected because of their potential of high As concentrations. Arsenic concentrations were determined by hydride generation - atomic fluorescence spectrometry (HG-AFS) after digestion with aqua regia (3:1 HCl and HNO3). The elements Fe, Na, Al, Si, Mg, Ca, S, P, and K were measured on the same solutions by inductively coupled plasma optical emission spectrometry (ICP-OES). The identification of discrete minerals was aided by scanning electron microscopy (SEM) and chemical compositions were obtained by electron-probe microanalyses (EMPA). Our study indicates that the average As concentrations significantly change from 9.0 ppm in the Peace River Formation to 3.0 ppm in the Tampa Member of the Arcadia Formation. As concentrations for all Hawthorn samples vary from 0.07 to 68.98 ppm ( μ = 5.6, σ = 7.1). Our detailed mineralogical and geochemical study demonstrates that: (1) The As in the Hawthorn group varies from the formation to formation and is mostly concentrated in trace minerals, such as pyrite; (2) Concentrations of the As in pyrite crystals can vary drastically from a minimum of 0 ppm to a maximum of 8260 ppm; (3) Pyrite is an unevenly distributed throughout the Hawthorn Group; (4) Phosphate and organic material, clays, and iron oxides contain lower As concentrations contrasted to pyrite; (5) Pyrite occurs in framboidal and euhedral forms. Because phosphorous, arsenic and sulfur are chemically closely related, they often occur together in nature, thus posing a potential problem for the phosphate industry. There have been several occurrences of swine fatalities due to arsenic poisoning as a result of phosphate feed supplements. Information about the concentration, distribution and mineralogical association of naturally occurring As is important, because this is a first step to forecast its behavior during anthropogenic induced physico-chemical changes in the aquifer. Recently, aquifer storage and recovery (ASR) facilities in central Florida reported As concentrations in excess of 100 μ g/L in recovered water. The ASR storage zone is the Suwannee Limestone, which directly underlies the Hawthorn sediments. It is crucial to the future of ASR in this area to understand the source and distribution of arsenic in the overlying Hawthorn Group and the cycling of arsenic in the Florida platform.

Biologically agglutinated eukaryotic microfossil from Cryogenian cap carbonates.

PubMed

Moore, K R; Bosak, T; Macdonald, F A; Lahr, D J G; Newman, S; Settens, C; Pruss, S B

2017-07-01

Cryogenian cap carbonates that overlie Sturtian glacial deposits were formed during a post-glacial transgression. Here, we describe microfossils from the Kakontwe Formation of Zambia and the Taishir Formation of Mongolia-both Cryogenian age, post-Sturtian cap carbonates-and investigate processes involved in their formation and preservation. We compare microfossils from these two localities to an assemblage of well-documented microfossils previously described in the post-Sturtian Rasthof Formation of Namibia. Microfossils from both new localities have 10 ± 1 μm-thick walls composed of carbonaceous matter and aluminosilicate minerals. Those found in the Kakontwe Formation are spherical or ovoid and 90 ± 5 μm to 200 ± 5 μm wide. Structures found in the Taishir Formation are mostly spherical, 50 ± 5 μm to 140 ± 5 μm wide, with distinct features such as blunt or concave edges. Chemical and mineralogical analyses show that the walled structures and the clay fraction extracted from the surrounding sediments are composed of clay minerals, especially muscovite and illite, as well as quartz, iron and titanium oxides, and some dolomite and feldspar. At each locality, the mineralogy of the microfossil walls matched that of the clay fractions of the surrounding sediment. The abundance of these minerals in the walled microfossils relative to the surrounding carbonate matrix and microbial laminae, and the presence of minerals that cannot precipitate from solution (titanium oxide and feldspar), suggests that the composition represents the original mineralogy of the structures. Furthermore, the consistency in mineralogy of both microfossils and sediments across the three basins, and the uniformity of size and shape among mineral grains in the fossil walls indicate that these organisms incorporated these minerals by primary biological agglutination. The discovery of new, mineral-rich microfossil assemblages in microbially laminated and other fine-grained facies of Cryogenian cap carbonates from multiple localities on different palaeocontinents demonstrates that agglutinating eukaryotes were widespread in carbonate-dominated marine environments in the aftermath of the Sturtian glaciation. © 2017 John Wiley & Sons Ltd.

Re-evaluating the oceanic magnesium and magnesium isotope budgets - the contribution of authigenic mineral formation in marine sediments

NASA Astrophysics Data System (ADS)

Berg, R. D.; Solomon, E. A.

2016-12-01

Formation of authigenic minerals in marine sediments is a globally significant geochemical process for several major element cycles in the ocean on the 105-107 year time scale, including the sulfur, potassium, and calcium cycles. However, the significance of these processes to the magnesium (Mg) cycle have not yet been well constrained, and thus are not typically included in global oceanic Mg budgets. Exclusion of this authigenic sink for Mg affects work derived from the existing Mg and Mg isotope budgets in the fields of paleo-oceanography and global geochemical cycling. To robustly constrain the magnitude of this sedimentary Mg sink in continental slope, rise, and abyssal environments, we estimate rates of Mg uptake in marine sediments using reactive-transport modeling of 200 pore water solute concentration profiles measured during scientific ocean drilling expeditions. The depth-integrated rates of Mg uptake are extrapolated globally using statistical machine learning methods, which are particularly well-suited for using with the wide variety of environments represented in the ocean drilling dataset. Due to the differences in Mg isotope fractionation during formation of authigenic clays versus carbonates, the relative proportion of the Mg flux being sequestered by these minerals may have a major effect on the oceanic Mg isotope record. We evaluate the processes controlling Mg uptake (authigenic clay and carbonate formation) at representative continental margin locations using pore water Mg isotope measurements. Results indicate that rates of Mg uptake are over an order of magnitude higher in continental margin settings than in the abyssal environment, likely due to greater organic matter degradation resulting in higher rates of carbonate formation and in situ weathering of primary silicates to authigenic clays. Preliminary results show that authigenic mineral formation in marine sediments is a major sink for Mg in the ocean, rivaling the ridge-crest hydrothermal sink. The quantification of this Mg sink and associated Mg isotope fractionation provides more accurate constraints on the modern global Mg budget, and provides a benchmark for models and interpretations of the paleooceanographic Mg isotope record.

Clay mineralogy of the ocean sediments from the Wilkes Land margin, east Antarctica: implications on the paleoclimate, provenance and sediment dispersal pattern

NASA Astrophysics Data System (ADS)

Verma, Kamlesh; Bhattacharya, Sanjeeb; Biswas, P.; Shrivastava, Prakash K.; Pandey, Mayuri; Pant, N. C.

2014-11-01

Core U1359 collected from the continental rise off Wilkes Land, east Antarctica, is analyzed for the clay mineralogy and carbon content. The temporal variation of the clay mineralogical data shows a dominance of illite with chlorite, smectite and kaolinite in decreasing concentration. Clay mineral illite is negatively correlated with smectite which shows enrichment during 6.2-6.8, 5.5-5.8, 4.5 and 2.5 Ma. The mineralogical analyses on the silt size fraction (2-53 μm) of some selected samples were also carried out. The combined result of both the size fractions shows the presence of chlorite and illite in both size fractions, smectite and kaolinite only in clay size fraction (<2 μm) and similarity in the crystallinity and chemistry of illite in both fractions. Similar nature of illite in both fractions suggests negligible role of sorting probably due to the deposition from the waxing ice sheet. During times of ice growth, nearby cratonic east Antarctica shield provided biotite-rich sediments to the depositional site. On the other hand, the presence of smectite, only in the clay size fraction, suggests the effective role of sorting probably due to the deposition from distal source in ice retreat condition. During times of ice retreat, smectite-rich sediment derived from Ross Orogen is transported to the core site through surface or bottom water currents. Poor crystallinity of illite due to degradation further corroborates the ice retreat condition. The ice sheet proximal sediments of U1359 show that in the eastern part of Wilkes Land, the `warming' was initiated during late Miocene.

Influence of Compositional Variations on Floc Size and Strength

NASA Astrophysics Data System (ADS)

Yin, H.; Tan, X.; Reed, A. H.; Furukawa, Y.; Zhang, G.

2010-12-01

Clay-biopolymer micro aggregates or flocs are abundant in waters, including rivers, lakes, and oceans. Owing to their small size and charged surfaces, fine-grained inorganic sediment particles, mainly clays, interact actively with organic substances, such as organic matter and biogenic polymers, to form aggregates or flocs, typically in the size of 10-1000 μm. The flocs in ocean waters are also termed “marine snow”. These flocs are typically porous, tenuous, and soft in nature. During transport in suspension, they may breakdown and decrease in size if the turbulent shear stress exceeds their strength. They may also collide and form larger ones if the shear stress is relatively small. Since flocs of different size and structure settle at different velocities, understanding their strength is also of essential importance for sediment hydrodynamics, transport, and management. Our study focuses on investigating the influence of compositional variations on floc size and strength so that a better understanding of floc dynamics can be achieved. A laser diffraction-based Cilas® particle size and shape analyzer with controllable fluid circulation velocity was employed to conduct floc size measurements and shape imaging, the latter achieved by a high resolution inverted optical microscope, which is also installed with the size analyzer. Totally two clay minerals, kaolinite and illite, were tested as the model inorganic solid skeleton minerals for floc formation, and two biopolymers, anionic xanthan gum and neutral guar gum, were chosen as analogs of naturally occurring organic matter or biopolymers to simulate clay-biopolymer floc formation. Moreover, the concentration of both organic and inorganic phases was varied. The floc breakage or tensile strength was indirectly estimated by the varied fluid flow velocity in the particle size analyzer’s circulation system. For each individual composition, stable flocs were formed by three different fluid circulating velocities, resulting in different shearing stress in the fluid. Experimental results show that organic biopolymers can have profound influences on clay flocculation process and the resultant floc size and strength. Anionic xanthan gum tends to form smaller and weaker clay-biopolymer flocs than neutral guar gum, because the Coulombic repulsion forces develop between the two negatively charged constituents. Illite results in stronger clay-guar flocs than kaolinite, probably due to the relatively higher negative charges on illite surface. Generally, a bimodal distribution of floc size frequency was observed for all types of flocs. The maxim floc sizes range from 10-30 μm for kaolinite-xanthan flocs to 250-300 μm for kaolinite-guar flocs at a weight ratio of 1:1.

Enhanced magnetization of the Marlboro Clay as a product of soil pyrogenesis at the Paleocene-Eocene boundary?

NASA Astrophysics Data System (ADS)

Kent, Dennis V.; Lanci, Luca; Wang, Huapei; Wright, James D.

2017-09-01

The kaolinite-rich Marlboro Clay was deposited on the inner shelf in the Salisbury Embayment of the U.S. Atlantic margin at the onset of the carbon isotope excursion marking the 56 Ma Paleocene-Eocene boundary and is characterized by an anomalously high concentration of magnetic nanoparticles of enigmatic origin that give rise to notably intense bulk magnetization. Recent studies point to a magnetic assemblage that is dominated by single-domain magnetite particles that tend to be isolated rather than arranged in chains, the most distinguishing feature of magnetotactic bacteria fossils. On the other hand, it is very unlikely that the nanoparticles can be condensates of an impact plume given the meter-scale thickness of the Marlboro Clay. We obtained new data from a landward proximal site at Wilson Lake on the New Jersey Coastal Plain and find that the abrupt increase in magnetite nanoparticles is virtually coincident stratigraphically with the recently reported impact spherule layer at the base of the Marlboro Clay in the same core. Yet the high field magnetic susceptibility, a measure of total iron concentration, and strontium isotope values on bulk sediment, an indicator of sediment weathering provenance, are not different in the Marlboro Clay from the immediately underlying Vincentown Formation. We suggest that the distinctive magnetic properties of the Marlboro Clay originated from pyromagnetic soil enhancement by widespread wildfires on the adjoining drainage area. The pyrogenetic products were soon washed from the denuded landscape and rapidly deposited as mud-waves across the shelf, becoming the Marlboro Clay. A few percent of incinerated biomass ends up as calcite known as wood ash stone and can inherit its light carbon isotope composition. Disseminated wood ash stone entrained in the Marlboro Clay could contribute to the landward increase in amplitude of the carbon isotope excursion in bulk carbonate data. A plausible trigger for the initial conflagration is a fireball from the impact of a sizable extraterrestrial object at moderate range.

Aggregation and stability of anisotropic charged clay colloids in aqueous medium in the presence of salt.

PubMed

Ali, Samim; Bandyopadhyay, Ranjini

2016-01-01

Na-montmorillonite nanoclay is a colloid of layered mineral silicate. When dispersed in water, this mineral swells on absorption of water and exfoliates into platelets with electric double layers on their surfaces. Even at low particle concentration, the aqueous dispersion can exhibit a spontaneous ergodicity breaking phase transition from a free flowing liquid to nonequilibrium, kinetically arrested and disordered states such as gels and glasses. In an earlier publication [Applied Clay Science, 2015, 114, 8592], we showed that the stability of clay gels can be enhanced by adding a salt later to the clay dispersion prepared in deionized water, rather than by adding the clay mineral to a previously mixed salt solution. Here, we directly track the collapsing interface of sedimenting clay gels using an optical method and show that adding salt after dispersing the clay mineral does indeed result in more stable gels even in very dilute dispersions. These weak gels are seen to exhibit a transient collapse after a finite delay time, a phenomenon observed previously in depletion gels. The velocity of the collapse oscillates with the age of the sample. However, the average velocity of collapse increases with sample age up to a peak value before decreasing at higher ages. With increasing salt concentration, the delay time for transient collapse decreases, while the peak value of the collapsing velocity increases. Using ultrasound attenuation spectroscopy, rheometry and cryogenic scanning electron microscopy, we confirm that morphological changes of the gel network assembly, facilitated by thermal fluctuations, lead to the observed collapse phenomenon. Since clay minerals are used extensively in polymer nanocomposites, as rheological modifiers, stabilizers and gas absorbents, we believe that the results reported in this work are extremely useful for several practical applications and also for understanding geophysical phenomena such as the formation and stability of quicksand and river deltas.

Formation of metal clusters in halloysite clay nanotubes

DOE PAGES

Vinokurov, Vladimir A.; Stavitskaya, Anna V.; Chudakov, Yaroslav A.; ...

2017-02-16

We developed ceramic core-shell materials based on abundant halloysite clay nanotubes with enhanced heavy metal ions loading through Schiff base binding. These clay tubes are formed by rolling alumosilicate sheets and have diameter of c.50 nm, a lumen of 15 nm and length ~1 μm. This allowed for synthesis of metal nanoparticles at the selected position: (1) on the outer surface seeding 3-5 nm metal particles on the tubes; (2) inside the tube’s central lumen resulting in 10-12 nm diameter metal cores shelled with ceramic wall; and (3) smaller metal nanoparticles intercalated in the tube’s wall allowing up to 9more » wt% of Ru, and Ag loading. These composite materials have high surface area providing a good support for catalytic nanoparticles, and can also be used for sorption of metal ions from aqueous solutions.« less

Spatially resolved XRF, XAFS, XRD, STXM and IR investigation of a natural U-rich clay

NASA Astrophysics Data System (ADS)

Denecke, M. A.; Michel, P.; Schäfer, T.; Huber, F.; Rickers, K.; Rothe, J.; Dardenne, K.; Brendebach, B.; Vitova, T.; Elie, M.

2009-11-01

Combined spatially resolved hard X-ray μ-XRF and μ-XAFS studies using an X-ray beam with micrometer dimensions at the INE-Beamline for actinide research at ANKA and Beamline L at HASYLAB with those from scanning transmission soft X-ray microscopy (STXM) and synchrotron-based Fourier transform infrared microspectroscopy (μ-FTIR) recorded with beam spots in the nanometer range are used to study a U-rich clay originating from Autunian shales in the Permian Lodève Basin (France). This argillaceous formation is a natural U deposit associated with organic matter (bitumen). Results allow us to differentiate between possible mechanisms leading to U enrichment: likely U immobilization via reaction with organic material associated with clay mineral. Such investigations support development of reliable assessment of the long term radiological safety for proposed nuclear waste disposal sites.

Formation of metal clusters in halloysite clay nanotubes

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

Vinokurov, Vladimir A.; Stavitskaya, Anna V.; Chudakov, Yaroslav A.

We developed ceramic core-shell materials based on abundant halloysite clay nanotubes with enhanced heavy metal ions loading through Schiff base binding. These clay tubes are formed by rolling alumosilicate sheets and have diameter of c.50 nm, a lumen of 15 nm and length ~1 μm. This allowed for synthesis of metal nanoparticles at the selected position: (1) on the outer surface seeding 3-5 nm metal particles on the tubes; (2) inside the tube’s central lumen resulting in 10-12 nm diameter metal cores shelled with ceramic wall; and (3) smaller metal nanoparticles intercalated in the tube’s wall allowing up to 9more » wt% of Ru, and Ag loading. These composite materials have high surface area providing a good support for catalytic nanoparticles, and can also be used for sorption of metal ions from aqueous solutions.« less

Reconstructing a hydrogen-driven microbial metabolic network in Opalinus Clay rock.

PubMed

Bagnoud, Alexandre; Chourey, Karuna; Hettich, Robert L; de Bruijn, Ino; Andersson, Anders F; Leupin, Olivier X; Schwyn, Bernhard; Bernier-Latmani, Rizlan

2016-10-14

The Opalinus Clay formation will host geological nuclear waste repositories in Switzerland. It is expected that gas pressure will build-up due to hydrogen production from steel corrosion, jeopardizing the integrity of the engineered barriers. In an in situ experiment located in the Mont Terri Underground Rock Laboratory, we demonstrate that hydrogen is consumed by microorganisms, fuelling a microbial community. Metagenomic binning and metaproteomic analysis of this deep subsurface community reveals a carbon cycle driven by autotrophic hydrogen oxidizers belonging to novel genera. Necromass is then processed by fermenters, followed by complete oxidation to carbon dioxide by heterotrophic sulfate-reducing bacteria, which closes the cycle. This microbial metabolic web can be integrated in the design of geological repositories to reduce pressure build-up. This study shows that Opalinus Clay harbours the potential for chemolithoautotrophic-based system, and provides a model of microbial carbon cycle in deep subsurface environments where hydrogen and sulfate are present.

Formation of metal clusters in halloysite clay nanotubes

PubMed Central

Vinokurov, Vladimir A.; Stavitskaya, Anna V.; Chudakov, Yaroslav A.; Ivanov, Evgenii V.; Shrestha, Lok Kumar; Ariga, Katsuhiko; Darrat, Yusuf A.; Lvov, Yuri M.

2017-01-01

Abstract We developed ceramic core-shell materials based on abundant halloysite clay nanotubes with enhanced heavy metal ions loading through Schiff base binding. These clay tubes are formed by rolling alumosilicate sheets and have diameter of c.50 nm, a lumen of 15 nm and length ~1 μm. This allowed for synthesis of metal nanoparticles at the selected position: (1) on the outer surface seeding 3–5 nm metal particles on the tubes; (2) inside the tube’s central lumen resulting in 10–12 nm diameter metal cores shelled with ceramic wall; and (3) smaller metal nanoparticles intercalated in the tube’s wall allowing up to 9 wt% of Ru, and Ag loading. These composite materials have high surface area providing a good support for catalytic nanoparticles, and can also be used for sorption of metal ions from aqueous solutions. PMID:28458738

Reconstructing a hydrogen-driven microbial metabolic network in Opalinus Clay rock

PubMed Central

Bagnoud, Alexandre; Chourey, Karuna; Hettich, Robert L.; de Bruijn, Ino; Andersson, Anders F.; Leupin, Olivier X.; Schwyn, Bernhard; Bernier-Latmani, Rizlan

2016-01-01

The Opalinus Clay formation will host geological nuclear waste repositories in Switzerland. It is expected that gas pressure will build-up due to hydrogen production from steel corrosion, jeopardizing the integrity of the engineered barriers. In an in situ experiment located in the Mont Terri Underground Rock Laboratory, we demonstrate that hydrogen is consumed by microorganisms, fuelling a microbial community. Metagenomic binning and metaproteomic analysis of this deep subsurface community reveals a carbon cycle driven by autotrophic hydrogen oxidizers belonging to novel genera. Necromass is then processed by fermenters, followed by complete oxidation to carbon dioxide by heterotrophic sulfate-reducing bacteria, which closes the cycle. This microbial metabolic web can be integrated in the design of geological repositories to reduce pressure build-up. This study shows that Opalinus Clay harbours the potential for chemolithoautotrophic-based system, and provides a model of microbial carbon cycle in deep subsurface environments where hydrogen and sulfate are present. PMID:27739431

Inland aeolian deposits of the Iberian Peninsula: Sand dunes and clay dunes of the Duero Basin and the Manchega Plain. Palaeoclimatic considerations

NASA Astrophysics Data System (ADS)

Bernat Rebollal, M.; Pérez-González, A.

2008-12-01

This paper describes the latest research on the geomorphological characteristics, formation environment and chronology of the main inland aeolian deposits from the south-eastern Duero Basin (DB) and the Manchega Plain (MP) of the Iberian Peninsula. Similarities and differences between the aeolian deposits of these two locations are summarised. Wind deflation from the Guadiana and Júcar alluvial systems created the aeolian deposits of the MP. These deposits are mainly composed of quartz sands. However, in the San Juan alluvial plain (MP) there is a large extent of clay dunes formed by exposure to prevalent winds of seasonal playa-lakes with salt and clay sediments. In the DB, wind remobilisation of the small particles from Quaternary terraces and Tertiary arkosic sediments left aeolian deposits of quartz-feldspar sands. Textural parameters of the aeolian deposits show large variations depending on the location and the original deposit. Thus, in the DB the aeolian sands derived from the deflation of fluvial sediments are better sorted and smaller in grain size than those created by the deflation of arkosic sediments. Morphologically, simple and compound parabolic dunes (U-V forms, hemicyclic, lobate and elongate), crescentic and linear dunes, climbing dunes and blowout dunes have been recognized at both sites. Barchan and dome dunes are present only in the DB while "lunette lunette-clay dunes" are found only in the MP. In both locations, the large extent of aeolian sand sheets and the predominance of simple and compound parabolic dunes indicates the active role of sparse vegetation cover in the formation of this aeolian system. In the DB, dunes were formed by southwest and west winds, while in the MP the aeolian morphologies indicate that the prevalent winds were west and northwest. The chronology of the dune deposits is being determined with luminescence (TL-OSL) dating and Mass Spectrometry Analysis ( 14C-AMS). In this way, the aeolian activity and stabilisation stages can be established, the latter well marked in the DB through soil A horizon development. Thus, the main sand dune formation in the DB and the eastern regions of the MP occurred between 13.5 and 7 ka BP, during the cold and arid Younger Dryas episode and the Early Holocene. The clay dunes of the MP accumulated mainly from 29 to 19 ka BP that corresponds with Heinrich events HE-3 and HE-2 and the Last Glacial Maximum. However, clay dunes were also formed between 13.5 and 7 ka BP. In both locations, there have been reactivations of some sand deposits in the recent Holocene, with maximum activity around 5-2 ka BP and 0.5-0.2 ka BP. On the other hand, three marked stages of stabilisation of the DB aeolian system have been established with 14C-AMS, around 10.2, 6.2 and 1.2 ka BP. Finally, the main winds contributing to dune construction were also responsible for the deflation processes with the formation of erosional depressions.

Spatial prediction of Soil Organic Carbon contents in croplands, grasslands and forests using environmental covariates and Generalized Additive Models (Southern Belgium)

NASA Astrophysics Data System (ADS)

Chartin, Caroline; Stevens, Antoine; van Wesemael, Bas

2015-04-01

Providing spatially continuous Soil Organic Carbon data (SOC) is needed to support decisions regarding soil management, and inform the political debate with quantified estimates of the status and change of the soil resource. Digital Soil Mapping techniques are based on relations existing between a soil parameter (measured at different locations in space at a defined period) and relevant covariates (spatially continuous data) that are factors controlling soil formation and explaining the spatial variability of the target variable. This study aimed at apply DSM techniques to recent SOC content measurements (2005-2013) in three different landuses, i.e. cropland, grassland, and forest, in the Walloon region (Southern Belgium). For this purpose, SOC databases of two regional Soil Monitoring Networks (CARBOSOL for croplands and grasslands, and IPRFW for forests) were first harmonized, totalising about 1,220 observations. Median values of SOC content for croplands, grasslands, and forests, are respectively of 12.8, 29.0, and 43.1 g C kg-1. Then, a set of spatial layers were prepared with a resolution of 40 meters and with the same grid topology, containing environmental covariates such as, landuses, Digital Elevation Model and its derivatives, soil texture, C factor, carbon inputs by manure, and climate. Here, in addition to the three classical texture classes (clays, silt, and sand), we tested the use of clays + fine silt content (particles < 20 µm and related to stable carbon fraction) as soil covariate explaining SOC variations. For each of the three land uses (cropland, grassland and forest), a Generalized Additive Model (GAM) was calibrated on two thirds of respective dataset. The remaining samples were assigned to a test set to assess model performance. A backward stepwise procedure was followed to select the relevant environmental covariates using their approximate p-values (the level of significance was set at p < 0.05). Standard errors were estimated for each of the three models. The backward stepwise procedure selected coordinates, elevation and clays + fine silt content as environment covariates to model SOC variation in cropland soils; latitude, precipitation, and clays + fine silt content (< 20 µm) for grassland soils; and latitude, elevation, topographic position index and clays + fine silt content (< 20 µm) for forest soils. The validation of the models gave a R² of 0.62 for croplands, 0.38 for grasslands, and 0.35 for forests. These results will be developed and discussed based on implications of natural against anthropogenic drivers on SOC distribution for these three landuses. To finish, a map combining detailed information of SOC content for agricultural soils and forests was for the first time computed for the Walloon region.

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

NASA Technical Reports Server (NTRS)

Orenberg, J. B.; Handy, J.; Quinn, R.

1992-01-01

Because of the power of remote sensing reflectance spectroscopy in determining mineralogy, it has been used as the major method of identifying a possible mineral analogue of the martian surface. A summary of proposed martian surface compositions from reflectance spectroscopy before 1979 was presented by Singer et al. Since that time, iron-rich montmorillonite clay, nanocrystalline or nanophase hematite, and palagonite have been suggested as Mars soil analogue materials. Palagonite in petrological terms is best described as an amorphous, hydrated, ferric iron, silica gel. Montmorillonite is a member of the smectite clay group, and its structure is characterized by an octahedral sheet in coordination with two tetrahedral sheets in which oxygen atoms are shared. The crystal unity of montmorillonite is well defined in contrast to palagonite where it is considered amorphous or poorly crystalline at best. Because of the absence of the diagnostic strong 2.2-micron reflectance band characteristic of clays in the near-infrared (NIR) spectrum of Mars and palagonite and based upon a consideration of wide wavelength coverage (0.3-50 microns), Roush et al. concluded that palagonite is a more likely Mars surface analogue. In spite of the spectral agreement of palagonite and the Mars reflectance spectrum in the 2.2-micron region, palagonite shows poor correspondence with the results of the Viking LR experiment. In contrast, iron-rich montmorillonite clays show relatively good agreement with the results of the Viking LR experiment. This spectral study was undertaken to evaluate the spectral properties of mixtures of palagonite and Mars analogue iron-rich montmorillonite clay (16-18 wt. percent Fe as Fe2O3) as a Mars surface mineralogical model. Mixtures of minerals as Mars surface analogue materials have been studied before, but the mixtures were restricted to crystalline clays and iron oxides.

Nanophase Carbonates on Mars: Implications for Carbonate Formation and Habitability

NASA Technical Reports Server (NTRS)

Archer, P. Douglas, Jr.; Lauer, H. Vern; Ming, Douglas W.; Niles, Paul B.; Morris, Richard V.; Rampe, Elizabeth B.; Sutter, Brad

2014-01-01

Despite having an atmosphere composed primarily of CO2 and evidence for abundant water in the past, carbonate minerals have only been discovered in small amounts in martian dust [1], in outcrops of very limited extent [2, 3], in soils in the Northern Plains (the landing site of the 2007 Phoenix Mars Scout Mission) [4] and may have recently been detected in aeolian material and drilled and powdered sedimentary rock in Gale Crater (the Mars Science Laboratory [MSL] landing site) [5]. Thermal analysis of martian soils by instruments on Phoenix and MSL has demonstrated a release of CO2 at temperatures as low as 250-300 degC, much lower than the traditional decomposition temperatures of calcium or magnesium carbonates. Thermal decomposition temperature can depend on a number of factors such as instrument pressure and ramp rate, and sample particle size [6]. However, if the CO2 released at low temperatures is from carbonates, small particle size is the only effect that could have such a large impact on decomposition temperature, implying the presence of extremely fine-grained (i.e., "nanophase" or clay-sized) carbonates. We hypothesize that this lower temperature release is the signature of small particle-sized (clay-sized) carbonates formed by the weathering of primary minerals in dust or soils through interactions with atmospheric water and carbon dioxide and that this process may persist under current martian conditions. Preliminary work has shown that clay-sized carbonate grains can decompose at much lower temperatures than previously thought. The first work took carbonate, decomposed it to CaO, then flowed CO2 over these samples held at temperatures >100 degC to reform carbonates. Thermal analysis confirmed that carbonates were indeed formed and transmission electron microsopy was used to determine crystal sized were on the order of 10 nm. The next step used minerals such as diopside and wollastonite that were sealed in a glass tube with a CO2 and H2O source. After reacting these materials for a number of hours, thermal analysis demonstrated the formations of carbonates that decomposed at temperatures as low as 500 degC [7]. Further work is underway to carry out the weathering process under more Mars-like conditions (low pressure and low temperature) to determine if the carbonate decomposition temperature can be shifted to even lower temperatures, consistent with what has been detected by thermal analysis instruments on Mars.

Evidence of ancient alteration and subaqueous activity in Oxia Planum, the candidate landing site for Exomars 2020

NASA Astrophysics Data System (ADS)

Quantin-Nataf, Cathy; Carter, John; Thollot, Patrick; Loizeau, Damien; Davis, Joel; Grindrod, Peter; lozach, Loic

2017-04-01

The ExoMars 2018 mission (ESA) has for scientific objectives to search for signs of past and present life on Mars, to investigate the water/geochemical environment as a function of depth in the shallow subsurface, to study to Martian atmospheric trace gases and to characterize the surface environment. The landing site has to be relevant with regard to these objectives while fitting the restrictive engineering constrains. From the scientific point of view, the site must be ancient, from the Early Mars period, for which many scientific evidences favor the existence of a water-related cycle. In this paper, we present the unique location called Oxia Planum, a wide clay bearing plain located between 16° and 19° North and -23° to -28° East proposed as landing site for Exomars 2020 mission. Oxia Planum is located between Ares Vallis and Marwth Vallis in a wide basin just at the outlet of Cogoon Vallis System, with elevations ranging from -2800 m down to -3100 m. The regional compositional mapping of Oxia planum has been achieved based on OMEGA data at 2.5 km/pix well as CRISM multispectral data at 200 m/pix. Mg/Fe phyllosilicates, identified and mapped based on their diagnostic absorptions at 1.4, 1.9 and 2.3 µm are exposed over about 80% of the ellipse surface. The entire unit with phyllosilicates signatures corresponds to a light-toned layered unit that is observed over a large range of elevations (from -2600 m to -3100m) suggesting that like in Marwth Vallis region, the layered and altered formation overlaps a pre-existing topography . The age returned from crater count on the clay rich formation is 3.9 Ga. At the top or embedded within the layered formation, several fluvial morphologies such as former valleys or inverted channels are observed. Also, at the top of the layered clay-rich formation, a deltaic deposit is observed suggesting sub-aqueous episodes postdating the altered layered formation. In terms of mineralogy, the putative delta fan shows layers enriched in hydrated silica. This delta fan implies a second and distinct period of alteration in Oxia Planum signed by a distinct mineralogy. In term of age, the delta has a too small surface to allow a confident age assignment from crater count. We can only state that the delta-fan is older than 3.5 Ga. Oxia Planum recorded at least two clearly distinct alteration environments and contexts: 1) the alteration of the Noachian layers and 2) the fluvio-deltaic system post-dating the Noachian clay rich unit. Deciphering the formation environments for such diverse altered rocks would fulfill the goals of the ExoMars Rover.

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).

Water saturation of hydrothermal smectite-rich clay might have promoted slope instability prior to the 1998 debris avalanche at Casita volcano, Nicaragua

NASA Astrophysics Data System (ADS)

Delmelle, P.; Opfergelt, S.; Boivin, P.; Delvaux, B.

2006-12-01

In October 1998, a relatively small collapse (1 600 000 cubic meters) of a pre-existing scarp occurred on the southern flank of the dormant Casita volcano, Nicaragua. It resulted in a debris avalanche, which quickly transformed into a disastrous debris flow that destroyed two towns and killed more than 2500 people. The failure was shown to be triggered by an excess pore water pressure within highly fractured rocks, following prolonged seasonal rains and precipitations from Hurricane Mitch. This pressure was linked to the water saturation of a hydrothermally-altered clay bedrock impeding in-depth infiltration. Yet, the nature and amounts of the clay material involved in the slope failure were still unknown. Here we report on physical, chemical and mineralogical investigations aimed at quantifying the clay content, and identifying the layer silicates of the hydrothermally-altered clays uncovered by the 1998 debris avalanche. The fine clay material was exceptionally rich in smectite (up to 50 wt. percent), which swells upon wetting and shrinks during dry conditions (Opfergelt et al., 2006, Geophys. Res. Lett., 33 (15), L15305). The smectite belonged to the beidellite-montmorillonite series. The pervasive presence of water-saturated smectitic clay strongly reduced the permeability in depth, and also altered the rheological and mechanical properties of both the pre-failure rock mass and flow materials. The shrink-swell behavior progressively decreased the rock's shear strength, and gradually destabilized the overlying rock mass in the decades and centuries before the landslide, thereby contributing to slope instability. Prolonged intense rainfall led to the formation of incipient weak failure surfaces in the superficial rock mass. As provoked by water saturation, this process was likely favored by the rapid change of the mechanical properties of smectite-rich clays deposited in fracture, joint and gouge interfaces. We suggest that hazard assessments associated with unstable volcanic slopes, especially on volcanoes hosting a long-lived hydrothermal system, should include the potential long and short-term impacts of swelling clays.

Distribution, fate and formation of non-extractable residues of a nonylphenol isomer in soil with special emphasis on soil derived organo-clay complexes.

PubMed

Riefer, Patrick; Klausmeyer, Timm; Schäffer, Andreas; Schwarzbauer, Jan; Schmidt, Burkhard

2011-01-01

Anthropogenic contaminants like nonylphenols (NP) are added to soil, for instance if sewage-sludge is used as fertilizer in agriculture. A commercial mixture of NP consists of more than 20 isomers. For our study, we used one of the predominate isomers of NP mixtures, 4-(3,5-dimethylhept-3-yl)phenol, as a representative compound. The aim was to investigate the fate and distribution of the isomer within soil and soil derived organo-clay complexes. Therefore, (14)C- and (13)C-labeled NP was added to soil samples and incubated up to 180 days. Mineralization was measured and soil samples were fractionated into sand, silt and clay; the clay fraction was further separated in humic acids, fulvic acids and humin. The organo-clay complexes pre-incubated for 90 or 180 days were re-incubated with fresh soil for 180 days, to study the potential of re-mobilization of incorporated residues. The predominate incorporation sites of the nonylphenol isomer in soil were the organo-clay complexes. After 180 days of incubation, 22 % of the applied (14)C was mineralized. The bioavailable, water extractable portion was low (9 % of applied (14)C) and remained constant during the entire incubation period, which could be explained by an incorporation/release equilibrium. Separation of organo-clay complexes, after extraction with solvents to release weakly incorporated, bioaccessible portions, showed that non-extractable residues (NER) were preferentially located in the humic acid fraction, which was regarded as an effect of the chemical composition of this fraction. Generally, 27 % of applied (14)C was incorporated into organo-clay complexes as NER, whereas 9 % of applied (14)C was bioaccessible after 180 days of incubation. The re-mobilization experiments showed on the one hand, a decrease of the bioavailability of the nonylphenol residues due to stronger incorporation, when the pre-incubation period was increased from 90 to 180 days. On the other hand, a shift of these residues from the clay fraction to other soil fractions was observed, implying a dynamic behavior of incorporated residues, which may result in bioaccessibility of the NER of nonylphenol.

Interfacial reactions between humic-like substances and lateritic clay: application to the preparation of "geomimetic" materials.

PubMed

Goure-Doubi, Herve; Martias, Céline; Lecomte-Nana, Gisèle Laure; Nait-Ali, Benoît; Smith, Agnès; Thune, Elsa; Villandier, Nicolas; Gloaguen, Vincent; Soubrand, Marilyne; Konan, Léon koffi

2014-11-15

The aim of this study was to understand the mechanisms responsible for the strengthening of "geomimetic" materials, especially the chemical bonding between clay and humic substances. The mineral matter is lateritic clay which mainly consists in kaolinite, goethite, hematite and quartz. The other starting products are fulvic acid (FA) and lime. The preparation of these geomimetic materials is inspired from the natural stabilization of soils by humic substances occurring over thousands of years. The present process involves acidic and alkaline reactions followed by a curing period of 18days at 60°C under a water saturated atmosphere. The acceleration of the strengthening process usually observed in soils makes this an original process for treatment of soils. The consolidation of the "geomimetic" materials could result from two major phenomena: (i) chemical bonding at the interface between the clay particles and iron compounds and the functional groups of the fulvic acid, (ii) a partial dissolution of the clay grains followed by the precipitation of the cementitious phases, namely calcium silicate hydrates, calcium aluminate hydrates and mixed calcium silicum and aluminum hydrates. Indeed, the decrease of the BET specific area of the lateritic clay after 24 h of reaction with FA added to the structural reorganization observed between 900 and 1000°C in the "geomimetic" material, and to the results of adsorption measurements, confirm the formation of organo-ferric complexes. The presence of iron oxides in clay, in the form of goethite, appears to be another parameter in favor of a ligand exchange process and the creation of binding bridges between FA and the mineral matter. Indeed all faces of goethite are likely to be involved in complexation reactions whereas in lateritic clay only lateral faces could be involved. The results of the adsorption experiments realized at a local scale will improve our understandings about the process of adsorption of FA on lateritic clays and its involvement in the strengthening process of materials. Copyright © 2014 Elsevier Inc. All rights reserved.

Color variations of the Quaternary Red Clay in southern China and its paleoclimatic implications

NASA Astrophysics Data System (ADS)

Hu, Xue-Feng; Du, Yan; Guan, Chun-Lei; Xue, Yong; Zhang, Gan-Lin

2014-04-01

The red clay and red weathering crust are widely distributed in southern China. To study the possible relationship between soil color and paleoclimatic environment, three color parameters, lightness (L*), redness (a*) and yellowness (b*), of twelve Quaternary Red Clay (QRC) profiles in southern China were measured using a colorimeter. Colors of the QRC profiles vary vertically: a* and b* generally increase downward and L* decreases downwards. Colors of the QRC also show spatial variation: a* and b* generally increase towards the equator; whereas L* increases away from it. Both a* and b* are positively significantly correlated with clay (< 2 μm) content, free Fe (Fed), Fed/Fet ratios and other soil weathering indices of the QRC (ρ < 0.05), and the correlations between a* and the weathering indices are much stronger than those between b* and the indices. a* mainly reflects hematite content in soils. Compared with magnetic susceptibility (χ), a* of the QRC is a more promising paleoclimatic indicator, although it is sometimes disturbed by uneven parent materials and dissolution of hematite by water logging. The upward decrease of a* of the QRC profiles reflects a cooling and drying paleoclimate since the end of the Last Interglacial, and the spatial variation of a* coincides with more optimum hydrothermal conditions in lower-latitude areas of southern China.

Silicon Isotopic Fractionation in a Tropical Soil-Plant System

NASA Astrophysics Data System (ADS)

Opfergelt, S.; Delstanche, S.; Cardinal, D.; Andre, L.; Delvaux, B.

2006-12-01

Silica fluxes to soil solutions and water streams are controlled by both abiotic and biotic processes occurring in a Si soil-plant cycle that can be significant in comparison with Si weathering input and hydrological output. The quantification of Si-isotopic fractionation by these processes is highly promising to study the Si soil-plant cycle. Therein, the fate of aqueous monosilicic acid H4SiO4, as produced by silicate weathering, may take four paths: (1) uptake by plants and recycling through falling litter, (2) formation of clay minerals, (3) specific adsorption onto Al and Fe oxides, (4) leaching in drainage waters and export from watersheds. Here we report on detailed Si-isotopic compositions of various Si pools in a tropical soil-plant system involving old stands of banana (Musa acuminata Colla, cv Grande Naine) cropped on a weathering sequence of soils derived from andesitic volcanic ash and pumice deposits in Cameroon, West Africa. Si-isotopic compositions were measured by MC-ICP-MS in dry plasma mode with external Mg doping with a reproducibility of 0.08 permil (2stdev). Results were expressed as delta29Si vs NBS28. The compositions were determined in plant parts, bulk soils, clay fractions (less than 2um) and stream waters used for crop irrigation. Of the weathering sequence, we selected young (Y) and old (O) volcanic soils (vs). Yvs are rich in weatherable minerals, and contain large amounts of pumice gravels; their clay fraction (10-35 percent) contains allophane, halloysite and ferrihydrite. Oppositely, Ovs are strongly weathered and fine clayey soils (75-96 percent clay) rich in halloysite, kaolinite, gibbsite and goethite. Intra-plant fractionation between roots and shoots and within shoots confirmed our previous data measured on banana plants grown in hydroponics. The bulk plant isotopic composition was heavier at Ovs than at Yvs giving a fractionation factor per atomic mass unit between plants and their irrigation water Si source (+0.61 permil) of -0.33 (Ovs) and -0.56 permil (Yvs), close to the fractionation factor previously measured in hydroponics (-0.40 permil). The average delta29Si of phytoliths in banana plants was +0.17 permil. In the topsoil, the isotopic composition of Yvs ( 0.21 permil) was close to that of unweathered pumice (-0.20 permil). The Ovs were significantly lighter (-0.73 permil), confirming published data pointing to lighter isotopic composition with increased weathering. Heavier bulk plants at Ovs might be related to a heavier residual soil solution due to: (i) the formation of lighter clay minerals at Ovs (clay fraction: -0.94 permil) than at Yvs (-0.60 permil), and (ii) the quantitative adsorption of silica onto iron oxides (see Delstanche et al., 2006, AGU), more abundant in weathered Ovs. Our data support the view that plants can induce a strong imprint on the continental cycle of silicon, just as clay formation and possibly Si adsorption onto iron oxides can do. The quantification of Si-isotopic fractionation in the soil-plant system requires, however, further studies involving all the Si pools to achieve a comprehensive understanding of this cycle.

Pore Structure and Diagenetic Controls on Relative Permeability: Implications for Enhanced Oil Recovery and CO2 Storage

NASA Astrophysics Data System (ADS)

Feldman, J.; Dewers, T. A.; Heath, J. E.; Cather, M.; Mozley, P.

2016-12-01

Multiphase flow in clay-bearing sandstones of the Morrow Sandstone governs the efficiency of CO2 storage and enhanced oil recovery at the Farnsworth Unit, Texas. This formation is the target for enhanced oil recovery and injection of one million metric ton of anthropogenically-sourced CO2. The sandstone hosts eight major flow units that exhibit distinct microstructural characteristics due to diagenesis, including: "clean" macro-porosity; quartz overgrowths constricting some pores; ghost grains; intergranular porosity filled by microporous authigenic clay; and feldspar dissolution. We examine the microstructural controls on macroscale (core scale) relative permeability and capillary pressure behavior through: X-ray computed tomography, Robomet.3d, and focused ion beam-scanning electron microscopy imaging of the pore structure of the major flow units of the Morrow Sandstone; relative permeability and capillary pressure in the laboratory using CO2, brine, and oil at reservoir pressure and effective stress conditions. The combined data sets inform links between patterns of diagenesis and multiphase flow. These data support multiphase reservoir simulation and performance assessment by the Southwest Regional Partnership on Carbon Sequestration (SWP). Funding for this project is provided by the U.S. Department of Energy's National Energy Technology Laboratory through the SWP under Award No. DE-FC26-05NT42591. 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 National Nuclear Security Administration under contract DE-AC04-94AL85000.

Detailed gravity survey to help seismic microzonation: Mapping the thickness of unconsolidated deposits in Ottawa, Canada

NASA Astrophysics Data System (ADS)

Lamontagne, M.; Thomas, M.; Silliker, J.; Jobin, D.

2011-11-01

In this study, measurements of gravity were made to map and model the thickness of Quaternary deposits (sand and clay) overlying Ordovician limestones in a suburb of Ottawa (Orléans, Ontario). Because ground motion amplification is partly related to the thickness of unconsolidated deposits, this work helps refine the assessment of the earthquake damage potential of the area. It also helps the mapping of clay basins, which can locally exceed 100 m in thickness, where ground motion amplification can occur. Previous work, including well log data and seismic methods, have yielded a wealth of information on near-surface geology in Orléans, thereby providing the necessary constraints to test the applicability of gravity modeling in other locations where other methods cannot always be used. Some 104 gravity stations were occupied in an 8 × 12 km test area in the Orléans. Stations were accurately located with differential GPS that provided centimetric accuracy in elevation. Densities of the unconsolidated Quaternary deposits (Champlain Sea clay) determined on core samples and densities determined on limestone samples from outcrops were used to constrain models of the clay layer overlying the higher density bedrock formations (limestone). The gravity anomaly map delineates areas where clay basins attain > 100 m depth. Assuming a realistic density for the Champlain Sea clays (1.9-2.1 g/cm 3), the thickness over the higher density bedrock formations (Ordovician carbonate rocks) was modeled and compared with well logs and two seismic reflection profiles. The models match quite well with the information determined from well logs and seismic methods. It was found that gravity and the thickness of unconsolidated deposits are correlated but the uncertainties in both data sets preclude the definition of a direct correlation between the two. We propose that gravity measurements at a local scale be used as an inexpensive means of mapping the thickness of unconsolidated deposits in low-density urban areas. To obtain meaningful results, three conditions must exist. Firstly, elevations of gravity stations must be measured accurately using differential GPS; secondly, that the regional gravity field must be well defined, and thirdly, that the local geology be simple enough to be realistically represented with a two-layer model.

Experimental study and modelling of selenite sorption onto illite and smectite clays.

PubMed

Missana, T; Alonso, U; García-Gutiérrez, M

2009-06-15

This study provides a large set of experimental selenite sorption data for pure smectite and illite. Similar sorption behavior existed in both clays: linear within a large range of the Se concentrations investigated (from 1x10(-10) to 1x10(-3) M); and independent of ionic strength. Selenite sorption was also analysed in the illite/smectite system with the clays mixed in two different proportions, as follows: (a) 30% illite-70% smectite and (b) 43% illite-57% smectite. The objective of the study was to provide the simplest model possible to fit the experimental data, a model also capable of describing selenite sorption in binary illite/smectite clay systems. Selenite sorption data, separately obtained in the single mineral systems, were modeled using both a one- and a two-site non-electrostatic model that took into account the formation of two complexes at the edge sites of the clay. Although the use of a two-site model slightly improved the fit of data at a pH below 4, the simpler one-site model reproduced satisfactorily all the sorption data from pH 3 to 8. The complexation constants obtained by fitting sorption data of the individual minerals were incorporated into a model to predict the adsorption of selenium in the illite/smectite mixtures; the model's predictions were consistent with the experimental adsorption data.

A microstructural study of SAFOD gouge from actively creeping San Andreas Fault zone; Implications for shear localization models

NASA Astrophysics Data System (ADS)

Blackburn, E. D.; Hadizadeh, J.; Babaie, H. A.

2009-12-01

The prevailing models of shear localization in fault gouges are mainly based on experimental aggregates that necessarily neglect the effects of chemical and mechanical maturation with time. The SAFOD cores have provided a chance to test whether cataclasis as a deformation mechanism and factors such as porosity and particle size, critical in some existing shear localization models continue to be critical in mature gouges. We studied a core sample from 3194m MD in the SAFOD phase 3, which consists of intensely foliated shale-siltstone cataclasites in contact with less deformed shale. Microstructures were studied in 3 perpendicular planes with reference to foliation using high resolution scanning electron microscopy, cathodoluminescence imaging, X-ray fluorescence mapping, and energy dispersive X-ray spectroscopy. The cataclastic foliation, recognizable at length scales >100 μm, is primarily defined by bands of clay gouge with distinct microstructure, clay content, and porosity. Variations in elemental composition and porosity of the clay gouge were measured continuously across the foliation. Prominent features within the foliation bands include lens-shaped clusters of highly brecciated and veined siltstone fragments, pyrite smears, and pyrite-cemented cataclasites. The microstructural relations and chemical data provide clear evidence of multiple episodes of veining and deformation with some possibility of relative age determination for the episodes. There is evidence of syn-deformation hydrothermal changes including growth and brittle shear of pyrite, alteration of host shale clays to illite-smectite clays and Fe-rich smectite. Evidence of grain-boundary corrosion of non-clay mineral fragments suggests pressure solution creep. The gouge porosity estimates varied from 0-18% (about 3% in less deformed shale) with the highest value in the bands with abundant siltstone fragments. The banding is mechanically significant since it pervasively segregates the gouge into regions of low clay content, high-porosity and regions of low-porosity, high clay content. It appears from our data that shear localization in the gouge involves pressure solution as well as cataclastic flow assisted by alteration-softening. While the porous bands are potential conduits for fluid flow and could be sites for pressure solution creep, the clay-rich bands could serve as sites of shear localization due to their lower dilatancy rate. A better understanding of interaction between the two deformation mechanisms might shed light on the nature of microearthquake activity in the creeping segment of the SAF.

Grain Size Distribution in Mudstones: A Question of Nature vs. Nurture

NASA Astrophysics Data System (ADS)

Schieber, J.

2011-12-01

Grain size distribution in mudstones is affected by the composition of the source material, the processes of transport and deposition, and post-depositional diagenetic modification. With regard to source, it does make a difference whether for example a slate belt is eroded vs a stable craton. The former setting tends to provide a broad range of detrital quartz in the sub 62 micron size range in addition to clays and greenschist grade rock fragments, whereas the latter may be biased towards coarser quartz silt (30-60 microns), in addition to clays and mica flakes. In flume experiments, when fine grained materials are transported in turbulent flows at velocities that allow floccules to transfer to bedload, a systematic shift of grain size distribution towards an increasingly finer grained suspended load is observed as velocity is lowered. This implies that the bedload floccules are initially constructed of only the coarsest clay particles at high velocities, and that finer clay particles become incorporated into floccules as velocity is lowered. Implications for the rock record are that clay beds deposited from decelerating flows should show subtle internal grading of coarser clay particles; and that clay beds deposited from continuous fast flows should show a uniform distribution of coarse clays. Still water settled clays should show a well developed lower (coarser) and upper (finer) subdivision. A final complication arises when diagenetic processes, such as the dissolution of biogenic silica, give rise to diagenetic quartz grains in the silt to sand size range. This diagenetic silica precipitates in fossil cavities and pore spaces of uncompacted muds, and on casual inspection can be mistaken for detrital quartz. In distal mudstone successions close to 100 % of "apparent" quartz silt can be of that origin, and reworking by bottom currents can further enhance a detrital perception by producing rippled and laminated silt beds. Although understanding how size distributions in mudstones evolve is considered central to problems in hillslope, fluvial, aeolian, coastal, and submarine systems, one can not simply measure distributions and hope to arrive at an answer. The complex origins of mudstones are reflected in their very broad compositional range, and multiple overprinted processes have to be considered in order to make sense out of observed grain size distributions.

Implications of Smectite Subduction at the Costa Rican Convergent Margin

NASA Astrophysics Data System (ADS)

Cardace, D.; Morris, J. D.; Underwood, M. B.; Spinelli, G.

2003-12-01

Legs 205/170 of the Ocean Drilling Program (ODP) drilled a reference section on the incoming plate and sites at the toe of the sedimentary prism at the Costa Rican convergent margin. Complete sediment subduction has been documented, with the prism described by Leg 205/170 shipboard scientists as a paleoslump prism. Despite sediment subduction, Costa Rican arc lava geochemistry shows little sediment signal. Though subduction erosion has been posited as a mechanism for damping the geochemical sediment signal, this abstract addresses whether the clay content and distribution in the subducting pile can (a) play a role in localizing the decollement and (b) impact subduction of sediment to depth. X-ray diffraction (XRD) analyses of bulk sediment, with biogenic silica determinations, have been carried out for samples from the prism, through the decollement, to the underthrust sediments. Clay fractions have been isolated and silica studied for a subset of these samples. XRD peak areas of bulk samples were transformed into relative abundances via matrix singular value decomposition (Fisher and Underwood, 1995, Proc. ODP, Init. Repts., 156: 29-37), and adjusted following silica determination; volcanic ash has been neglected as a sedimentary component. Average relative weight percents of dominant minerals and biogenic silica (bSiO2) for prism toe units (Site 1040) are: P1A (silty clay, 74.8 m thick) 82 wt% clay, 5 wt% quartz, 13 wt% plagioclase, 0 wt% calcite; P1B (silty clay, 296.4 m thick) 82.1 wt% clay, 6.0 wt% quartz, 10.4 wt% plagioclase, 0 wt% calcite, 1.4 wt% bSiO2. Below the decollement, underthrust abundances are: U1A (clayey diatomite, 13.2 m thick) 82.7 wt% clay, 5.2 wt% quartz, 8.9 wt% plagioclase, 0 wt% calcite, 3.2 wt% bSiO2; U1B (clayey diatomite, 38.2 m thick) 80.7 wt% clay, 4.4 wt% quartz, 6.6 wt% plagioclase, 0 wt% calcite, 8.2 wt% bSiO2; U2 (silty claystone, 57.1 m thick) 84.8 wt% clay, 4.5 wt% quartz, 6.8 wt% plagioclase, 0 wt% calcite, 3.9 wt% bSiO2; U3A (siliceous nannofossil chalk, 18.1 m thick) 44.1 wt% clay, 2.0 wt% quartz, 5.6 wt% plagioclase, 31.8 wt% calcite, 16.5 wt% bSiO2; U3B (siliceous nannofossil chalk, 75.55 m thick) 1.9 wt% clay, 0 wt% quartz, 1.1 wt% plagioclase, 92.4 wt% calcite, 4.7 wt% bSiO2; and U3C (siliceous nannofossil chalk, 80.18 m thick) 6.6 wt% clay, 6.1 wt% quartz, 4.6 wt% plagioclase, 74.1 wt% calcite, 8.7 wt% bSiO2. XRD peak areas for clay fractions of prism samples above and in the decollement (Site 1254 ˜Site 1040, 300-370 mbsf) were transformed into relative weight percent data with Biscaye weighting factors. Smectites ranged from 77-93 wt%, illites ranged from 0-4 wt%, and kaolinites/chlorites ranged from 5-20 wt%. The maximum smectite value was obtained in the lower decollement. Bulk mineralogy data for sediments subducting at Costa Rica show that the prism and uppermost underthrust sediments are 80-93 wt% clay sized minerals. Clay mineralogy suggests that the smectite maximum occurs in the lower decollement and decreases dramatically below. Low biogenic silica abundances persist down core, emphasizing the importance of clays to the subducting section at Costa Rica.

How to fracture formations (in Spanish)

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

del Risco V.M.

1971-01-01

Government-owned Petroleos del Peru has found the limited-entry fracturing technique to be the most suitable under prevailing conditions for its NW. Peruvian oil fields. There, most formations available for stimulation are low- permeability and highly compact sands interbedded with thin and thick layers of clay. After experimenting with 8 different commercially available methods, a detailed analysis of the results showed the Shoot-Frac system to be the most effective.

How desert varnish forms?

NASA Astrophysics Data System (ADS)

Perry, Randall S.; Kolb, Vera M.; Lynne, Bridget Y.; Sephton, Mark A.; Mcloughlin, Nicola; Engel, Michael H.; Olendzenski, Lorraine; Brasier, Martin; Staley, James T., Jr.

2005-09-01

Desert varnish is a black, manganese-rich rock coating that is widespread on Earth. The mechanism underlying its formation, however, has remained unresolved. We present here new data and an associated model for how desert varnish forms, which substantively challenges previously accepted models. We tested both inorganic processes (e.g. clays and oxides cementing coatings) and microbial methods of formation. Techniques used in this preliminary study include SEM-EDAX with backscatter, HRTEM of focused ion beam prepared (FIB) wafers and several other methods including XRPD, Raman spectroscopy, XPS and Tof-SIMS. The only hypothesis capable of explaining a high water content, the presence of organic compounds, an amorphous silica phase (opal-A) and lesser quantities of clays than previously reported, is a mechanism involving the mobilization and redistribution of silica. The discovery of silica in desert varnish suggests labile organics are preserved by interaction with condensing silicic acid. Organisms are not needed for desert varnish formation but Bacteria, Archaea, Eukarya, and other organic compounds are passively incorporated and preserved as organominerals. The rock coatings thus provide useful records of past environments on Earth and possibly other planets. Additionally this model also helps to explain the origin of key varnish and rock glaze features, including their hardness, the nature of the "glue" that binds heterogeneous components together, its layered botryoidal morphology, and its slow rate of formation.

Measurements of Acoustic Backscatter of the Deep Sea Floor Using a Deeply Towed Vehicle.

DTIC Science & Technology

1985-12-01

Mackenzie,1960; McKinney and Anderson,1964; Jones, et ai.,1964, Clay and Rona,1965; Hastrup ,1970). A second category was more interested in the implications...calibration. Application Note 205-2. Hastrup , O.L., 1970, Digital analysis of acoustical reflectivity in the Tyrrhenian abys- sal plain, Journal of the

Stratigraphy and hydrologic conditions at the Brookhaven National Laboratory and vicinity, Suffolk County, New York, 1994-97

USGS Publications Warehouse

Scorca, Michael P.; Dorsch, William R.; Paquette, Douglas E.

1999-01-01

Brookhaven National Laboratory (BNL) has installed many test borings as part of an effort to delineate the extent of ground-water contamination at the site. In 1994, the U.S. Geological Survey began a study in cooperation with BNL to define the stratigraphy in the 28-square-mile area encompassing BNL, and to monitor ground-water levels in the 300 squaremile area of central Suffolk County that surrounds BNL. The uppermost geologic units at BNL are of Pleistocene age. These sediments are underlain unconformably by the Matawan Group-Magothy Formation, undifferentiated (referred to as the Magothy Formation), of Cretaceous age, which typically consists of light- to dark-gray, variably sorted sand interbedded with light- to dark-gray clay layers; it also contains beds of grayish-brown to brownish-gray sand. Bed thicknesses differ substantially within each boring and tend to be laterally discontinuous as a result of their terrestrial deltaic depositional environment, although a prominent clay unit, referred to as the ?grayish-brown clay? in this report, was encountered at many borings. Pollen-sample analyses confirm that this unit is of Cretaceous age and is the uppermost unit of Cretaceous sediments in several parts of the study area. The upper surface of the Cretaceous deposits is irregular within the 28-square-mile study area and has relief of about 120 feet. Several prominent channels and ridges in the surface are aligned generally northwest-southeast. The Cretaceous surface beneath BNL is characterized more by local erosional features than by the regional cuesta shape that was suggested by previous authors. The overlying Pleistocene-aged units include (1) a sand layer overlain by the Gardiners Clay, (2) the Gardiners Clay, and (3) upper Pleistocene deposits, which include the Upton unit, glacial outwash, glaciolacustrine deposits, and terminal moraine deposits. The sand unit below the Gardiners Clay was the first Pleistocene unit to be deposited atop the irregular surface of the Cretaceous deposits in this area. The Gardiners Clay was deposited during a major rise in sea level as the sea encroached into parts of the present-day BNL study area. The shallow part of the upper Pleistocene deposits generally consists of light-brown sand and gravel but overlies green to grayish-green, variably sorted sand, silt, and clay at altitudes of 50 to 70 feet below sea level in some parts of the study area. This lower part of the upper Pleistocene deposits in the study area was referred to by previous investigators as the unidentified unit and has been designated as the Upton unit in this report. The discharge of ground water to the Peconic and Carmans Rivers locally affects the water-table configuration. The main ground-water divide on Long Island is about 0.5 miles north of the site; a secondary divide originates near the start of flow of the Peconic River and extends east-southeastward toward the South Fork. The water-table configuration on the BNL site is affected by pumping from supply wells and remediation wells, by infiltration of the water through recharge basins, by discharge from the sewage-treatment plant, and by local near-surface clay units. The horizontal hydraulic gradient at BNL typically is 0.001 foot per foot but can steepen near recharge basins and pumping wells. Vertical flow gradients within the upper Pleistocene deposits (upper glacial aquifer) were as large as 0.007 foot per foot (downward) in the northern part of BNL and were negligible in the southern part. Downward vertical gradients between the lower part of the upper glacial aquifer and the upper part of the Magothy Formation (Magothy aquifer) were about 0.018 foot per foot throughout the site.

Oligomerization reactions of deoxyribonucleotides on montmorillonite clay - The effect of mononucleotide structure on phosphodiester bond formation

NASA Technical Reports Server (NTRS)

Ferris, James P.; KAMALUDDIN

1989-01-01

The formation of oligomers from deoxynucleotides, catalyzed by Na(+)-montmorillonite, was investigated with special attention given to the effect of the monomer structure on the phosphodiester bond formation. It was found that adenine deoxynucleotides bind more strongly to montmorillonite than do the corresponding ribonucleotides and thymidine nucleotides. Tetramers of 2-prime-dpA were detected in the reaction of 2-prime-d-5-prime-AMP with a water-soluble carbodiimide EDAC in the presence of Na(+)-montmorillonite, illustrating the possible role of minerals in the formation of biopolymers on the primitive earth.

Evaluation of Used Fuel Disposition in Clay-Bearing Rock

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

Jove-Colon, Carlos F.; Weck, Philippe F.; Hammond, Glenn Edward

Deep geological disposal of nuclear waste in clay/shale/argillaceous rock formations has received much consideration given its desirable attributes such as isolation properties (low permeability), geochemically reduced conditions, slow diffusion, sorbtive mineralogy, and geologically widespread (Jové Colón et al., 2014). There is a wealth of gained scientific expertise on the behavior of clay/shale/ argillaceous rock given its focus in international nuclear waste repository programs that includes underground research laboratories (URLs) in Switzerland, France, Belgium, and Japan. Jové Colón et al. (2014) have described some of these investigative efforts in clay rock ranging from site characterization to research on the engineered barriermore » system (EBS). Evaluations of disposal options that include nuclear waste disposition in clay/shale/argillaceous rock have determined that this host media can accommodate a wide range of waste types. R&D work within the Used Fuel Disposition Campaign (UFDC) assessing thermal effects and fluid-mineral interactions for the disposition of heat-generating waste have so far demonstrated the feasibility for the EBS and clay host rock to withstand high thermal loads. This report represents the continuation of disposal R&D efforts on the advancement and refinement of coupled Thermal-Hydrological-Mechanical-Chemical (THMC), hydrothermal experiments on clay interactions, used fuel degradation (source term), and thermodynamic modeling and database development. The development and implementation of a clay/shale/argillite reference case described in Jové Colón et al. (2014) for FY15 will be documented in another report (Mariner et al. 2015) – only a brief description will be given here. This clay reference case implementation is the result of integration efforts between the GDSA PA and disposal in argillite work packages. The assessment of sacrificial zones in the EBS is being addressed through experimental work along with 1D reactive-transport and reaction path modeling. The focus of these investigations into the nature of sacrificial zones is to evaluate the chemical effects of heterogeneous chemical reactions at EBS interfaces. The difference in barrier material types and the extent of chemical reactions within these interfacial domains generates changes in mineral abundances. These mineralogical alterations also result in volume changes that, although small, could affect the interface bulk porosity. As in previous deliverables, this report is structured according to various national laboratory contributions describing R&D activities applicable to clay/shale/argillite media.« less

Petrography and geochemistry characteristics of the lower Cretaceous Muling Formation from the Laoheishan Basin, Northeast China: implications for provenance and tectonic setting

NASA Astrophysics Data System (ADS)

Song, Yu; Liu, Zhaojun; Meng, Qingtao; Wang, Yimeng; Zheng, Guodong; Xu, Yinbo

2017-06-01

The petrography, mineralogy and geochemistry of sedimentary rocks from the lower Cretaceous Muling Formation (K1ml) in the Laoheishan basin, northeast (NE) China are studied to determine the weathering intensity, provenance and tectonic setting of the source region. Petrographic data indicate the average quartz-feldspar-lithic fragments (QFL) of the sandstone is Q = 63 %, F = 22 %, and L = 15 %. Lithic fragments mainly contain volcanic clasts that derived from surrounding basement. X-ray diffraction (XRD) data reveal abundant clay and detrital minerals (e.g. quartz), as well as minor calcite in the fine-grained sediments. The Hf contents and element concentration ratios such as Al2O3/TiO2, Co/Th, La/Sc, and La/Th are comparable to sediments derived from felsic and intermediate igneous rocks. The strong genetic relationship with the igneous rocks from the northwest and northeast areas provides evidence that the sediments of the Muling Formation (K1ml) in the Laoheishan basin have been derived from this area. The chemical index of alteration (CIA) and index of chemical variability (ICV) reveal an intensive weathering in the source region of the sediments. The multidimensional tectonic discrimination diagrams indicate that the source rocks of K1ml are mainly derived from the collision system. However, they may also comprise sediments derived from the continental rift system. The results are consistent with the geology of the study area.

Crystallization and textural porosity of synthetic clay minerals.

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

Carrado, K. A.; Csencsits, R.; Thiyagarajan, P.

2002-12-01

The crystallization of synthetic layered magnesium silicate hectorite clays from both silica sol and organosilane sources is compared. For the silica sol-derived clays, a templating method is employed wherein organic or polymeric molecules are included during clay crystallization that are then removed from the composites via calcination. The mechanism of silane-derived hectorite formation is followed by XRD, TGA, 29Si MAS NMR, and small angle X-ray scattering (SAXS), and results are compared to those obtained for the sol-derived hectorite. The mechanism appears to be similar but the rate is approximately doubled when the silane is used rather than silica sol. Analyticalmore » transmission electron microscopy (TEM) is exploited to glean structural morphology information towards resolving the nature of the resulting pore network structures. Results are compared with nitrogen adsorption-desorption isotherm behavior; dominant hysteresis loops are present in the type IV isotherms. Pore size distributions based on both the adsorption and desorption isotherms are compared. Small angle neutron scattering (SANS) experiments reveal that the average particle size increases as synthetic laponite < sol-derived hectorite < silane-derived hectorite < natural hectorite. Contrast matching SANS studies in aqueous and organic solvents are carried out to extract information about pore accessibility.« less

Abiotically-formed, primary dolomite in the mid-Eocene lacustrine succession at Gebel El-Goza El-Hamra, NE Egypt: An approach to the role of smectitic clays

NASA Astrophysics Data System (ADS)

Wanas, H. A.; Sallam, E.

2016-08-01

This study discusses the role of smectitic clays in the formation of an abiotic (physio-chemical) primary dolomite within an evaporative alkaline-saline marginal lake system, in the absence of carbonate precursor and microbes. The present work has been achieved in terms of textural, mineralogical, and geochemical characteristics of dolostones in the Mid-Eocene (Bartonian) lacustrine succession cropping out at Gebel El-Goza El-Hamra (Shabrawet area, NE Egypt). This lacustrine succession is 15-16 m thick, and made up of alternating horizontal beds of dolostone, marlstone and mudrock that show some pedogenic and subaerial exposure features. The dolostones are composed mainly of dolomite (60-90%), smectite (20-30%) and quartz grains (5-10%). The dolomite comprises fine-crystalline rhombs to micro-spherical crystals with no obvious relics of microbial activity and/or carbonate precursor. It is, ordered, nearly stoichiometric (with 46-50% mole of MgCO3) and has δ18O and δ13C values ranging from + 0.44 to + 2.96 VPDB ‰, and 0.93 to - 8.95 VPDB ‰, respectively. The smectite occurs as thin mats that are commonly intergrown and associated with dolomite. Mineralogical, textural and stable isotopic results of the dolomite indicated that the dolomite was formed as an abiotic primary precipitate in alkaline saline lacustrine systems. In this respect, the gel-like highly viscous smectitic medium plus progressive CO2 degassing, elevated evaporation, low sedimentation rate, low sulphates level and alkaline soil solution lowered the kinetic barriers of dolomite precipitation from solution and promoted the incorporation of Mg2 + in the structure of dolomite. Consequently, the presence of smectitic clays in evaporative saline lakes is significant for dolomite formation because they can generate a gel-like highly viscous medium and provide Mg2 + that can facilitate the physcio-chemical precipitation of primary dolomite from solution at ambient temperatures. However, more work is needed to better characterize the role of clays during dolomite formation in alkaline lacustrine environments at ambient temperatures.

Carbonate microfacies analysis of penecontemporaneous dolomites of the Carnian Travenanzes Formation (Southern Alps, Italy)

NASA Astrophysics Data System (ADS)

Niebergall, Simon Michael; Breda, Anna; Preto, Nereo; Habler, Gerlinde; Peckmann, Jörn; Meister, Patrick

2016-04-01

Abundant dolomite (MgCa(CO3)2) occurs in the Middle and Late Triassic carbonate record of the Tethys realm. Whereas dolomite formation is largely related to late diagenesis and/or hydrothermal activity, Preto et al. (2015) suggested a primary origin of dolomite beds and nodules intercalated in clay rich deposits of the Carnian Travenanzes Formation (Fm.; Dolomites, Venetian Alps) based on a transmission electron microscopy study. Thus, dolomites of the Travenanzes Fm. are supposed to have formed during or soon after deposition and its petrographic features may still be indicative of the geochemical conditions prevalent in the depositional setting. The Travenanzes Fm. records both carbonate and siliciclastic input, reflecting a transitional continental to shallow marine environment (Breda and Preto, 2011) with alternations of alluvial plains, sabkhas and/or ephemeral lakes. The goal of this study is to determine the microfacies of the dolomites of the Travenanzes Fm. and to discuss possible depositional environments and scenarios of penecontemporaneous dolomite formation. The samples were taken from the Dibona section described by Breda and Preto (2011). Optical microscopy documented three different types of dolomite: (1) Microcrystalline nodular dolomite shows abundant clay interlayers and fenestral pores filled with coelestine and barite. The homogenous microcrystalline dolomite was further investigated by electron backscatter diffraction (EBSD) mapping, revealing an anhedral to subhedral microstructure of grains ranging from 2 to 10 micrometers in diameter. Some dolomite grew as spherules within the clay matrix. (2) Dolomite pebbles show semi-rounded edges in a dolosparitic matrix. (3) Dolomite with mm- to cm-scale lamination shows regularly spaced undulation with the cuspate side directed upwards. The laminae are also commonly affected by brittle or plastic deformation. Based on the petrographic observations, the following conclusions can be drawn: (1) While the clay abundance reflects a high siliciclastic input in an alluvial plain to marginal marine setting, the nodular dolomite is consistent with growth under vadose conditions, where solutes are transported by capillary flow. (2) Reworking and synsedimentary deformation indicate a depositional environment with temporarily high water energy, either due to tidal currents or storm events. Nevertheless, the lack of fossils precludes common marine conditions. The presence of evaporite minerals, even though they may have formed as secondary phases, suggests hypersaline conditions during deposition. (3) Laminated dolomites agree with formation in a hypersaline coastal ephemeral lake or sabkha environment. The lamination has been interpreted as a result of layered microbial mats, but could be alternatively explained by periodically alternating sediment input. Diverse facies distribution reflects alternating ephermal lake/peritidal and subaerial vadose conditions in a transitional marine to terrestrial environment. Accordingly, the mode of dolomite formation is expected to have varied along with the environmental conditions. Breda, A., Preto, N. (2011) Anatomy of an Upper Triassic continental to marginal-marine system: the mixed siliciclastic-carbonate Travenanzes Formation (Dolomites, Northern Italy). Sedimentology 58, 1613-1647. Preto et al. (2015) Primary dolomite in the Late Triassic Travenanzes Formation Dolomites, Northern Italy: Facies control and possible bacterial influence. Sedimentology 62, 697-716.

Alluvial fan facies of the Yongchong Basin: Implications for tectonic and paleoclimatic changes during Late Cretaceous in SE China

NASA Astrophysics Data System (ADS)

Chen, Liuqin; Steel, Ronald J.; Guo, Fusheng; Olariu, Cornel; Gong, Chenglin

2017-02-01

Late Cretaceous continental redbeds, the Guifeng Group of the Yongchong Basin in SE China have been investigated to conduct detailed fan facies description and interpretation. Tectonic activities determined the alluvial fan development along the basin margin, but the alluvial facies was linked with paleoclimate changes. The Guifeng Group is divided into the Hekou, Tangbian and Lianhe formations in ascending order. The Hekou conglomerates are typically polymict, moderately sorted with erosional bases, cut-and-fill features, normal grading and sieve deposits, representing dominant stream-flows on alluvial fans during the initial opening stage of the basin infill. The Tangbian Formation, however, is characterized by structureless fine-grained sediments with dispersed coarse clasts, and couplets of conglomerate and sandstone or siltstone and mudstone, recording a change to a playa and ephemeral lake environments with occasional stream flooding, thus indicating a basin expanding stage. The hallmark of the Lianhe Formation is disorganized, poorly sorted conglomerates lack of erosional bases, and a wide particle-size range from clay to boulders together reflect mud-rich debris-flows accumulating on fans, likely related to reactivation of faulting along the northwestern mountain fronts during a post-rift stage. The depositional system changes from stream-flows up through playa with ephemeral streams to debris-flows during the accumulation of the three formations are thus attributed to different source rocks and climatic conditions. Therefore, the fluvial-dominated fans of the Hekou Formation recorded a subhumid paleoclimate (Coniacian-Santonian Age). The dominant semiarid climate during the Campanian Age produced abundant fine-grained sediments in the playa and ephemeral lake environments of the Tangbian Formation. A climatic change towards more humidity during the late stage of the Guifeng Group (Maastrichtian Age) probably yielded high deposition rate of coarse clasts in debris-flow dominated fans of the Lianhe Formation. Thus the Late Cretaceous climate changes are inferred to have influenced and preserved signals in the alluvial stratigraphy of the Yongchong Basin.

Turbidity and Suspended Solids Levels and Loads in a Sediment Enriched Stream: Implications for Impacted Lotic and Lentic Ecosystems

DTIC Science & Technology

2007-01-01

surficial sediment survey of the entire lake , Auer 0 40 80 0 40 80 0 40 80 120 et al. (1996) observed particularly high clastics content (e.g., clay...analysis. In Turbidity in Lake Ontario . Limnol. and Oceanogr. 43:187-199. and Other Sediment Surrogates Workshop, Reno, NV, April James, W.F. and J.W... Lake . These sediment inputs have important implications for the lake , within the context of two on-going rehabilitation programs aimed at contaminated

Evidence of cyclic climatic changes recorded in clay mineral assemblages from a continental Paleocene-Eocene sequence, northwestern Argentina

NASA Astrophysics Data System (ADS)

Do Campo, Margarita; Bauluz, Blanca; del Papa, Cecilia; White, Timothy; Yuste, Alfonso; Mayayo, Maria Jose

2018-06-01

The continental Paleocene-Eocene sequence investigated in this study belongs to the Salta Group, deposited in an intracontinental rift, the Salta Basin (NW Argentina), that evolved from the lower Cretaceous to the middle Paleogene, and is subdivided into the Pirgua, the Balbuena and the Santa Barbara Subgroups. The Maíz Gordo Formation (200 m thick) is the middle unit of the Santa Bárbara Subgroup, deposited during late post-rift sedimentation. We studied the mineralogy of fine-grained horizons of this formation by X-ray diffraction and Scanning Electron Microscopy (SEM) in order to examine the connection between vertical changes in clay mineralogy in alluvial sediments and paleosols, and global paleoclimatic changes registered during the Paleogene. Paleosols vary from calcic vertisols in the lowermost levels, to inseptisols and gleysols in intermediate positions, to gleyed oxisols in the upper section, indicating increased chemical weathering through time. Clay mineral relative abundances vary with a general increase in kaolinite content from bottom to top. However, at one site there are significant variations in kaolinite/muscovite (Kln/Ms) that define five cycles of kaolinite abundance and Kln/Ms. that indicate cyclic patterns of paleoprecipitation and paleotemperature. These are interpreted as several short-lived hyperthermals during the Paleocene-early Eocene in the Southern Hemisphere, which correlate with well-established episodes of warmth documented from the Northern Hemisphere.

Re-injection feasibility study of fracturing flow-back fluid in shale gas mining

NASA Astrophysics Data System (ADS)

Kang, Dingyu; Xue, Chen; Chen, Xinjian; Du, Jiajia; Shi, Shengwei; Qu, Chengtun; Yu, Tao

2018-02-01

Fracturing flow-back fluid in shale gas mining is usually treated by re-injecting into formation. After treatment, the fracturing flow-back fluid is injected back into the formation. In order to ensure that it will not cause too much damage to the bottom layer, feasibility evaluations of re-injection of two kinds of fracturing fluid with different salinity were researched. The experimental research of the compatibility of mixed water samples based on the static simulation method was conducted. Through the analysis of ion concentration, the amount of scale buildup and clay swelling rate, the feasibility of re-injection of different fracturing fluid were studied. The result shows that the swelling of the clay expansion rate of treated fracturing fluid is lower than the mixed water of treated fracturing fluid and the distilled water, indicating that in terms of clay expansion rate, the treated fracturing flow-back fluid is better than that of water injection after re-injection. In the compatibility test, the maximum amount of fouling in the Yangzhou oilfield is 12mg/L, and the maximum value of calcium loss rate is 1.47%, indicating that the compatibility is good. For the fracturing fluid with high salinity in the Yanchang oilfield, the maximum amount of scaling is 72mg/L, and the maximum calcium loss rate is 3.50%, indicating that the compatibility is better.

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

Diagenesis and clay mineral formation at Gale Crater, Mars

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

Bridges, J. C.; Schwenzer, S. P.; Leveille, R.

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

Cordão Formation: loess deposits in the southern coastal plain of the state of Rio Grande do Sul, Brazil.

PubMed

Lopes, Renato P; Dillenburg, Sergio R; Schultz, Cesar L

2016-01-01

Loess consists of silt-dominated sediments that cover ~10% of the Earth's surface. In southern South America it occurs in Argentina, Bolivia, Paraguay and Uruguay, and its presence in southern Brazil was never studied in detail. Here is proposed a new lithostratigraphic unit, Cordão Formation, consisting of loess deposits in the southern Brazilian coastal plain. It consists of fine-very fine silt with subordinate sand and clay, found mostly in lowland areas between Pleistocene coastal barriers. These sediments are pale-colored (10YR hue) and forms ~1,5-2,0 meter-thick stable vertical walls. The clay minerals include illite, smectite, interstratified illite/smectite and kaolinite, the coarser fraction is mostly quartz and plagioclase. Caliche and iron-manganese nodules are also present. The only fossils found so far are rodent teeth and a tooth of a camelid (Hemiauchenia paradoxa). Luminescence ages indicate that this loess was deposited in the latest Pleistocene, between ~30 and 10 kyrs ago, and its upper portion was modified by erosion and accumulation of clay and organic matter in the Holocene. The estimated accumulation rate was ~630 g/m2/year. The probable source of this loess is the Pampean Aeolian System of Argentina and it would have been deposited by the increased aeolian processes of the last glacial.

Subglacial till formation: Microscale processes within the subglacial shear zone

NASA Astrophysics Data System (ADS)

Hart, Jane K.

2017-08-01

This was a study of subglacial deformation till genesis from a modern temperate glacier, at Skálafellsjökull, Iceland. Detailed microscale properties of till samples (from Scanning Electron Microscope [SEM] and thin section analysis) were examined from a glacial site with in situ subglacial process monitoring and an exposed subglacial surface in the foreland. Two lithofacies were examined, a grey sandy till derived from the ash and basalt, and a silty reddish brown till derived from oxidized paleosols and/or tephra layers. These also represented a clay-content continuum from low (0.3%) to high (22.3%). The evolution from debris to subglacial till was investigated. This included a reduction in grain-size (21% for grey lithology, 13% reddish brown lithology), and reduction in rounding (RA) (32% for the grey lithology, 26% for the reddish brown lithology), and the quantification and analysis of the different grain erosion/comminution processes in the resultant till. It was shown that the microstructures within a till were dependent on shear strain and glaciological conditions (deformation history). The low clay content tills were dominated by linear structures (lineations and boudins, and anisotropic microfabric) whilst the higher clay content tills were dominated by rotational structures (turbates and plaster, and isotropic microfabric). These results are important in our understanding of the formation of both modern and Quaternary tills and informs our reconstruction of past glacial dynamics.

Diagenesis and clay mineral formation at Gale Crater, Mars

DOE PAGES

Bridges, J. C.; Schwenzer, S. P.; Leveille, R.; ...

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

Atomic force microscopy measurements of bacterial adhesion and biofilm formation onto clay-sized particles

PubMed Central

Huang, Qiaoyun; Wu, Huayong; Cai, Peng; Fein, Jeremy B.; Chen, Wenli

2015-01-01

Bacterial adhesion onto mineral surfaces and subsequent biofilm formation play key roles in aggregate stability, mineral weathering, and the fate of contaminants in soils. However, the mechanisms of bacteria-mineral interactions are not fully understood. Atomic force microscopy (AFM) was used to determine the adhesion forces between bacteria and goethite in water and to gain insight into the nanoscale surface morphology of the bacteria-mineral aggregates and biofilms formed on clay-sized minerals. This study yields direct evidence of a range of different association mechanisms between bacteria and minerals. All strains studied adhered predominantly to the edge surfaces of kaolinite rather than to the basal surfaces. Bacteria rarely formed aggregates with montmorillonite, but were more tightly adsorbed onto goethite surfaces. This study reports the first measured interaction force between bacteria and a clay surface, and the approach curves exhibited jump-in events with attractive forces of 97 ± 34 pN between E. coli and goethite. Bond strengthening between them occurred within 4 s to the maximum adhesion forces and energies of −3.0 ± 0.4 nN and −330 ± 43 aJ (10−18 J), respectively. Under the conditions studied, bacteria tended to form more extensive biofilms on minerals under low rather than high nutrient conditions. PMID:26585552

Association of actinides with microorganisms and clay: Implications for radionuclide migration from waste-repository sites

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

Ohnuki, T.; Francis, A.; Kozai, N.

2010-04-01

We conducted a series of basic studies on the microbial accumulation of actinides to elucidate their migration behavior around backfill materials used in the geological disposal of radioactive wastes. We explored the interactions of U(VI) and Pu(VI) with Bacillus subtilis, kaolinite clay, and within a mixture of the two, directly analyzing their association with the bacterium in the mixture by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The accumulation of U by the mixture rose as the numbers of B. subtilis cells increased. Treating the kaolinite with potassium acetate (CH{sub 3}COOK) removed approximately 80% of the associated uraniummore » while only 65% was removed in the presence of B. subtilis. TEM-EDS analysis confirmed that most of the U taken from solution was associated with B. subtilis. XANES analyses revealed that the oxidation state of uranium associated with B. subtilis, kaolinite, and with the mixture containing both was U(VI). The amount of Pu sorbed by B. subtilis increased with time, but did not reach equilibrium in 48 h; in kaolinite alone, equilibrium was attained within 8 h. After 48 h, the oxidation state of Pu in the solutions exposed to B. subtilis and to the mixture had changed to Pu(V), whereas the oxidation state of the Pu associated with both was Pu(IV). In contrast, there was no change in the oxidation state of Pu in the solution nor on kaolinite after exposure to Pu(VI). SEM-EDS analysis indicated that most of the Pu in the mixture was associated with the bacteria. These results suggest that U(VI) and Pu(VI) preferentially are sorbed to bacterial cells in the presence of kaolinite clay, and that the mechanism of accumulation of U and Pu differs. U(VI) is sorbed directly to the bacterial cells, whereas Pu(VI) first is reduced to Pu(V) and then to Pu(IV), and the latter is associated with the cells. These results have important implications on the migrations of radionuclides around the repository sites of geological disposal. Microbial cells compete with clay colloids for radionuclides accumulation, and because of their higher affinity and larger size, the microbes accumulate radionuclides and migrate much slower than do the clay colloids. Additionally, biofilm coatings formed on the fractured rock surfaces also accumulate radionuclides, thereby retarding radionuclide migration.« less

Sorption and desorption of carbamazepine from water by smectite clays.

PubMed

Zhang, Weihao; Ding, Yunjie; Boyd, Stephen A; Teppen, Brian J; Li, Hui

2010-11-01

Carbamazepine is a prescription anticonvulsant and mood stabilizing pharmaceutical administered to humans. Carbamazepine is persistent in the environment and frequently detected in water systems. In this study, sorption and desorption of carbamazepine from water was measured for smectite clays with the surface negative charges compensated with K+, Ca2+, NH4+, tetramethylammonium (TMA), trimethylphenylammonium (TMPA) and hexadecyltrimethylammonium (HDTMA) cations. The magnitude of sorption followed the order: TMPA-smectite≥HDTMA-smectite>NH4-smectite>K-smectite>Ca-smectite⩾TMA-smectite. The greatest sorption of carbamazepine by TMPA-smectite is attributed to the interaction of conjugate aromatic moiety in carbamazepine with the phenyl ring in TMPA through π-π interaction. Partitioning process is the primary mechanism for carbamazepine uptake by HDTMA-smectite. For NH4-smectite the urea moiety in carbamazepine interacts with exchanged cation NH4+ by H-bonding hence demonstrating relatively higher adsorption. Sorption by K-, Ca- and TMA-smectites from water occurs on aluminosilicate mineral surfaces. These results implicate that carbamazepine sorption by soils occurs primarily in soil organic matter, and soil mineral fractions play a secondary role. Desorption of carbamazepine from the sorbents manifested an apparent hysteresis. Increasing irreversibility of desorption vs. sorption was observed for K-, Ca-, TMA-, TMPA- and HDTMA-clays as aqueous carbamazepine concentrations increased. Desorption hysteresis of carbamazepine from K-, Ca-, NH4-smectites was greater than that from TMPA- and HDTMA-clays, suggesting that the sequestrated carbamazepine molecules in smectite interlayers are more resistant to desorption compared to those sorbed by organic phases in smectite clays. Copyright © 2010 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

New approach of a transient ICP-MS measurement method for samples with high salinity.

PubMed

Hein, Christina; Sander, Jonas Michael; Kautenburger, Ralf

2017-03-01

In the near future it is necessary to establish a disposal for high level nuclear waste (HLW) in deep and stable geological formations. In Germany typical host rocks are salt or claystone. Suitable clay formations exist in the south and in the north of Germany. The geochemical conditions of these clay formations show a strong difference. In the northern ionic strengths of the pore water up to 5M are observed. The determination of parameters like K d values during sorption experiments of metal ions like uranium or europium as homologues for trivalent actinides onto clay stones are very important for long term safety analysis. The measurement of the low concentrated, not sorbed analytes commonly takes place by inductively coupled plasma mass spectrometry (ICP-MS). A direct measurement of high saline samples like seawater with more than 1% total dissolved salt content is not possible. Alternatives like sample clean up, preconcentration or strong dilution have more disadvantages than advantages for example more preparation steps or additional and expensive components. With a small modification of the ICP-MS sample introduction system and a home-made reprogramming of the autosampler a transient analysing method was developed which is suitable for measuring metal ions like europium and uranium in high saline sample matrices up to 5M (NaCl). Comparisons at low ionic strength between the default and the transient measurement show the latter performs similarly well to the default measurement. Additionally no time consuming sample clean-up or expensive online dilution or matrix removal systems are necessary and the analysation shows a high sensitivity due to the data processing based on the peak area. Copyright © 2016 Elsevier B.V. All rights reserved.

Geochemistry of rare earth elements in Permian coals from the Huaibei Coalfield, China

USGS Publications Warehouse

Zheng, Lingyun; Liu, Gaisheng; Chou, C.-L.; Qi, C.; Zhang, Y.

2007-01-01

The rare earth elements (REEs) in coals are important because of: (a) REE patterns can be an indicator of the nature of source rocks of the mineral matter as well as sedimentary environments; (b) REEs abundance in coal may have industrial-significance. In this study, a total of thirty-four samples of Permian coal, partings, roof, and floor were collected from the Huaibei Coalfield, Anhui Province, China. Abundances of rare earth elements (REEs) and other elements in the samples were determined by inductively coupled-plasma mass spectrometry (ICP-MS) and inductively coupled-plasma atomic emission spectrometry (ICP-AES). The results show that the REEs are enriched in coals in the Huaibei Coalfield as compared with Chinese and U.S. coals and the world coal average. Coals in the Lower Shihezi Formation (No. 7, 5, and 4 Coals) and Upper Shihezi Formation (No. 3) have higher REE abundances than the coals in Shanxi Formation (No. 10). Magmatic intrusion resulted in high enrichment of REEs concentrations in No. 5 and 7 Coals. The REE abundances are positively correlated with the ash content. The mineral matter in these coals is mainly made up of clay minerals and carbonates. The REEs are positively correlated with lithophile elements including Si, Al, Ti, Fe, and Na, which are mainly distributed in clay minerals, indicating that REEs are contained mainly in clay minerals. The REE abundances in coals normalized by the ash are higher than that in partings. REEs abundances of coals cannot be accounted for by the REE content in the mineral matter, and some REEs associated with organic matter in coals. ?? 2007 Elsevier Ltd. All rights reserved.

Epigenetic formation of amethyst-bearing geodes from Los Catalanes gemological district, Artigas, Uruguay, southern Paraná Magmatic Province

NASA Astrophysics Data System (ADS)

Duarte, L. C.; Hartmann, L. A.; Vasconcellos, M. A. Z.; Medeiros, J. T. N.; Theye, T.

2009-07-01

Giant geodes (up to 4 m long) in the massive central portions of altered basalt lavas from the Paraná Magmatic Province, southern Brazil and Uruguay, form a world-class source of amethyst and agate. Although the origin of the cavities has been ascribed to degassing of the lava at > 1150 °C, field evidence is conclusive that the giant amethyst-agate-filled geodes were formed by hydrothermal processes at low temperatures. We propose an epigenetic and hydrothermal model for the origin of giant geodes. This model includes hydrothermal brecciation during an early brittle stage and the late formation of the cavities (geodes). In the brittle stage an overpressured aqueous fluid affected the basalt in a P, T field delimited by temperatures between 100 and 150 °C and vapor pressures between 1.2 and 5.5 bar. The fluids were capable of lifting the roof and fracturing the host rock along new subhorizontal and subvertical fractures and breccias in the massive lava. The formation of these structures occurred at shallow depths, unit-by-unit. To open the cavities, dissolution of the now altered basalt to clay minerals is necessary. The process is closely linked to the highest alteration grade of mineralized lavas in Los Catalanes gemological district. Dissolution processes are observed in micrometer-scale in the studied basalts. The primary mineralogy, consisting of labradorite (± andesine) +augite + pigeonite + mesostasis (K-rich), was altered during the interaction of large volumes of hot aqueous fluid with the rock. The alteration of pigeonite and its replacement by smectite is observed around the cavities, followed by the precipitation of amorphous silica and microcrystalline quartz in clay-rich sites. Associated zeolites (heulandite + clinoptilolite) fill the newly formed cavities in progressive stages of hydrothermal alteration. Our data indicate that the temperatures were less than 200 °C and probably less than 150 °C; cavity formation occurred after alteration of the basalt to more than 60 vol.% clay minerals. We thus suggest that cavities related to geode formation are of epigenetic origin.

Environmental significance of Upper Miocene phosphorites at hominid sites in the Lukeino Formation (Tugen Hills, Kenya)

NASA Astrophysics Data System (ADS)

Dericquebourg, Perrine; Person, Alain; Ségalen, Loïc; Pickford, Martin; Senut, Brigitte; Fagel, Nathalie

2015-08-01

The Lukeino Formation contains an important sedimentary and fossiliferous record of the late Miocene (6.09-5.68 Ma), which has in particular yielded the fossil remains of the oldest East African bipedal hominid called Orrorin tugenensis. This fluvio-lacustrine sedimentary succession crops out in the Kenyan part of the East African Rift. It is mainly composed of clay to sandy clay deposits intercalated with volcanic ash horizons, and localized layers of carbonates and diatomites. A detailed sedimentological and mineralogical study of the Lukeino Formation was conducted to throw light on the environmental conditions in which the hominids lived. Several centimetric, relatively continuous and indurated phosphatic horizons, of sedimentary origin, were identified at two sites (Sunbarua and Kapcheberek). Mineralogical (XRD) and geochemical analyses as well as observations by SEM, which was coupled with an energy dispersive spectroscopy (EDS) microprobe, indicate that the autochthonous phosphate layers are composed of a micritic matrix of francolite (38-93%), with incorporation of silicates in variable proportions from one layer to another. The phosphate matrix contains very well preserved and abundant diatom frustules in the basal phosphate layer. These diatoms are identified as Aulacoseira granulata, implying a pH of 7.8-8.2 for freshwaters of the Palaeolake Lukeino. Calcitic tubular structures, linked to a possible bacterial origin, are also observed locally. Phosphate layers occur abruptly within a thick clay-sandy series, associated with an intense runoff phase during the deposition of this interval of the Lukeino Formation. The massive and cyclic input of phosphorus to the lake promoted productivity to the stage where it caused a diatom bloom. The establishment of several phosphate horizons testifies to successive phases of eutrophication of Palaeolake Lukeino. The diatom cells provided some of the organic matter, which was decomposed by bacterial activity at the bottom of the lake in suboxic conditions, but in insufficient quantities to fully form the phosphatic materials. The rest of the organic matter needed for phosphogenesis came from terrigenous supply (plant debris), suggesting the presence of dense vegetation in the catchment of the Palaeolake Lukeino, during this well-drained interval of deposition of the Lukeino Formation.

Illitization within bentonite engineered barrier system in clay repositories for nuclear waste and its effect on the swelling stress: a coupled THMC modeling study

NASA Astrophysics Data System (ADS)

Zheng, L.; Rutqvist, J.; Birkholzer, J. T.; Liu, H. H.

2014-12-01

Geological repositories for disposal of high-level nuclear waste generally rely on a multi-barrier system to isolate radioactive waste from the biosphere. An engineered barrier system (EBS), which comprises in many design concepts a bentonite backfill, is widely used. Clay formations have been considered as a host rock throughout the world. Illitization, the transformation of smectite to illite, could compromise some beneficiary features of EBS bentonite and clay host rock such as sorption and swelling capacity. It is the major determining factor to establish the maximum design temperature of the repositories because it is believed that illitization could be greatly enhanced at temperatures higher than 100 oC. However, existing experimental and modeling studies on the occurrence of illitization and related performance impacts are not conclusive, in part because the relevant couplings between the thermal, hydrological, chemical, and mechanical (THMC) processes have not been fully represented in the models. Here we present a fully coupled THMC simulation study of a generic nuclear waste repository in a clay formation with a bentonite-backfilled EBS. Two scenarios were simulated for comparison: a case in which the temperature in the bentonite near the waste canister can reach about 200 oC and a case in which the temperature in the bentonite near the waste canister peaks at about 100 oC. The model simulations demonstrate that illitization is in general more significant under higher temperature. However, the quantity of illitization is affected by many chemical factors and therefore varies a great deal. The most important chemical factors are the concentration of K in the pore water as well as the abundance and dissolution rate of K-feldspar. For the particular case and bentonite properties studied, the reduction in swelling stress as a result of chemical changes vary from 2% up to 70% depending on chemical and temperature conditions, and key mechanical parameters. The modeling work is illustrative in light of the relative importance of different processes occurring in EBS bentonite and clay host rock at higher than 100 oC conditions, and could be of greater use when site specific data are available.

Dynamics of radiocesium exchange and interstratification in anhydrous clay interlayers: Bridging the atom and single crystal scales

NASA Astrophysics Data System (ADS)

Lammers, L. N.; Pestana, L. R.; Schaettle, K. B.; Head-Gordon, T.

2016-12-01

High structural charge clay minerals govern the transport and retention of radiocesium in soils and clay-rich geologic repositories. Cation exchange capacities in these phases are typically assumed to be limited to fast-exchanging basal and high-affinity edge sites, while ions in anhydrous interlayers, usually K+, are considered non-exchangeable. However, recent high resolution imaging and spectroscopic studies have demonstrated that Cs ions can in fact exchange with interlayer K without the formation of a hydrated intermediate.1,2 These exchange reactions result in sharp exchange fronts wherein K+ ions are completely replaced by Cs+ at the exchange interface, and the rate of exchange varies from layer to layer, resulting in the formation of interstratified structures (i.e., randomly alternating layers of exchanged and pristine interlayers). Currently, this process cannot be explained by any known exchange mechanism, and consequently, no kinetic expressions are available to account for this phenomenon in models of subsurface radiocesium fate and transport. We present a mesoscale model for direct exchange in anhydrous clay interlayers that is based on the kinetics of single ion migration events. Single atom migration kinetics derived from density functional theory (DFT) calculations are used as inputs to kinetic Monte Carlo (kMC) simulations, which capture the collective dynamics of the exchange process over length- and timescales relevant for implementation in reactive transport models. Potential energy surfaces derived from DFT demonstrate that exchange of Cs+ for K+ in anhydrous interlayers lowers the energy barrier to K ion migration by 145 kJ/mol, leading to a positive feedback mechanism that generates atomically sharp exchange fronts. Our work demonstrates the application of "coarse-graining" techniques to develop models for processes with characteristic length- and timescales not accessible by direct atomistic simulation. 1 Okumura T. et al. (2014) Direct observation of cesium at the interlayer region in phlogopite mica. Microscopy 63(1), 65-72. 2 Fuller A. J. et al. (2015) Caesium incorporation and retention in illite interlayers. Appl. Clay Sci. 108, 128-134.

Studying methane migration mechanisms at Walker Ridge, Gulf of Mexico, via 3D methane hydrate reservoir modeling

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

Nole, Michael; Daigle, Hugh; Mohanty, Kishore

We have developed a 3D methane hydrate reservoir simulator to model marine methane hydrate systems. Our simulator couples highly nonlinear heat and mass transport equations and includes heterogeneous sedimentation, in-situ microbial methanogenesis, the influence of pore size contrast on solubility gradients, and the impact of salt exclusion from the hydrate phase on dissolved methane equilibrium in pore water. Using environmental parameters from Walker Ridge in the Gulf of Mexico, we first simulate hydrate formation in and around a thin, dipping, planar sand stratum surrounded by clay lithology as it is buried to 295mbsf. We find that with sufficient methane beingmore » supplied by organic methanogenesis in the clays, a 200x pore size contrast between clays and sands allows for a strong enough concentration gradient to significantly drop the concentration of methane hydrate in clays immediately surrounding a thin sand layer, a phenomenon that is observed in well log data. Building upon previous work, our simulations account for the increase in sand-clay solubility contrast with depth from about 1.6% near the top of the sediment column to 8.6% at depth, which leads to a progressive strengthening of the diffusive flux of methane with time. By including an exponentially decaying organic methanogenesis input to the clay lithology with depth, we see a decrease in the aqueous methane supplied to the clays surrounding the sand layer with time, which works to further enhance the contrast in hydrate saturation between the sand and surrounding clays. Significant diffusive methane transport is observed in a clay interval of about 11m above the sand layer and about 4m below it, which matches well log observations. The clay-sand pore size contrast alone is not enough to completely eliminate hydrate (as observed in logs), because the diffusive flux of aqueous methane due to a contrast in pore size occurs slower than the rate at which methane is supplied via organic methanogenesis. Therefore, it is likely that additional mechanisms are at play, notably bound water activity reduction in clays. Three-dimensionality allows for inclusion of lithologic heterogeneities, which focus fluid flow and subsequently allow for heterogeneity in the methane migration mechanisms that dominate in marine sediments at a local scale. Incorporating recently acquired 3D seismic data from Walker Ridge to inform the lithologic structure of our modeled reservoir, we show that even with deep adjective sourcing of methane along highly permeable pathways, local hydrate accumulations can be sourced either by diffusive or advective methane flux; advectively-sourced hydrates accumulate evenly in highly permeable strata, while diffusively-sourced hydrates are characterized by thin strata-bound intervals with high clay-sand pore size contrasts.« less

Enrichment of trace elements in the clay size fraction of mining soils.

PubMed

Gomes, Patrícia; Valente, Teresa; Braga, M Amália Sequeira; Grande, J A; de la Torre, M L

2016-04-01

Reactive waste dumps with sulfide minerals promote acid mine drainage (AMD), which results in water and soil contamination by metals and metalloids. In these systems, contamination is regulated by many factors, such as mineralogical composition of soil and the presence of sorption sites on specific mineral phases. So, the present study dedicates itself to understanding the distribution of trace elements in different size fractions (<2-mm and <2-μm fractions) of mining soils and to evaluate the relationship between chemical and mineralogical composition. Cerdeirinha and Penedono, located in Portugal, were the waste dumps under study. The results revealed that the two waste dumps have high degree of contamination by metals and arsenic and that these elements are concentrated in the clay size fraction. Hence, the higher degree of contamination by toxic elements, especially arsenic in Penedono as well as the role of clay minerals, jarosite, and goethite in retaining trace elements has management implications. Such information must be carefully thought in the rehabilitation projects to be planned for both waste dumps.

Measurements of Acoustic Backscatter of the Deep Sea Floor Using a Deeply Towed Vehicle

DTIC Science & Technology

1985-12-01

McKinney and Anderson,1964; Jones, et al.,1964, Clay and Rona,1965; Hastrup ,1970). A second category was more interested in the implications of the... Hastrup , O.L., 1970, Digital analysis of acoustical reflectivity in the Tyrrhenian abys- sal plain, Journal of the Acoustical Society of America, vol. 70

Relationships between electrical properties and petrography of El-Maghara sandstone formations, Egypt

NASA Astrophysics Data System (ADS)

Kassab, Mohamed A.; Gomaa, Mohamed M.; Lala, Amir M. S.

2017-06-01

Realization of electrical and petrography of rocks is absolutely necessary for geophysical investigations. The petrographical, petrophysical and electrical properties of sandstone rocks (El-Maghara Formation, North Sinai, Egypt) will be discussed in the present work. The goal of this paper was to highlight interrelations between electrical properties in terms of frequency (conductivity, permittivity and impedance) and petrography, as well as mineral composition. Electrical properties including (conductivity and dielectric constant) were measured at room temperature and humidity of (∼35%). The frequency range used will be from 10 Hz to 100 kHz. Slight changes between samples in electrical properties were found to result from changes in composition and texture. Electrical properties generally change with grain size, shape, sorting, mineralogy and mineral composition. The dielectric constant decreases with frequency and increases with increasing clay content. The conductivity increases with the increase in conductor channels among electrodes. Many parameters can combine together to lead to the same electrical properties. The samples are mainly composed of sand with clay and carbonate.

Sediments in Arctic sea ice: Implications for entrainment, transport and release

USGS Publications Warehouse

Nurnberg, D.; Wollenburg, I.; Dethleff, D.; Eicken, H.; Kassens, H.; Letzig, T.; Reimnitz, E.; Thiede, Jorn

1994-01-01

Despite the Arctic sea ice cover's recognized sensitivity to environmental change, the role of sediment inclusions in lowering ice albedo and affecting ice ablation is poorly understood. Sea ice sediment inclusions were studied in the central Arctic Ocean during the Arctic 91 expedition and in the Laptev Sea (East Siberian Arctic Region Expedition 1992). Results from these investigations are here combined with previous studies performed in major areas of ice ablation and the southern central Arctic Ocean. This study documents the regional distribution and composition of particle-laden ice, investigates and evaluates processes by which sediment is incorporated into the ice cover, and identifies transport paths and probable depositional centers for the released sediment. In April 1992, sea ice in the Laptev Sea was relatively clean. The sediment occasionally observed was distributed diffusely over the entire ice column, forming turbid ice. Observations indicate that frazil and anchor ice formation occurring in a large coastal polynya provide a main mechanism for sediment entrainment. In the central Arctic Ocean sediments are concentrated in layers within or at the surface of ice floes due to melting and refreezing processes. The surface sediment accumulation in central Arctic multi-year sea ice exceeds by far the amounts observed in first-year ice from the Laptev Sea in April 1992. Sea ice sediments are generally fine grained, although coarse sediments and stones up to 5 cm in diameter are observed. Component analysis indicates that quartz and clay minerals are the main terrigenous sediment particles. The biogenous components, namely shells of pelecypods and benthic foraminiferal tests, point to a shallow, benthic, marine source area. Apparently, sediment inclusions were resuspended from shelf areas before and incorporated into the sea ice by suspension freezing. Clay mineralogy of ice-rafted sediments provides information on potential source areas. A smectite maximum in sea ice sediment samples repeatedly occurred between 81??N and 83??N along the Arctic 91 transect, indicating a rather stable and narrow smectite rich ice drift stream of the Transpolar Drift. The smectite concentrations are comparable to those found in both Laptev Sea shelf sediments and anchor ice sediments, pointing to this sea as a potential source area for sea ice sediments. In the central Arctic Ocean sea ice clay mineralogy is significantly different from deep-sea clay mineral distribution patterns. The contribution of sea ice sediments to the deep sea is apparently diluted by sedimentary material provided by other transport mechanisms. ?? 1994.

Influence of Biochar on Deposition and Release of Clay Colloids in Saturated Porous Media.

PubMed

Haque, Muhammad Emdadul; Shen, Chongyang; Li, Tiantian; Chu, Haoxue; Wang, Hong; Li, Zhen; Huang, Yuanfang

2017-11-01

Although the potential application of biochar in soil remediation has been recognized, the effect of biochar on the transport of clay colloids, and accordingly the fate of colloid-associated contaminants, is unclear to date. This study conducted saturated column experiments to systematically examine transport of clay colloids in biochar-amended sand porous media in different electrolytes at different ionic strengths. The obtained breakthrough curves were simulated by the convection-diffusion equation, which included a first-order deposition and release terms. The deposition mechanisms were interpreted by calculating Derjaguin-Landau-Verwey-Overbeek interaction energies. A linear relationship between the simulated deposition rate or the attachment efficiency and the fraction of biochar was observed ( ≥ 0.91), indicating more favorable deposition in biochar than in sand. The interaction energy calculations show that the greater deposition in biochar occurs because the half-tube-like cavities on the biochar surfaces favor deposition in secondary minima and the nanoscale physical and chemical heterogeneities on the biochar surfaces increase deposition in primary minima. The deposited clay colloids in NaCl can be released by reduction of ionic strength, whereas the presence of a bivalent cation (Ca) results in irreversible deposition due to the formation of cation bridging between the colloids and biochar surfaces. The deposition and release of clay colloids on or from biochar surfaces not only change their mobilizations in the soil but also influence the efficiency of the biochar for removal of pollutants. Therefore, the influence of biochar on clay colloid transport must be considered before application of the biochar in soil remediation. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

[Elimination of carbendazim from fruit conditioning waters by adsorption on different materials].

PubMed

Giry, G; Ayele, J; Gauthier, C

2001-07-01

The main aim of this work is to test different materials (activated carbon and other more "rustic" materials like clay and coal) as potential adsorbents in order to evaluate their adsorption capacity for carbendazime. The experiments were realized with certified carbendazim or with benlate solutions left to change long enough to suppose all the benomyl converted into carbendazim. The results were introduced through adsorption kinetic and isotherm forms or interpreted according to the Langmuir model. They pointed out that final elimination percentages of certified carbendazim don't exceed 55%. But even the activated carbon remains the most effective adsorbent, clay and coal present an interesting adsorption capacity, 45% for clay (but its performance is varied), 35% for coal. The presence of formulation additives has an inhibitive effect whatever the materials is. Some adsorption attempts with clay and coal mixtures (100 mg l(-1) of each one) were realized, there isn't a cumulative adsorption, final percentages of elimination are about 45%. Characterization attempts of the adsorbents pointed out that all the materials have a negative global surface charge. But clay possesses a surface charge far more negative than coal, sodipolary lap of carbendazim can further the adsorption. The measures of surface functions according to Boehm titration and capillary rising technique showed that coal differentiates from the other materials by its high capacity to establish Lifshitz-Van der Waals interactions. Carbendazim molecule can present a dipolary moment which could lead to the formation of hydrogen bonds. But results of capillary rising are to be considered by surface unities that could explain the superior adsorption capacity of clay (internal surface: 800m2 g(-1)).

Clay Mineralogy of AN Alluvial Aquifer in a Mountainous, Semiarid Terrain, AN Example from Rifle, Colorado

NASA Astrophysics Data System (ADS)

Elliott, W. C.; Lim, D.; Zaunbrecher, L. K.; Pickering, R. A.; Williams, K. H.; Navarre-Sitchler, A.; Long, P. E.; Noel, V.; Bargar, J.; Qafoku, N. P.

2015-12-01

Alluvial sediments deposited along the Colorado River corridor in the semi-arid regions of central to western Colorado can be important hosts for legacy contamination including U, V, As and Se. These alluvial sediments host aquifers which are thought to provide important "hot spots" and "hot moments" for microbiological activity controlling organic carbon processing and fluxes in the subsurface. Relatively little is known about the clay mineralogy of these alluvial aquifers and the parent alluvial sediments in spite of the fact that they commonly include lenses of silt-clay materials. These lenses are typically more reduced than coarser grained materials, but zones of reduced and more oxidized materials are present in these alluvial aquifer sediments. The clay mineralogy of the non-reduced parent alluvial sediments of the alluvial aquifer located in Rifle, CO (USA) is composed of chlorite, smectite, illite, kaolinite and quartz. The clay mineralogy of non-reduced fine-grained materials at Rifle are composed of the same suite of minerals found in the sediments plus a vermiculite-smectite intergrade that occurs near the bottom of the aquifer near the top of the Wasatch Formation. The clay mineral assemblages of the system reflect the mineralogically immature character of the source sediments. These assemblages are consistent with sediments and soils that formed in a moderately low rainfall climate and suggestive of minimal transport of the alluvial sediments from their source areas. Chlorite, smectite, smectite-vermiculite intergrade, and illite are the likely phases involved in the sorption of organic carbon and related microbial redox transformations of metals in these sediments. Both the occurrence and abundance of chlorite, smectite-vermiculite, illite and smectite can therefore exert an important control on the contaminant fluxes and are important determinants of biogeofacies in mountainous, semiarid terrains.

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.

Geology and resources of the Andersonville, Georgia, kaolin and bauxite district

USGS Publications Warehouse

Cofer, Harland E.; Manker, John Phillip

1983-01-01

The kaolin and kaolin-rich sediments of the Andersonville district were deposited in an estuary environment with restricted circulation and little tidal or longshore current influence. Micaceous kaolinitic clays were deposited during late Paleocene time on broad, shallow water flats between deeper water distributary channels in the estuarine system. During the cycle of deposition, kaolinitic sediments were temporarily exposed to weathering leading to bauxitization and further kaolinization. Subsequently, subaerial and/or subaqueous erosion planed off and redeposited some of the weathering products as organic-rich clays and silts, berthierine-bearing clays, and rarely as colluvial bauxite and sedimentary bauxitic clays. Upon resubmergence, gibbsite-rich, porous bauxite, and bauxitic clays were exposed to silica-saturated water of the estuary. Gibbsite reacted with silica to form kaolinite and resulted in the formation of the transitional (bauxitic) clays overlying the bauxite. Kaolinitic sediments transported by streams again spread over the altered and redeposited material. At the close of the kaolin depositional period movement along the Andersonville Fault Zone and related faults changed the basinal configuration, and the area of the uplifted (southern) block of the fault was exposed to weathering and bauxitization for a limited period of time. General submergence again occurred and much of the district was covered by marine and brackish water, ending the period of commercial kaolin deposition. The kaolin and bauxite deposits in the Andersonville district form a broad belt 15 kilometers wide and 22 kilometers long trending in a northwest-southeastward direction. Most of the kaolin and bauxite of commercial value occur within a narrow 10-kilometer-wide zone in the belt. The reserves of kaolin suitable for refractory and chemical use are approximately 290 million tonnes. Paramarginal resources of sandy kaolin suitable for refractory, chemical, or aluminum manufacture after beneficiation are approximately 240 million tonnes. Indicated and inferred reserves of bauxite and bauxitic clay are 1.8 million tonnes and 7.3 million tonnes respectively.

In Situ Study of CO2 and H2O Partitioning Between Na-Montmorillonite and Variably Wet Supercritical Carbon Dioxide

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

Loring, John S.; Ilton, Eugene S.; Chen, Jeffrey

Shale formations play fundamental roles in large-scale geologic carbon sequestration (GCS) aimed primarily to mitigate climate change, and in smaller-scale GCS targeted mainly for CO2-enhanced gas recovery operations. In both technologies, CO2 is injected underground as a supercritical fluid (scCO2), where interactions with shale minerals could influence successful GCS implementation. Reactive components of shales include expandable clays, such as montmorillonites and mixed-layer illite/smectite clays. In this work, we used in situ X-ray diffraction (XRD) and in situ infrared (IR) spectroscopy to investigate the swelling/shrinkage and water/CO2 sorption of a pure montmorillonite, Na-SWy-2, when the clay is exposed to variably hydratedmore » scCO2 at 50 °C and 90 bar. Measured interlayer spacings and sorbed water concentrations at varying levels of scCO2 hydration are similar to previously reported values measured in air at ambient pressure over a range of relative humidities. IR spectra show evidence of both water and CO2 intercalation, and variations in peak shapes and positions suggest multiple sorbed types with distinct chemical environments. Based on the intensity of the asymmetric CO stretching band of the CO2 associated with the Na-SWy-2, we observed a significant increase in sorbed CO2 as the clay expands from a 0W to a 1W state, suggesting that water props open the interlayer so that CO2 can enter. However, as the clay transitions from a 1W to a 2W state, CO2 desorbs sharply. These observations were placed in the context of two conceptual models concerning hydration mechanisms for expandable clays and were also discussed in light of recent theoretical studies on CO2-H2O-clay interactions. The swelling/shrinkage of expandable clays could affect solid volume, porosity, and permeability of shales. Consequently, the results from this work could aid predictions of shale caprock integrity in large-scale GCS, as well as methane transmissivity in enhanced gas recovery operations.« less

Comparative characterization of the quaternary deposits of Northwest Peninsular Malaysia by wash boring and CPTU site investigation methods

NASA Astrophysics Data System (ADS)

Selamat, Mohamad R.; Rosli, Ros N.; Ramli, Muhd H.; Azmi, Mastura; Kumaravelu, Prakash; Govindasamy, Darvintharen

2017-10-01

A site investigation by wash boring method was carried out in the compound of the Engineering Campus, Universiti Sains Malaysia, in Northwest Peninsular Malaysia. The subsurface soils of the region are known to be comprised of quaternary deposits including the prominent marine clays of the Gula formation. The conventional Standard Penetration Test, or SPT, was carried out for every 1.5m depth. The 18 disturbed samples collected were tested for grain size distribution, Atterberg limits, and specific gravity; and categorized according to the unified soil classification system. The results indicate low SPT numbers, or SPTN, i.e. SPTN<4 for depths lesser than 10m, slightly high SPTN, i.e. 4≤SPTN≤8 for depths between 10 and 12m, and very high SPTN, i.e. SPTN>8 for depths deeper than 12m. Samples from shallower than 12m were mostly classified as low plasticity clay, or CL, which represents the soft marine clay while the underlying materials were mostly sands, namely poorly graded sand, or SP, silty sand, or SM, clayey sand, or SC, and well graded sand, or SW. Another site investigation by the CPTU method was also carried out 5m from the wash boring position, penetrating the entire soft clay stratum, thus giving another marine clay characterization in addition to the one given by the first method. The CPTU results generally gave SPTN≤2 for depths lesser than 8m, 2≤;SPTN≤4 for depths between 8 and 12m, and SPTN=23 at 12.5m, where the CPTU test terminated. The CPTU method classified the soft materials as sensitive fine grains, clays, and clayey silts to silty clays. Thus the CPTU results did not agree very well with the conventional wash boring SPT results in terms of the SPTN obtained. Nevertheless both methods equally identified the prominent presence of the soft marine clay stratum in the top 12.5m and the underlying strong sandy bed with higher bearing capacity values.

Evaluation of used fuel disposition in clay-bearing rock

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

Jove-Colon, Carlos F.; Hammond, Glenn Edward; Kuhlman, Kristopher L.

The R&D program from the DOE Used Fuel Disposition Campaign (UFDC) has documented key advances in coupled Thermal-Hydrological-Mechanical-Chemical (THMC) modeling of clay to simulate its complex dynamic behavior in response to thermal and hydrochemical feedbacks. These efforts have been harnessed to assess the isolation performance of heat-generating nuclear waste in a deep geological repository in clay/shale/argillaceous rock formations. This report describes the ongoing disposal R&D efforts on the advancement and refinement of coupled THMC process models, hydrothermal experiments on barrier clay interactions, used fuel and canister material degradation, thermodynamic database development, and reactive transport modeling of the near-field under non-isothermalmore » conditions. These play an important role to the evaluation of sacrificial zones as part of the EBS exposure to thermally-driven chemical and transport processes. Thermal inducement of chemical interactions at EBS domains enhances mineral dissolution/precipitation but also generates mineralogical changes that result in mineral H2O uptake/removal (hydration/dehydration reactions). These processes can result in volume changes that can affect the interface / bulk phase porosities and the mechanical (stress) state of the bentonite barrier. Characterization studies on bentonite barrier samples from the FEBEX-DP international activity have provided important insight on clay barrier microstructures (e.g., microcracks) and interactions at EBS interfaces. Enhancements to the used fuel degradation model outlines the need to include the effects of canister corrosion due the strong influence of H2 generation on the source term.« less

Acid-base properties of 2:1 clays. I. Modeling the role of electrostatics.

PubMed

Delhorme, Maxime; Labbez, Christophe; Caillet, Céline; Thomas, Fabien

2010-06-15

We present a theoretical investigation of the titratable charge of clays with various structural charge (sigma(b)): pyrophyllite (sigma(b) = 0 e x nm(-2)), montmorillonite (sigma(b) = -0.7 e x nm(-2)) and illite (sigma(b) = -1.2 e x nm(-2)). The calculations were carried out using a Monte Carlo method in the Grand Canonical ensemble and in the framework of the primitive model. The clay particle was modeled as a perfect hexagonal platelet, with an "ideal" crystal structure. The only fitting parameters used are the intrinsic equilibrium constants (pK(0)) for the protonation/deprotonation reactions of the broken-bond sites on the lateral faces of the clay particles, silanol, =SiO(-) + H(+) --> =SiOH, and aluminol, =AlO(-1/2) + H(+) --> =AlOH(+1/2). Simulations are found to give a satisfactory description of the acid-base titration of montmorillonite without any additional fitting parameter. In particular, combining the electrostatics from the crystal substitutions with ionization constants, the simulations satisfactorily catch the shift in the titration curve of montmorillonite according to the ionic strength. Change in the ionic strength modulates the screening of the electrostatic interactions which results in this shift. Accordingly, the PZNPC is found to shift toward alkaline pH upon increasing the permanent basal charge. Unlike previous mean field model results, a significant decrease in PZNPC values is predicted in response to stack formation. Finally, the mean field approach is shown to be inappropriate to study the acid-base properties of clays.

Relevance of magnetic properties for the characterisation of burnt clays and archaeological tiles

NASA Astrophysics Data System (ADS)

Beatrice, C.; Coïsson, M.; Ferrara, E.; Olivetti, E. S.

The archaeomagnetism of pottery, bricks and tiles is typically employed for dating inferences, yet the magnetic properties of ancient ceramics can also be convenient for their characterisation, to evaluate the technological conditions applied for their production (temperature, atmosphere, and duration of firing), as well as to distinguish groups of sherds having different provenance. In this work, the measurement of hysteresis loops has been applied and combined with colour survey to characterise the magnetic properties of burnt clays and archaeological tiles. Four calcareous and non-calcareous clays, along with seventeen tile fragments excavated from the sites of the ancient Roman towns of Pompeii and Gravina di Puglia, in Southern Italy, are examined. The ferrimagnetic character of the clays, in general, enhances with increasing firing temperatures until vitrification processes occur (900-1000 °C) dissolving iron oxides and dispersing the colour and magnetic properties they provide. High values of saturation magnetization are observed in clays with relevant calcareous content after firing above 900 °C, which results in the formation of Ca-silicates able to delay the onset of the vitrification processes. Magnetic properties of the tiles have been evaluated in terms of the high coercivity (i.e. mainly ferrimagnetic) or low coercivity behaviour (i.e. including relevant paramagnetic and superparamagnetic contributions). Enhanced ferrimagnetic character, mostly depending on the growth in number and volume of iron oxide particles, is associated with the development of an intense reddish hue.

Impact of spreading olive mill waste water on agricultural soils for leaching of metal micronutrients and cations.

PubMed

Aharonov-Nadborny, R; Tsechansky, L; Raviv, M; Graber, E R

2017-07-01

Olive mill waste water (OMWW) is an acidic (pH 4-5), saline (EC ∼ 5-10 mS cm -1 ), blackish-red aqueous byproduct of the three phase olive oil production process, with a high chemical oxygen demand (COD) of up to 220,000 mg L -1 . OMWW is conventionally disposed of by uncontrolled dumping into the environment or by semi-controlled spreading on agricultural soils. It was hypothesized that spreading such liquids on agricultural soils could result in the release and mobilization of indigenous soil metals. The effect of OMWW spreading on leaching of metal cations (Na, K, Mg, Mn, Fe, Cu, Zn) was tested in four non-contaminated agricultural soils having different textures (sand, clay loam, clay, and loam) and chemical properties. While the OMWW contributed metals to the soil solution, it also mobilized indigenous soil metals as a function of soil clay content, cation exchange capacity (CEC), and soil pH-buffer capacity. Leaching of soil-originated metals from the sandy soil was substantially greater than from the loam and clay soils, while the clay loam was enriched with metals derived from the OMWW. These trends were attributed to cation exchange and organic-metal complex formation. The organic matter fraction of OMWW forms complexes with metal cations; these complexes may be mobile or precipitate, depending on the soil chemical and physical environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Vesicular delivery of crystalline calcium minerals to ECM in biomineralized nanoclay composites

NASA Astrophysics Data System (ADS)

Katti, Kalpana S.; Ambre, Avinash H.; Payne, Scott; Katti, Dinesh R.

2015-04-01

The mechanisms of mineralization and new bone formation were explored in newly formed extracellular matrix in a nanoclay based composite. Nanoclay films were prepared by intercalating the clays with amino acids and using the amino acids for mineralization of hydroxyapatite. The biomineralized hydroxyapatite (HAP) inside nanoclay galleries or in situ HAP/clay was further used to make films (substrates) using polycaprolactone (PCL) that were seeded with mesenchymal stem cells in a two-stage seeding process. SEM imaging experiments performed on PCL/in situ HAPclay composite films seeded with human MSCs indicated formation of matrix vesicles. The vesicles appear to emerge from the cells that are adhered to the nanoclay HAP films and also deposited in the extracellular space. Vesicles are also observed to be embedded in the cells or under the surface of cells. Crystalline structures with Ca and P were found inside vesicles. The Ca/P ratios obtained using energy dispersive spectroscopy indicate values ranging from below 0.7 to the stoichiometric HAP value of 1.67. The Ca/P ratios were obtained to be closer to the stoichiometric value for single seeding experiments as compared to the double seeding experiments indicating more new bone formation in double seeding experiments. New bone formation with bone mimetic mineralization is thus observed on the in situ HAP nanoclay PCL samples. Hence the PCL/in situ HAPclay composites besides being osteoinductive are also capable of providing a favorable micro-environment for cell dependent processes involved in bone mineral formation.

Oriented clay nanopaper from biobased components--mechanisms for superior fire protection properties.

PubMed

Carosio, F; Kochumalayil, J; Cuttica, F; Camino, G; Berglund, L

2015-03-18

The toxicity of the most efficient fire retardant additives is a major problem for polymeric materials. Cellulose nanofiber (CNF)/clay nanocomposites, with unique brick-and-mortar structure and prepared by simple filtration, are characterized from the morphological point of view by scanning electron microscopy and X-ray diffraction. These nanocomposites have superior fire protection properties to other clay nanocomposites and fiber composites. The corresponding mechanisms are evaluated in terms of flammability (reaction to a flame) and cone calorimetry (exposure to heat flux). These two tests provide a wide spectrum characterization of fire protection properties in CNF/montmorrilonite (MTM) materials. The morphology of the collected residues after flammability testing is investigated. In addition, thermal and thermo-oxidative stability are evaluated by thermogravimetric analyses performed in inert (nitrogen) and oxidative (air) atmospheres. Physical and chemical mechanisms are identified and related to the unique nanostructure and its low thermal conductivity, high gas barrier properties and CNF/MTM interactions for char formation.

Complete Defluorination of Perfluorinated Compounds by Hydrated Electrons Generated from 3-Indole-acetic-acid in Organomodified Montmorillonite

PubMed Central

Tian, Haoting; Gao, Juan; Li, Hui; Boyd, Stephen A.; Gu, Cheng

2016-01-01

Here we describe a unique process that achieves complete defluorination and decomposition of perfluorinated compounds (PFCs) which comprise one of the most recalcitrant and widely distributed classes of toxic pollutant chemicals found in natural environments. Photogenerated hydrated electrons derived from 3-indole-acetic-acid within an organomodified clay induce the reductive defluorination of co-sorbed PFCs. The process proceeds to completion within a few hours under mild reaction conditions. The organomontmorillonite clay promotes the formation of highly reactive hydrated electrons by stabilizing indole radical cations formed upon photolysis, and prevents their deactivation by reaction with protons or oxygen. In the constrained interlayer regions of the clay, hydrated electrons and co-sorbed PFCs are brought in close proximity thereby increasing the probability of reaction. This novel green chemistry provides the basis for in situ and ex situ technologies to treat one of the most troublesome, recalcitrant and ubiquitous classes of environmental contaminants, i.e., PFCs, utilizing innocuous reagents, naturally occurring materials and mild reaction conditions. PMID:27608658

Potentialité d'utilisation d'argiles marocaines de Jbel Kharrou dans l'industrie céramique

NASA Astrophysics Data System (ADS)

El Yakoubi, Nadia; Aberkan, M'hamed; Ouadia, Mohamed

2006-08-01

The Ordovician clays of Jbel Kharrou (Rehamna, Morocco) have been studied for their use in ceramic industry. The realised studies were carried out on two samples B1 and B2, the most representative, taken from a clay dominated formation that outcrops 25 km east of the Skhour Rehamna city. The chemical analyses, mineralogical studies and advanced technological tests undertaken on the two samples indicate that these clays can be considered as non-refractory material, so they can be used to the manufacturing of ceramic products: soil and wall tiles, sanitary, pottery, etc. The tested briquettes, cooked at 1040 °C, remain flat, without deformation or defects; they are of cream white dye. These briquettes show a high mechanical resistance to the flexion, the loss in weight remains tolerable with cooking, lightly elevated (12% ); it can be corrected by the addition of a grease-remover. To cite this article: N. El Yakoubi et al., C. R. Geoscience 338 (2006).

Heterogeneity of organic matter distribution in relation to a transgressive systems tract: Kimmeridge Clay (Jurassic), England

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

Herbin, J.P.; Muller, C.; Geyssant, J.

1991-03-01

The Kimmeridge clay has been drilled in four continuously cored boreholes put down to sample the organic carbon content of the formation. Three of them sited in the Cleveland basin (Yorkshire) prove over 200 m of strata ranging from Mutabilis to Pectinatus zones; the fourth, completing a 35 km transect, proves the lower part of the Kimmeridge clay of the thinner Eastern England shelf. The results show the total organic carbon content (TOC) increasing by 50% when traced from shelf into the basin where deeper bathymetry and more rapid sedimentation have favored preservation of organic matter. The study of stratigraphicalmore » variation of % TOC enables evaluation of fundamental problems of these cycles in which organic matter is one of the major constituents. Such cycles exist throughout the Jurassic and Lower-Middle Cretaceous sequences but a transgressive systems tract such as that of the Kimmeridgian Stage enables the phenomenon to be studied in detail.« less

Clay catalyzed RNA synthesis under Martian conditions: Application for Mars return samples.

PubMed

Joshi, Prakash C; Dubey, Krishna; Aldersley, Michael F; Sausville, Meaghen

2015-06-26

Catalysis by montmorillonites clay minerals is regarded as a feasible mechanism for the abiotic production and polymerization of key biomolecules on early Earth. We have investigated a montmorillonite-catalyzed reaction of the 5'-phosphorimidazolide of nucleosides as a model to probe prebiotic synthesis of RNA-type oligomers. Here we show that this model is specific for the generation of RNA oligomers despite deoxy-mononucleotides adsorbing equally well onto the montmorillonite catalytic surfaces. Optimum catalytic activity was observed over a range of pH (6-9) and salinity (1 ± 0.2 M NaCl). When the weathering steps of early Earth that generated catalytic montmorillonite were modified to meet Martian soil conditions, the catalytic activity remained intact without altering the surface layer charge. Additionally, the formation of oligomers up to tetramer was detected using as little as 0.1 mg of Na⁺-montmorillonite, suggesting that the catalytic activity of a Martian clay return sample can be investigated with sub-milligram scale samples. Copyright © 2015 Elsevier Inc. All rights reserved.

Low-temperature, mineral-catalyzed air oxidation: a possible new pathway for PAH stabilization in sediments and soils.

PubMed

Ghislain, Thierry; Faure, Pierre; Biache, Coralie; Michels, Raymond

2010-11-15

Reactivity of polycyclic aromatic hydrocarbons (PAHs) in the subsurface is of importance to environmental assessment, as they constitute a highly toxic hazard. Understanding their reactivity in the long term in natural recovering systems is thus a key issue. This article describes an experimental investigation on the air oxidation of fluoranthene (a PAH abundant in natural systems polluted by industrial coal use) at 100°C on different mineral substrates commonly found in soils and sediments (quartz sand, limestone, and clay). Results demonstrate that fluoranthene is readily oxidized in the presence of limestone and clay, leading to the formation of high molecular weight compounds and a carbonaceous residue as end product especially for clay experiments. As demonstrated elsewhere, the experimental conditions used permitted the reproduction of the geochemical pathway of organic matter observed under natural conditions. It is therefore suggested that low-temperature, mineral-catalyzed air oxidation is a mechanism relevant to the stabilization of PAHs in sediments and soils.

Evaluation of Used Fuel Disposition in Clay-Bearing Rock

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

Jové Colón, Carlos F.; Weck, Philippe F.; Sassani, David H.

2014-08-01

Radioactive waste disposal in shale/argillite rock formations has been widely considered given its desirable isolation properties (low permeability), geochemically reduced conditions, anomalous groundwater pressures, and widespread geologic occurrence. Clay/shale rock formations are characterized by their high content of clay minerals such as smectites and illites where diffusive transport and chemisorption phenomena predominate. These, in addition to low permeability, are key attributes of shale to impede radionuclide mobility. Shale host-media has been comprehensively studied in international nuclear waste repository programs as part of underground research laboratories (URLs) programs in Switzerland, France, Belgium, and Japan. These investigations, in some cases a decademore » or more long, have produced a large but fundamental body of information spanning from site characterization data (geological, hydrogeological, geochemical, geomechanical) to controlled experiments on the engineered barrier system (EBS) (barrier clay and seals materials). Evaluation of nuclear waste disposal in shale formations in the USA was conducted in the late 70’s and mid 80’s. Most of these studies evaluated the potential for shale to host a nuclear waste repository but not at the programmatic level of URLs in international repository programs. This report covers various R&D work and capabilities relevant to disposal of heat-generating nuclear waste in shale/argillite media. Integration and cross-fertilization of these capabilities will be utilized in the development and implementation of the shale/argillite reference case planned for FY15. Disposal R&D activities under the UFDC in the past few years have produced state-of-the-art modeling capabilities for coupled Thermal-Hydrological-Mechanical-Chemical (THMC), used fuel degradation (source term), and thermodynamic modeling and database development to evaluate generic disposal concepts. The THMC models have been developed for shale repository leveraging in large part on the information garnered in URLs and laboratory data to test and demonstrate model prediction capability and to accurately represent behavior of the EBS and the natural (barrier) system (NS). In addition, experimental work to improve our understanding of clay barrier interactions and TM couplings at high temperatures are key to evaluate thermal effects as a result of relatively high heat loads from waste and the extent of sacrificial zones in the EBS. To assess the latter, experiments and modeling approaches have provided important information on the stability and fate of barrier materials under high heat loads. This information is central to the assessment of thermal limits and the implementation of the reference case when constraining EBS properties and the repository layout (e.g., waste package and drift spacing). This report is comprised of various parts, each one describing various R&D activities applicable to shale/argillite media. For example, progress made on modeling and experimental approaches to analyze physical and chemical interactions affecting clay in the EBS, NS, and used nuclear fuel (source term) in support of R&D objectives. It also describes the development of a reference case for shale/argillite media. The accomplishments of these activities are summarized as follows: Development of a reference case for shale/argillite; Investigation of Reactive Transport and Coupled THM Processes in EBS: FY14; Update on Experimental Activities on Buffer/Backfill Interactions at elevated Pressure and Temperature; and Thermodynamic Database Development: Evaluation Strategy, Modeling Tools, First-Principles Modeling of Clay, and Sorption Database Assessment;ANL Mixed Potential Model For Used Fuel Degradation: Application to Argillite and Crystalline Rock Environments.« less

Paleoecological interpretation of a middle Pennsylvanian coal bed in the central Appalachian basin, U.S.A.

USGS Publications Warehouse

Eble, C.F.; Grady, W.C.

1990-01-01

At least 180 small spore species assignable to 62 miospore genera have been identified from the Middle Pennsylvanian Hernshaw coal bed in southern West Virginia, and its stratigraphic equivalent, the Fire Clay coal bed, in eastern Kentucky. The established natural affinities of a majority of these miospore taxa indicate that the Hernshaw-Fire Clay peat swamp supported a diverse flora consisting of arborescent and "herbaceous" lycopods, ferns (tree-like and small varities), calamities and cordaites. Four floral groupings are recognized in the Hernshaw-Fire Clay coal bed. The inferred paleoecology and vertical stratification of each of these four floral groupings is similar in structure to the "phasic" floral communities found in modern domed peat systems, suggesting that the ancient Hernshaw-Fire Clay peat swamp was a domed deposit. Compositional characteristics (petrographic make up, ash yield and sulfur content) associated with the four groupings are consistent with, and support this interpretation. Where uninterrupted by inorganic partings, the Hernshaw-Fire Clay coal bed commonly contains basal coal layers dominated by Lycospora-bearing arborescent lycopods, with successive increments showing a progression to a more fern- and "herbaceous"-lycopod-dominant flora in younger layers. These observations are corroborated by petrographic analyses, which show the bed to be compositionally stratified. Increments dominated by Lycospora have high vitrinite contents, in contrast to increments containing increased percentages of fern- and "herbaceous"-lycopod-affiliated taxa that are enriched in inertinite macerals. The volcanic ash fall, preserved as the flint-clay parting in the Hernshaw-Fire Clay coal bed, had a considerable effect on the development of the ancient Hernshaw-Fire Clay peat swamp. Besides interrupting peat formation, the presence of an inorganic substrate represent a major change in edaphic conditions within the swamp. This disruption is demonstrated by a change in palynflora and by the establishment and proliferation of some plant groups, notably cordaites and calamites, that may have been better adapted to growth on mineral soils. These palynologic and petrographic relationships, thought to be indicative of a domed peat-swamp origin, are not confined to the Hernshaw-Fire Clay coal bed, but appear to be characteristic of many coal beds in the Appalachian basin, and also of coal beds in other basins. ?? 1990.

Thallium (Tl) sorption onto illite and smectite: Implications for Tl mobility in the environment

NASA Astrophysics Data System (ADS)

Martin, Loïc A.; Wissocq, Aubéry; Benedetti, M. F.; Latrille, Christelle

2018-06-01

Clay minerals play a relevant role in the transport and fate of trace elements in the environment. Though illite has been referred as an important Thallium (Tl) bearing phase in soils, mechanisms and affinity of thallium for clay minerals remain poorly known. This study investigated the sorption behavior of thallium as Tl(I) onto illite and smectite, two clay minerals occurring mainly in soils and sediments. Different sorption experiments were carried out under various pH conditions and Tl concentrations, in competition with sodium and calcium at a constant ionic strength of 0.01 mol L-1. Our results showed that illite displayed more affinity than smectite for thallium. With illite, the distribution coefficients (Kd in L kg-1) varied between 102.75 ± 0.17 and 104.0 ± 0.17 in Na solutions versus between 102.25 ± 0.17 and 103.0 ± 0.17 in Ca solutions, depending on pH. With smectite, Kd (in L kg-1) ranged between 102.50 ± 0.16 and 103.20 ± 0.16 and between 101.25 ± 0.16 and 101.95 ± 0.16 in Na and Ca solutions, respectively. Sorption behavior was described with the Multi-Site Ion Exchanger model and selectivity coefficients with respect to protons were calculated for the first time. In all cases, independently of clay mineral and background electrolyte, low capacity but highly reactive sites were dominant in thallium uptake, highlighting Tl affinity for those sites. Moreover, the exchangeable and reversible interactions between Tl+ and clays reactive sites suggested that in changing conditions, thallium could be released in solution. The role of clay minerals in thallium environmental cycle is evident and confirmed illite to be a dominant Tl bearing phase, in some environment competing with manganese oxides. Compared to others Tl bearing mineral phases, clays are ranked as follows: MnO2 > illite > smectite ∼ ferrihydrite ≥ Al2O3 ∼ goethite > SiO2. Finally, over the three monovalent cations (Tl, Rb, Cs) Tl is the one less sorbed on illite independently of the background cations.

New evidence for the catastrophic demise of a prehistoric settlement (the Lajia Ruins) in the Guanting Basin, upper Yellow River, NW China

NASA Astrophysics Data System (ADS)

Zhao, Hui; Huang, Chun Chang; Zheng, Zixing; Hu, Ying; Zhang, Yuzhu; Guo, Yongqiang; Zhou, Qiang

2017-09-01

The Lajia Ruins in the Guanting Basin, NW China, are a product of the prehistoric Qijia Culture. Like Pompeii, they are a rare example of an archaeological site preserved by a natural disaster and are therefore important in archaeology, anthropology and geology. However, the nature of the disaster(s) responsible for the destruction of the site remains controversial. Most studies have focused on an earthquake and a red clay layer directly overlying the site and a detailed stratigraphic study of the mid-Holocene sedimentary strata combined with other intervals of red clay deposition (hence possible disasters) is lacking. We identified a mid-Holocene paleosol sequence (the Shanglajia section) at the site which contains two layers of red clay, dated to 3950 a BP and 3500 a BP, intercalated within the mid-Holocene paleosol (S0). Subsequent multi-proxy analysis indicated that the characteristics of the two red clay layers resemble those of typical Tertiary red clay deposits and the modern gully deposit at the foot of the Great Red Hills, but are distinctly different from those of the slackwater deposits of the Yellow River and the mid-Holocene paleosol. Our results suggest that, at 3950 a BP and 3500 a BP, two large-scale rainstorm-induced mudflow events, originating from the gullies to the north, flooded the Lajia area on the second terrace of the Yellow River, devastating and burying the human settlements. We infer that the intensified erosion and mass wasting were caused by human activity; in addition, natural factors such as rainstorms and earthquakes, may also have played an important role in triggering catastrophic mudflow events in the Tertiary Red Clay deposits. Overall, our results provide further insights into prehistoric man-land relationships in this environmentally sensitive region which may have implications for modern land use in this region of China and elsewhere.

The role of clay minerals in the preservation of organic matter in sediments of Qinghai Lake, NW China

USGS Publications Warehouse

Yu, Bingsong; Dong, Hailiang; Jiang, Hongchen; Lv, Guo; Eberl, Dennis D.; Li, Shanying; Kim, Jinwook

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.

Tipping Point for Expansion of Layered Aluminosilicates in Weakly Polar Solvents: Supercritical CO2.

PubMed

Schaef, Herbert T; Loganathan, Narasimhan; Bowers, Geoffrey M; Kirkpatrick, R James; Yazaydin, A Ozgur; Burton, Sarah D; Hoyt, David W; Thanthiriwatte, K Sahan; Dixon, David A; McGrail, B Peter; Rosso, Kevin M; Ilton, Eugene S; Loring, John S

2017-10-25

Layered aluminosilicates play a dominant role in the mechanical and gas storage properties of the subsurface, are used in diverse industrial applications, and serve as model materials for understanding solvent-ion-support systems. Although expansion in the presence of H 2 O is well-known to be systematically correlated with the hydration free energy of the interlayer cation, particularly in environments dominated by nonpolar solvents (i.e., CO 2 ), uptake into the interlayer is not well-understood. Using novel high-pressure capabilities, we investigated the interaction of dry supercritical CO 2 with Na-, NH 4 -, and Cs-saturated montmorillonite, comparing results with predictions from molecular dynamics simulations. Despite the known trend in H 2 O and that cation solvation energies in CO 2 suggest a stronger interaction with Na, both the NH 4 - and Cs-clays readily absorbed CO 2 and expanded, while the Na-clay did not. The apparent inertness of the Na-clay was not due to kinetics, as experiments seeking a stable expanded state showed that none exists. Molecular dynamics simulations revealed a large endothermicity to CO 2 intercalation in the Na-clay but little or no energy barrier for the NH 4 - and Cs-clays. Indeed, the combination of experiment and theory clearly demonstrate that CO 2 intercalation of Na-montmorillonite clays is prohibited in the absence of H 2 O. Consequently, we have shown for the first time that in the presence of a low dielectric constant, gas swelling depends more on the strength of the interaction between the interlayer cation and aluminosilicate sheets and less on that with solvent. The finding suggests a distinct regime in layered aluminosilicate swelling behavior triggered by low solvent polarizability, with important implications in geomechanics, storage, and retention of volatile gases, and across industrial uses in gelling, decoloring, heterogeneous catalysis, and semipermeable reactive barriers.

Mineralogical compositions of fault rocks from surface ruptures of Wenchuan earthquake and implication of mineral transformation during the seismic cycle along Yingxiu-Beichuan fault, Sichuan Province, China

NASA Astrophysics Data System (ADS)

Dang, Jiaxiang; Zhou, Yongsheng; He, Changrong; Ma, Shengli

2018-06-01

There are two co-seismic bedrock surface ruptures from the Mw 7.9 Wenchuan earthquake in the northern and central parts of the Beichuan-Yingxiu fault, Sichuan Province, southwest China. In this study, we report on the macrostructure of the fault rocks and results from X-ray powder diffraction analysis of minerals from rocks in the fault zone. The most recent fault gouge (the gouge produced by the most recent co-seismic fault movement) in all the studied outcrops is dark or grayish-black, totally unconsolidated and ultrafine-grained. Older fault gouges in the same outcrops are grayish or yellowish and weakly consolidated. X-ray powder diffraction analysis results show that mineral assemblages in both the old fault gouge and the new fault gouge are more complicated than the mineral assemblages in the bedrock as the fault gouge is rich in clay minerals. The fault gouge inherited its major rock-forming minerals from the parent rocks, but the clay minerals in the fault gouge were generated in the fault zone and are therefore authigenic and synkinematic. In profiles across the fault, clay mineral abundances increase as one traverses from the bedrock to the breccia to the old gouge and from the old gouge to the new gouge. Quartz and illite are found in all collected gouge samples. The dominant clay minerals in the new fault gouge are illite and smectite along the northern part of the surface rupture and illite/smectite mixed-layer clay in the middle part of the rupture. Illite/smectite mixed-layer clay found in the middle part of the rupture indicates that fault slip was accompanied by K-rich fluid circulation. The existence of siderite, anhydrite, and barite in the northern part of the rupture suggests that fault slip at this locality was accompanied by acidic fluids containing ions of Fe, Ca, and Ba.

Controlling weathering and erosion intensity on the southern slope of the Central Himalaya by the Indian summer monsoon during the last glacial

NASA Astrophysics Data System (ADS)

Kuwahara, Yoshihiro; Masudome, Yukiko; Paudel, Mukunda Raj; Fujii, Rie; Hayashi, Tatsuya; Mampuku, Mami; Sakai, Harutaka

2010-03-01

This paper reports the results of clay mineral analysis (the amount of clay fraction, clay mineral assemblages, illite crystallinity) of samples collected from a drilled core (Rabibhawan (RB) core) located in the west-central part of the Kathmandu Basin on the southern slope of the Central Himalaya. The amount of clay fraction in the core sediments between 12 m and 45 m depth (corresponding to ca. 17-76 ka), which belong to the Kalimati Formation, is variable and shows three clay-poor zones (19-31 ka, 44-51 ka, and 66-75 ka). The variations correspond with those of illite crystallinity index (Lanson index (LI) and modified Lanson index (MLI)) and kaolinite/illite ratio as well as the fossil pollen and diatom records reported by previous workers. These data reveal the following transformations occurring during the weathering process in this area: micas(mainlymuscovite)→illite(→illite-smectitemixedlayermineral(R=1))→kaolinite The sedimentation rate (~ 50 cm/kyr) of clay-poor zones that correspond to dry climate intervals is only half that of clay-rich zones (~ 120 cm/kyr) that correspond to wet climate intervals, indicating weakened chemical weathering and erosion and low suspended discharge during dry climate intervals. The clay-poor zones commonly show unique laminite beds with very fine, authigenic calcite, which was probably precipitated under calm and high calcite concentration conditions caused by low precipitation and run-off. The variations between dry and wet conditions in this area as deduced from clay minerals appear to follow the Indian Summer Monsoon Index (ISMI) (30°N-30°S, 1 July) and northern hemisphere summer insolation (NHSI) signals (30°N) at 1 July, especially during the dry climate zones, whereas the wet maxima of the wet climate zones somewhat deviate from the strongest NHSI. On the other hand, the dry-wet records lead markedly the SPECMAP stack (by about 5000 years). These results suggest that the Indian summer monsoon precipitation was strongly controlled by the NHSI or summer insolation difference between the Himalayan-Tibetan Plateau and the subtropical Indian Ocean, showing a major fluctuation on the 23,000 years precessional cycle, and that it was not driven by changes in high-latitude ice volume, although the records of clay mineral indices during the wet intervals leave a question that other factors, in addition to insolation forcing, may play important roles in weathering, erosion, and sedimentation processes.

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

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

Bishop, Michael E.; Glasser, Paul; Dong, Hailiang

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 mechanismsmore » 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.« less

Geology and ground-water conditions in southern Nassau and southeastern Queens Counties, Long Island, New York

USGS Publications Warehouse

Perlmutter, N.M.; Geraghty, J.J.

1963-01-01

Test drilling, electrical logging, and water sampling of 'outpost' and other wells have revealed the existence of a deep confined body of salt water in the Magothy(?) formation beneath southwestern Nassau and southeastern Queens Counties, Long Island, N.Y. In connection with a test-drilling program, cooperatively sponsored by the U.S. Geological Survey, the Nassau County Department of Public Works, and the New York State Water Resources Commission (formerly Water Power and Control Commission), 13 wells ranging in depth from about 130 to 800 feet were drilled during 1952 and 1953 and screened at various depths in the Magothy(?) formation and Jameco gravel. On the basis of the preliminary geologic, hydrologic, and chemical data from these wells, a detailed investigation of ground-water conditions from the water table to the bedrock was begun in a 200-square-mile area in southern Nassau and southeastern Queens Counties. The Inain purposes of the investigation were to delineate the bodies of fresh and salty ground water in the project area, to relate their occurrence and movement to geologic and hydrologic conditions, to estimate the rate of encroachment, if any, of the salty water, and to evaluate the effectiveness of the existing network of outpost wells as detectors of salt-water encroachment. About a million people in the report area, residing mainly in southern Nassau County, are completely dependent on ground water as a source of supply. Fortunately, precipitation averages about 44 inches per year, of which approximately half is estimated to percolate into the ground-water reservoir. The ground water is contained in and moves through eight differentiated geologic units composed of unconsolidated gravel, sand, and clay, of Late Cretaceous, Pleistocene, and Recent age, having a maximum total thickness of about 1,700 feet. The underlying metamorphic and igneous crystalline basement rocks are of Precambrian age and are not water bearing. The water-yielding units from the surface down are (1) the upper Pleistocene deposits, (2) the principal artesian aquifer, composed of the Jameco gravel and Magothy(?) formation, and (3) the Lloyd sand member of the Raritar formation. The confining units are the '20-foot' clay, the Gardiners clay, and the clay member of the Raritan formation. The upper Pleistocene deposits contain an extensive unconfined body of fresh water. Fresh water under artesian conditions is contained in the principal artesian aquifer and the Lloyd sand member. The piezometric surface of the principal artesian aquifer is similar in shape to the south-ward-sloping water table; it ranges in altitude from about sea level to 55 feet above. The chemical quality of the fresh ground water in most of the area in all aquifers is good to excellent, and concentrations of dissolved solids and of chloride generally are below 100 ppm (parts per million) and 10 ppm, respectively. Analyses of water samples from selected wells show no progressive increase in concentration of chloride in most of the area. The data on quality of water have been used to delineate one major and several minor bodies of salty ground water. The wedgeshaped main confined salt-water body, in which the concentration of chloride reaches about 17,000 ppm, is in the Magothy(?) formation and Jameco gravel in extreme southwestern Nassau County and southeastern Queens County. The base of the salt-water wedge is about at the top of the clay member of the Raritan formation. Beneath the barrier beach in south-central and southeastern Nassau County a shallow extension of the main confined salt-water body contains as much as 4,000 ppm of chloride and is separated from the lower main salt-water body by fresh ground water. Shallow, thin bodies of unconfined salty ground water are common in the upper Pleistocene and Recent deposits adjacent to salty surface water in tidal creeks, bays, and the Atlantic

Insights into site formation at Rose Cottage Cave, South Africa, based on the analysis of sediment peels

NASA Astrophysics Data System (ADS)

Kloos, Peter; Miller, Christopher E.; Kritikakis, Panagiotis; Wadley, Lyn

2016-04-01

Rose Cottage Cave (RCC), in South Africa, has been a key site for explaining the origins of modern human behaviour and movement of early modern humans out of Africa. Nine sediment peels were made previously from the profile sections, preserving original materials that provide a record of cultural and environmental change during the late Pleistocene and Holocene. Here, we present the preliminary results of the study of the RCC sediment peels which aims to investigate site formation processes and the implications for site interpretation. Methods used include micromorphology and Fourier Transform Infrared spectroscopy coupled with detailed observations of the peels. The predominance of geogenic processes is demonstrated by the abundance of silt- and sand-sized quartz grains, which entered the site primarily through a crevice at the back of the cave. RCC lacks rich anthropogenic deposits as noted at other Middle Stone Age sites in southern Africa, but anthropogenic input to the sediment is indicated by the presence of charcoal, burnt bone, lithic fragments, fat-derived char and ashes. Clay coating fragments and chaotic microstructures demonstrate that bioturbation and colluvial reworking homogenised much of the deposit and may explain the absence of preserved bedding and rarity of combustion features. Downward movement of water through the sequence, indicated by clay coatings, is the likely cause for poor bone preservation and near lack of ashes at the site, as well as fluctuations in dose rate that have complicated luminescence dating studies. Evidence for diagenesis at the site is in the form of secondary apatite and gypsum. Sedimentary structures such as channel lag deposits and (silt and sand) laminae observed in peels dating between 60 and 35 ka BP suggest a high-energy sedimentary environment, which experienced flooding events that eroded underlying deposits and deposited large volumes of sediment. This explains why some of the post-Howiesons Poort layers contain few artefacts and implies that there may have been more human activity at the site during this time than has previously been suggested.

Preparation and Characterization of Guar-Montmorillonite Nanocomposites

PubMed Central

Mansa, Rola; Detellier, Christian

2013-01-01

Polymer-clay nanocomposites are highly sought-after materials, mainly due to their applicability in a variety of avenues. From the standpoint of the preparation of these nanocomposites, however, organic compatibility with clay and adherence to “green chemistry” concepts and principles can be limiting factors. As such, the objective was to prepare a biopolymer-modified clay nanocomposite using a simple and environmentally friendly method of preparation, whereby pre-treatment of the clay for organic compatibility was bypassed. Novel montmorillonite nanocomposites were prepared using neutral guar gum and cationic guar gum. X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed the formation of intercalated structures. A monolayer configuration of cationic guar within the interlayer space was indicated by XRD results, while treatment with neutral guar gum resulted in the observance of both monolayer and bilayer configurations. Additionally, TEM results indicated partial exfoliation. Results attributed from 13C cross polarization/magic angle spinning nuclear magnetic resonance spectroscopy (CP/MAS NMR) of the nanocomposites indicated peaks corresponding to the guar constituent, confirming the adsorption of the biopolymer. Inductively coupled plasma emission spectrometry (ICP-ES) results indicated the exchange of cations present in neutral guar gum with the sodium cations of montmorillonite, in the case of the neutral guar nanocomposites. PMID:28788384

pH profile of the adsorption of nucleotides onto montmorillonite. II - Adsorption and desorption of 5-prime-AMP in iron-calcium montmorillonite systems

NASA Technical Reports Server (NTRS)

Banin, A.; Lawless, J. G.; Mazzurco, J.; Church, F. M.; Margulies, L.; Orenberg, J. B.

1985-01-01

The interaction of 5-prime-AMP with montmorillonite saturated with various ratios of two metals found ubiquitously on the surface of earth, that is, iron and calcium, is investigated. Adsorption and desorption of the nucleotide were studied in the pH range of 2-12 at three levels of addition: 0.080, 0.268 and 0.803 mmole 5-prime-AMP per gram of clay. Two desorption stages were employed - H2O wash and NaOH extraction (pH = 12.0). 5-prime-AMP was preferentially adsorbed on the Fe-containing clays relative to the Ca clay. The nucleotide was fully recovered by the two desorption stages, mostly by the NaOH extraction. The evidence at hand indicates that 5-prime-AMP reaction with clay is affected by electrostatic interactions involving both attraction and repulsion forces. Some specific adsorption, possibly the result of covalent bonding and complex formation with the adsorbed ion, cannot be ruled out for iron but does not appear to operate for calcium. Changes in pH cause varying degrees of attaction and repulsion of 5-prime-AMP and may have been operating on the primitive earth, leading to sequences of adsorption and release of this biomolecule.

Archaeometrical analyses demonstrates that humans excavated clay from mardels on the Luxembourger Gutland plateau to produce ceramics.

NASA Astrophysics Data System (ADS)

Vanmourik, Jan; Braekmans, Dennis

2017-04-01

Mardels, small closed depressions, are distinctive landforms on the Luxembourger Gutland plateau. In the present landscape most mardels are shallow fens, filled with colluvial sediments. Slotboom (1963) investigated 108 mardels in the Luxembourger Gutland and ascribed the mardels in the Luxembourger Keuper marl formations to subsurface solution of gypsum inclusions, followed by collapse and subsidence of the overlying beds. The colluvial deposits in the mardels were palynologically dated as Post Roman. Schmalen (2001) published an actualized inventory of mardels in the Gutland. This inventory includes also mardels on the Lias marls, a formation without gypsum inclusions. Etienne et al. (2011) considered beside natural processes also anthropogenic factors as explanation for CD's in the Lorraine landscape. The sediments in the majority of the CD's were palynologically dated as Post Roman. Combined with the open character of the local vegetation this suggest that the majority of the mardels are probably abandoned Roman quarries. Slotboom and van Mourik (2015) showed that the fillings of the mardels on the Lias marls are Post-Roman, just as on the Keuper marls. To answer the question "are mardels natural subsidence basins or abandoned quarries" we need additional information from the soil archives. Firstly we must identify the process, responsible for the deposition of clay in the mardels. The majority of the mardels in the Gutland occur in clusters in deciduous forests. Earthworm activity in the forest soils promote lateral clay leaching and soil erosion and mardels function as sediment traps. Due to this process clay with the best properties for the production of ceramics occurred in mardels. This process was active during the whole Holocene. It is striking that we did not find Pre-Roman but only Post-Roman mardel fillings. Secondly we need information about the practice of clay, excavated from mardels. If mardels are really abandoned quarries, the excavated sediments must have been used, most probably for the production of ceramics. If we can find relicts of ceramics in the vicinity of mardels we can compare the composition of these ceramics with mardel clay. We could collect finds of Roman tile-works on the Lias marls (Kalefeld) and of Roman pottery on the Keuper marls (Biischtert) in the vicinity of mardels. Provenance analysis (XRF) demonstrated the similarity of chemical composition of mardel clay and ceramics. This indicates that the mardels on the Gutland plateau developed initially as natural depressions (sediment traps), on Strassen marls related to soil subsidence, caused by joints in the underlying Luxembourger sandstone, on Keuper marls to subsidence after soil subsurface dissolving of gypsum veins. The colluvial clay was used by the Romans for the production of ceramics. Due to the excavation reached the actual seizes. Colluvial clay accumulation restarted in the abandoned quarries. • Slotboom, R.T. (1963) Comparative geomorphological and palynological investigation of the pingos (Viviers) in the Haute Fagnes (Belgium) and the Mardellen in the Gutland (Luxembourg). Zeitschrift für Geomorphologie 7: 193-231. • Schmalen, C. (2002) Einige Mardellen Luxemburgs auf den Keuper-und Liasschichten des Forstamtbezirks Zentrum. Diplomarbeit in Studiengang Umweltplannung an der Fachhochschule Trier, Standort Birkenfeld, 2002. • Etienne, D., Ruffaldi, P., Goepp, S., Ritz, F., Georges-Leroy, M., Pollier, B., Dambrine, E. (2011) The origin of closed depressions in Northeastern France: A new assessment. Geomorphology 126: 121-131. • Slotboom, R.T., van Mourik, J.M. (2015) Pollen records of mardel deposits; the effects of climatic oscillations and land management on soil erosion in Gutland, Luxembourg. Catena 132 (2015) 72-88.

Chemical Processes and Thresholds in Hawaiin Soils

NASA Astrophysics Data System (ADS)

Chadwick, O.

2007-12-01

The Hawaiian Islands are a useful natural laboratory for studying soil development particularly those that can be understood using a matrix of chonosequences and climosequences. The islands are formed over a stationary mantle plume and then are carried to the northwest on the Pacific Plate. Thus the islands get older with distance from the hotspot; Kauai has remnant shield surfaces whose lavas date to about 4,000 ky. It is possible to sample soils that are developing on different age flows ranging from a few hundred years to a few million years. Additionally, individual volcanoes are impacted by differing amounts of rainfall depending on location with respect to the northeasterly trade winds. Whereas rainfall over the open ocean near Hawaii is about 700 mm, rainfall over the Islands ranges from 150 to 11,000 mm. Hawaii is minimally impacted by mineral aerosol additions compared to continental areas and this has a significant impact on soil development. More than 100 soil profiles have been sampled along the Hawaii time-climate matrix with some surprising results. For example, in arid soils might be expected to develop smectite clays, but they are rich in halloysite and allophane. Importantly, these same soils show a trend from high-Mg calcite to dolomite as carbonates accumulate within the profiles - this is one of the first documented occurrences of pedogenic dolomite that is not associated with high levels of salts. It appears that lack of smectite formation lowers the incorporation of Mg into silicate clays and increases its incorporation into carbonates. This is an unusual pedogenic process that seems to be enhanced by the lack of substantial amounts of mica in the basalt derived soils. The only mica is in surface horizons that receive dust derived from distant continents. Without mica there is no template to allow smectite clay formation under the rapid wetting and drying regimes encountered in the arid soils. At the same time that halloysite is forming, iron and aluminum oxides tend to move rapidly from poorly crystalline to crystalline forms, which in turn leads to formation of Oxisols under an arid climate regimes - Torrox formation without substantial climate change. By contrast, soils forming in humid environments along the same time trajectory take much longer to go through the same transformations (allophane to halloysite; poorly crystalline goethite to well crystallized goethite; poorly crystalline gibbsite to well crystallized gibbsite). The longer time required for transformation is related to wet rather than wet- dry cycles and interference by organic carbon in the transformation process. Thus whereas it takes about 400,000 years to form a Torrox, it takes more than three times that long to form a humid-zone Oxisol. In Hawaii we have identified several important thresholds in soil properties that have universal applicability: 1. the shift from udic to perudic soil moisture regime is accompanied by reduction related changes in soil properties particularly accumulation of organic matter and loss of iron-bound phosphorus; 2. shift from ustic to udic moisture leads to rapid loss of nutrients with far reaching implications for soil exchange properties and prehistoric land use, 3. the shift from from ustic to aridic soil conditions leads to greater losses of plant nutrients (bases, P, Si) due to greater wind erosion. Based on archeological evidence, it is clear that Polynesians made land-use decisions that incorporated observations of the soil properties associated with these thresholds.

Ries Bunte Breccia revisited: Indications for the presence of water in Itzing and Otting drill cores and implications for the emplacement process

NASA Astrophysics Data System (ADS)

Pietrek, Alexa; Kenkmann, Thomas

2016-07-01

We reassessed two drill cores of the Bunte Breccia deposits of the Ries crater, Germany. The objectives of our study were the documentation of evidence for water in the Bunte Breccia, the evaluation of how that water influenced the emplacement processes, and from which preimpact water reservoir it was derived. The Bunte Breccia in both cores can be structured into a basal layer composed mainly of local substrate material, overlain by texturally and compositionally diverse, crater-derived breccia units. The basal layer is composed of the youngest sediments (Tertiary clays and Upper Jurassic limestone) and has a razor-sharp boundary to the upper breccia units, which are composed of older rocks of Upper Jurassic to Upper Triassic age. Sparse material exchange occurred between the basal layer and the rest of the Bunte Breccia. Fluids predominantly came from the Tertiary and the Upper Triassic sandstone formation. In the basal layer, Tertiary clays were subjected to intense, ductile deformation, indicating saturation with water. This suggests that water was mixed into the matrix, creating a fluidized basal layer with a strong shear localization. In the upper units, Upper Triassic sandstones are intensely deformed by granular flow. The texture requires that the rocks were disaggregated into granular sand. Vaporization of pore water probably aided fragmentation of these rocks. In the Otting core, hot suevite (T > 600 °C) covered the Bunte Breccia shortly after its emplacement. Vertically oriented gas escape pipes in suevite partly emanate directly at the contact to the Bunte Breccia. They indicate that the Bunte Breccia contained a substantial amount of water in the upper part that was vaporized and escaped through these vents.

Microbially-accelerated consolidation of oil sands tailings. Pathway I: changes in porewater chemistry

PubMed Central

Siddique, Tariq; Kuznetsov, Petr; Kuznetsova, Alsu; Arkell, Nicholas; Young, Rozlyn; Li, Carmen; Guigard, Selma; Underwood, Eleisha; Foght, Julia M.

2014-01-01

Dispersed clay particles in mine tailings and soft sediments remain suspended for decades, hindering consolidation and challenging effective management of these aqueous slurries. Current geotechnical engineering models of self-weight consolidation of tailings do not consider microbial contribution to sediment behavior, however, here we show that microorganisms indigenous to oil sands tailings change the porewater chemistry and accelerate consolidation of oil sands tailings. A companion paper describes the role of microbes in alteration of clay chemistry in tailings. Microbial metabolism in mature fine tailings (MFT) amended with an organic substrate (hydrolyzed canola meal) produced methane (CH4) and carbon dioxide (CO2). Dissolution of biogenic CO2 lowered the pH of amended MFT to pH 6.4 vs. unamended MFT (pH 7.7). About 12% more porewater was recovered from amended than unamended MFT during 2 months of active microbial metabolism, concomitant with consolidation of tailings. The lower pH in amended MFT dissolved carbonate minerals, thereby releasing divalent cations including calcium (Ca2+) and magnesium (Mg2+) and increasing bicarbonate (HCO−3) in porewater. The higher concentrations increased the ionic strength of the porewater, in turn reducing the thickness of the diffuse double layer (DDL) of clay particles by reducing the surface charge potential (repulsive forces) of the clay particles. The combination of these processes accelerated consolidation of oil sands tailings. In addition, ebullition of biogenic gases created transient physical channels for release of porewater. In contrast, saturating the MFT with non-biogenic CO2 had little effect on consolidation. These results have significant implications for management and reclamation of oil sands tailings ponds and broad importance in anaerobic environments such as contaminated harbors and estuaries containing soft sediments rich in clays and organics. PMID:24711805

Microbially-accelerated consolidation of oil sands tailings. Pathway I: changes in porewater chemistry.

PubMed

Siddique, Tariq; Kuznetsov, Petr; Kuznetsova, Alsu; Arkell, Nicholas; Young, Rozlyn; Li, Carmen; Guigard, Selma; Underwood, Eleisha; Foght, Julia M

2014-01-01

Dispersed clay particles in mine tailings and soft sediments remain suspended for decades, hindering consolidation and challenging effective management of these aqueous slurries. Current geotechnical engineering models of self-weight consolidation of tailings do not consider microbial contribution to sediment behavior, however, here we show that microorganisms indigenous to oil sands tailings change the porewater chemistry and accelerate consolidation of oil sands tailings. A companion paper describes the role of microbes in alteration of clay chemistry in tailings. Microbial metabolism in mature fine tailings (MFT) amended with an organic substrate (hydrolyzed canola meal) produced methane (CH4) and carbon dioxide (CO2). Dissolution of biogenic CO2 lowered the pH of amended MFT to pH 6.4 vs. unamended MFT (pH 7.7). About 12% more porewater was recovered from amended than unamended MFT during 2 months of active microbial metabolism, concomitant with consolidation of tailings. The lower pH in amended MFT dissolved carbonate minerals, thereby releasing divalent cations including calcium (Ca(2+)) and magnesium (Mg(2+)) and increasing bicarbonate (HCO(-) 3) in porewater. The higher concentrations increased the ionic strength of the porewater, in turn reducing the thickness of the diffuse double layer (DDL) of clay particles by reducing the surface charge potential (repulsive forces) of the clay particles. The combination of these processes accelerated consolidation of oil sands tailings. In addition, ebullition of biogenic gases created transient physical channels for release of porewater. In contrast, saturating the MFT with non-biogenic CO2 had little effect on consolidation. These results have significant implications for management and reclamation of oil sands tailings ponds and broad importance in anaerobic environments such as contaminated harbors and estuaries containing soft sediments rich in clays and organics.

Tipping Point for Expansion of Layered Aluminosilicates in Weakly Polar Solvents: Supercritical CO 2

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

Schaef, Herbert T.; Loganathan, Narasimhan; Bowers, Geoffrey M.

Layered aluminosilicates play a dominant role in the mechanical and gas storage properties of the subsurface, are used in diverse industrial applications, and serve as model materials for understanding solvent-ion-support systems. Although expansion in the presence of H2O is well known to be systematically correlated with the hydration free energy of the interlayer cation, in environments dominated by non-polar solvents (i.e. CO2), uptake into the interlayer is not well-understood. Using novel high pressure capabilities, we investigated the interaction of super-critical CO2 with Na+-, NH4+-, and Cs+-saturated montmorillonite, comparing results with predictions from molecular dynamics simulations. Despite the known trend inmore » H2O, and that cation solvation energies in CO2 suggest a stronger interaction with Na+, both the NH4+- and Cs+-clays readily absorbed CO2 and expanded while the Na+-clay did not. The apparent inertness of the Na+-clay was not due to kinetics, as experiments seeking a stable expanded state showed that none exists. Molecular dynamics simulations revealed a large endothermicity to CO2 intercalation in the Na+-clay, but little or no energy barrier for the NH4+- and Cs+-clays. Consequently, we have shown for the first time that in the presence of a low dielectric constant gas swelling depends more on the strength of the interaction between interlayer cation and aluminosilicate sheets and less on that with solvent. The finding suggests a distinct regime in layered aluminosilicates swelling behavior triggered by low solvent polarizability, with important implications in geomechanics, storage and retention of volatile gases, and across industrial uses in gelling, decoloring, heterogeneous catalysis, and semi-permeable reactive barriers.« less

Toward Accurate Adsorption Energetics on Clay Surfaces

PubMed Central

2016-01-01

Clay minerals are ubiquitous in nature, and the manner in which they interact with their surroundings has important industrial and environmental implications. Consequently, a molecular-level understanding of the adsorption of molecules on clay surfaces is crucial. In this regard computer simulations play an important role, yet the accuracy of widely used empirical force fields (FF) and density functional theory (DFT) exchange-correlation functionals is often unclear in adsorption systems dominated by weak interactions. Herein we present results from quantum Monte Carlo (QMC) for water and methanol adsorption on the prototypical clay kaolinite. To the best of our knowledge, this is the first time QMC has been used to investigate adsorption at a complex, natural surface such as a clay. As well as being valuable in their own right, the QMC benchmarks obtained provide reference data against which the performance of cheaper DFT methods can be tested. Indeed using various DFT exchange-correlation functionals yields a very broad range of adsorption energies, and it is unclear a priori which evaluation is better. QMC reveals that in the systems considered here it is essential to account for van der Waals (vdW) dispersion forces since this alters both the absolute and relative adsorption energies of water and methanol. We show, via FF simulations, that incorrect relative energies can lead to significant changes in the interfacial densities of water and methanol solutions at the kaolinite interface. Despite the clear improvements offered by the vdW-corrected and the vdW-inclusive functionals, absolute adsorption energies are often overestimated, suggesting that the treatment of vdW forces in DFT is not yet a solved problem. PMID:27917256

Geochemical Fate and Transport of Sildenafil in Natural Soils

NASA Astrophysics Data System (ADS)

Turner, A. E.; Vulava, V. M.

2016-12-01

In recent years, pharmaceutical drugs have become of increasing concern to the health of our environment. As a result of wastewater treatment plant discharge and various sources of surface runoff, pharmaceuticals can be found in trace amounts in our most common water resources. Sildenafil, a drug marketed to treat erectile dysfunction, is amongst the top 20 most prescribed pharmaceutical products in the U.S. Sildenafil is a complex polar organic molecule with multiple amine functional groups, which gives it acid-base functionality. The most common pKa of this molecule is approximately 6.0 and water solubility ranges from 3.5 to 4.6 mg/L. The goal of this project is to examine the sorption and transport behavior of sildenafil in natural organic matter- (OM) and clay-rich soils. Soils used for this study were collected from undisturbed forested areas in Francis Marion National Forest, Charleston, SC. A series of batch sorption isotherm and column transport experiments were conducted with these soils. Sildenafil was analyzed using high performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC-MS) techniques. Batch sorption isotherm experiments produced nonlinear data for both OM- and clay-rich soil types. The data shows that sildenafil sorbs more strongly to the clay-rich soils than to the OM-rich soils. This suggests that sildenafil behaved as a cation and preferentially sorbed with the negatively-charged clay minerals. The transport behavior of sildenafil as determined by experiments with soil-packed glass chromatography columns confirmed this behavior. The resulting breakthrough curves show that sildenafil is strongly retarded in clay-rich soils. Our studies do not show degradation or transformation of sildenafil in soils. The results from this study have strong implications for environmental management of pharmaceutical chemical effluents and disposal.

Modeling the arrangement of particles in natural swelling-clay porous media using three-dimensional packing of elliptic disks

NASA Astrophysics Data System (ADS)

Ferrage, Eric; Hubert, Fabien; Tertre, Emmanuel; Delville, Alfred; Michot, Laurent J.; Levitz, Pierre

2015-06-01

Swelling clay minerals play a key role in the control of water and pollutant migration in natural media such as soils. Moreover, swelling clay particles' orientational properties in porous media have significant implications for the directional dependence of fluid transfer. Herein we investigate the ability to mimic the organization of particles in natural swelling-clay porous media using a three-dimensional sequential particle deposition procedure [D. Coelho, J.-F. Thovert, and P. M. Adler, Phys. Rev. E 55, 1959 (1997), 10.1103/PhysRevE.55.1959]. The algorithm considered is first used to simulate disk packings. Porosities of disk packings fall onto a single master curve when plotted against the orientational scalar order parameter value. This relation is used to validate the algorithm used in comparison with existing ones. The ellipticity degree of the particles is shown to have a negligible effect on the packing porosity for ratios ℓa/ℓb less than 1.5, whereas a significant increase in porosity is obtained for higher values. The effect of the distribution of the geometrical parameters (size, aspect ratio, and ellipticity degree) of particles on the final packing properties is also investigated. Finally, the algorithm is used to simulate particle packings for three size fractions of natural swelling-clay mineral powders. Calculated data regarding the distribution of the geometrical parameters and orientation of particles in porous media are successfully compared with experimental data obtained for the same samples. The results indicate that the obtained virtual porous media can be considered representative of natural samples and can be used to extract properties difficult to obtain experimentally, such as the anisotropic features of pore and solid phases in a system.

Geology of McLaughlin Crater, Mars: A Unique Lacustrine Setting with Implications for Astrobiology

NASA Technical Reports Server (NTRS)

Michalski, J. R.; Niles, P. B.; Rogers, A. D.; Johnson, S. S.; Ashley, J. W.; Golombek, M. P.

2016-01-01

McLaughlin crater is a 92-kmdiameter Martian impact crater that contained an ancient carbonate- and clay mineral-bearing lake in the Late Noachian. Detailed analysis of the geology within this crater reveals a complex history with important implications for astrobiology [1]. The basin contains evidence for, among other deposits, hydrothermally altered rocks, delta deposits, deep water (>400 m) sediments, and potentially turbidites. The geology of this basin stands in stark contrast to that of some ancient basins that contain evidence for transient aqueous processes and airfall sediments (e.g. Gale Crater [2-3]).

Physical stratigraphy, paleontology, and magnetostratigraphy of the USGS-Santee Coastal Reserve core (CHN-803), Charleston County, South Carolina

USGS Publications Warehouse

Edwards, Lucy E.; Gohn, G.S.; ,; Prowell, D.C.; Bybell, L.M.; Bardot, L.P.; Firth, J.V.; Huber, B.T.; Frederiksen, N.O.; MacLeod, K.G.

1999-01-01

The Santee Coastal Reserve core, a 545-ft-deep corehole in northeastern Charleston County, South Carolina, recovered sediments of Late Cretaceous, Paleocene, Eocene, and Quaternary age. The deepest sediments, the Donoho Creek Formation (545-475.7 ft), consist of 69.3 ft of muddy calcareous sand of marine origin. This formation is placed within the upper Campanian calcareous nannofossil Subzone CC 22c. The overlying Peedee Formation (475.7-367.1 ft) in the core consists of 108.6 ft of silty clay of marine origin. It is placed in upper Maastrichtian calcareous nannofossil Subzones CC 25b, CC 26a, and CC 26b. Combined fossil and paleomagnetic information indicates nearly continuous deposition. Foraminifers indicate an outer neritic paleobathymetric setting. The Rhems Formation sensu stricto (367.1-267.3 ft) consists of 99.8 ft of silty clay, muddy sand, and minor calcite-cemented, shelly sand of marine origin. It is apparently the product of rapid sediment accumulation during a short period of time in the early Paleocene (calcareous nannofossil Zone NP 1). The upper part of the Rhems Formation sensu Bybell and others (1998) (267.3-237.4 ft) consists of 29.9 ft of calcite-cemented muddy sand and burrowed fine sand of marine origin. It is placed in calcareous nannofossil Zone NP 4 and, because it shows normal polarity, likely represents the upper part of the lower Paleocene. This unit may be correlative with the lower part of the Lower Bridge Member of the Williamsburg Formation in its type area. The Lower Bridge Member of the Williamsburg Formation (237.4-125.0 ft) has an unconformable contact at 205.0 ft that divides the member into lower muddy sand beds and upper calcareous clay beds. Both are placed in the upper Paleocene calcareous nannofossil Zone NP 5. The Chicora Member of the Williamsburg Formation (125-51.5 ft) consists of 73.5 ft of muddy, shelly sand of marine origin. It is poorly dated but includes late Paleocene nannofossils (Zones NP 5 and NP 6). A mollusk-bryozoan limestone (51.5-42.0 ft) above the Chicora Member of the Williamsburg yields early Eocene calcareous nannofossils representing both Zone NP 9/10 and Zone NP 12, together with pollen and dinocysts that are younger. Sediments of middle and late Eocene, Oligocene, Miocene, and Pliocene ages were not recovered in the Santee Coastal Reserve core. The upper 42.0 ft of sediments represent Quaternary deposits and are included in the Wando Formation (42.0-28.0 ft) and the informal Silver Bluff beds (28.0-0 ft).

Application of 2D electrical resistivity imaging and cone penetration test (CPT) to assess the harzadous effect of near surface water on foundations in Lagos Nigeria

NASA Astrophysics Data System (ADS)

Adewoyin, O. O.; Joshua, E. O.; Akinyemi, M. L.; Omeje, M.; Joel, E. S.

2017-05-01

Adequate information on the condition of the subsurface is very important for site evaluation for engineering purposes. In this study two dimensional (2D) geoelectrical resistivity survey and cone penetration tests were conducted to study the hazardous effect of excess near surface water on the foundation of building in a reclaimed land located at Victoria Island area of Lagos State. The results of the inverted 2D geoelectrical resistivity data revealed three distinct geoelectrical layers characterized by low to moderate electrical resistivity of 2.23 and 129Ωm and 9.46 to 636Ωm respectively. The topsoil is characterized by wet sandy soil, which is underlain by sandy clay and banded at the below by a geologic formation of low resistivity which is suspected to be clay. The clay material may be responsible for the excess water retention observed in the area. The CPT method on the other hand revealed a geological formation of low resistance to penetration between 2-3 kg/cm2 from the topsoil to a depth of 7 m, which may be the effect of excess water in the near surface. This study revealed that the foundation of building may not be founded directly on the soil in any reclaimed land as this may result in collapse as a result of upward migration of water to the near surface.

Geometrical appearance and spatial arrangement of structural blocks of the Malan loess in NW China: implications for the formation of loess columns

NASA Astrophysics Data System (ADS)

Li, Yanrong; Zhang, Tao; Zhang, Yongbo; Xu, Qiang

2018-06-01

Loess, as one of the main Quaternary deposits, covers approximately 6% of the land surface of the Earth. Although loess is loose and fragile, loess columns are popular and they can stand stably for hundreds of years, thereby forming a spectacular landform. The formation of such special column-shaped soil structures is puzzling, and the underlying fundamentals remain unclear. The present study focuses on quantifying and examining the geometrical shape and spatial alignment of structural blocks of the Malan loess at different locations in the Loess Plateau of China. The structural blocks under investigation include clay- and silt-sized particles, aggregates, fragments, lumps, and columns, which vary in size from microns to tens of meters. Regardless of their size, the structural blocks of the Malan loess are found to be similar in shape, i.e., elongated with a length-to-width ratio of approximately 2.6. The aggregates, fragments, lumps, columns, and macropores between aggregates exhibit strong concentration in the vertical or subvertical alignment. These phenomena imply that the Malan loess is anisotropic and it is composed of a combination of vertically aligned strong units and vertically aligned weak segments. Based on this, "vertiloess" structure is proposed to denote this combination. The vertiloess structure prevents horizontal erosion, but favors spalling, peeling, toppling, falling and cracking-sliding of vertical loess pieces, thereby forming loess columns.

Stable isotopic evidence for fluid flow and fluid/rock interaction during thrust faulting in Pumpkin Valley shale and Rome Formation, east Tennessee

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

Butler, B.K.; Haase, C.S.

1989-08-01

The Pumpkin Valley Shale and the underlying Rome Formation form the lower portions of the Copper Creek and White Oak Mountain thrust sheets in east Tennessee. The Pumpkin Valley Shale consists of shale and mudstone with subordinate amounts of interbedded siltstone. The Rome Formation is composed predominantly of sandstone with interbedded shale and siltstone toward the base of the formation. The percentage of illite increases from 20% to over 80% of the bulk clay mineralogy toward the base of the section. Porosity is occluded by quartz, phyllosilicate, and calcite cements. Both formations contain calcite-filled and, less commonly, quartz-filled Alleghenian fracturesmore » and joints.« less

How long do natural waters “remember” release incidents of Marcellus Shale waters: a first order approximation using reactive transport modeling

DOE PAGES

Cai, Zhang; Li, Li

2016-12-13

Natural gas production from the Marcellus Shale formation has significantly changed energy landscape in recent years. Accidental release, including spills, leakage, and seepage of the Marcellus Shale flow back and produced waters can impose risks on natural water resources. With many competing processes during the reactive transport of chemical species, it is not clear what processes are dominant and govern the impacts of accidental release of Marcellus Shale waters (MSW) into natural waters. Here we carry out numerical experiments to explore this largely unexploited aspect using cations from MSW as tracers with a focus on abiotic interactions between cations releasedmore » from MSW and natural water systems. Reactive transport models were set up using characteristics of natural water systems (aquifers and rivers) in Bradford County, Pennsylvania. Results show that in clay-rich sandstone aquifers, ion exchange plays a key role in determining the maximum concentration and the time scale of released cations in receiving natural waters. In contrast, mineral dissolution and precipitation play a relatively minor role. The relative time scales of recovery τ rr, a dimensionless number defined as the ratio of the time needed to return to background concentrations over the residence time of natural waters, vary between 5 and 10 for Na, Ca, and Mg, and between 10 and 20 for Sr and Ba. In rivers and sand and gravel aquifers with negligible clay, τrr values are close to 1 because cations are flushed out at approximately one residence time. These values can be used as first order estimates of time scales of released MSW in natural water systems. This work emphasizes the importance of clay content and suggests that it is more likely to detect contamination in clay-rich geological formations. As a result, this work highlights the use of reactive transport modeling in understanding natural attenuation, guiding monitoring, and predicting impacts of contamination for risk assessment.« less

How long do natural waters “remember” release incidents of Marcellus Shale waters: a first order approximation using reactive transport modeling

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

Cai, Zhang; Li, Li

Natural gas production from the Marcellus Shale formation has significantly changed energy landscape in recent years. Accidental release, including spills, leakage, and seepage of the Marcellus Shale flow back and produced waters can impose risks on natural water resources. With many competing processes during the reactive transport of chemical species, it is not clear what processes are dominant and govern the impacts of accidental release of Marcellus Shale waters (MSW) into natural waters. Here we carry out numerical experiments to explore this largely unexploited aspect using cations from MSW as tracers with a focus on abiotic interactions between cations releasedmore » from MSW and natural water systems. Reactive transport models were set up using characteristics of natural water systems (aquifers and rivers) in Bradford County, Pennsylvania. Results show that in clay-rich sandstone aquifers, ion exchange plays a key role in determining the maximum concentration and the time scale of released cations in receiving natural waters. In contrast, mineral dissolution and precipitation play a relatively minor role. The relative time scales of recovery τ rr, a dimensionless number defined as the ratio of the time needed to return to background concentrations over the residence time of natural waters, vary between 5 and 10 for Na, Ca, and Mg, and between 10 and 20 for Sr and Ba. In rivers and sand and gravel aquifers with negligible clay, τrr values are close to 1 because cations are flushed out at approximately one residence time. These values can be used as first order estimates of time scales of released MSW in natural water systems. This work emphasizes the importance of clay content and suggests that it is more likely to detect contamination in clay-rich geological formations. As a result, this work highlights the use of reactive transport modeling in understanding natural attenuation, guiding monitoring, and predicting impacts of contamination for risk assessment.« less

Successive reactivation of older structures under variable heat flow conditions evidenced by K-Ar fault gouge dating in Sierra de Ambato, northern Argentine broken foreland

NASA Astrophysics Data System (ADS)

Nóbile, Julieta C.; Collo, Gilda; Dávila, Federico M.; Martina, Federico; Wemmer, Klaus

2015-12-01

The Argentine broken foreland has been the subject of continuous research to determine the uplift and exhumation history of the region. High-elevation mountains are the result of N-S reverse faults that disrupted a W-E Miocene Andean foreland basin. In the Sierra de Ambato (northern Argentine broken foreland) the reverse faults offset Neogene sedimentary rocks (Aconquija Fm., ˜9 Ma) and affect the basement comprising Paleozoic metamorphic rocks that have been dated at ˜477-470 Ma. In order to establish a chronology of these faults affecting the previous continuous basin we date the formation age of clay minerals associated with fault gouge using the K-Ar dating technique. Clay mineral formation is a fundamental process in the evolution of faults under the brittle regime (<<300 °C). K-Ar ages (9 fractions from 3 samples collected along a transect in the Sierra de Ambato) vary from Late Devonian to Late Triassic (˜360-220 Ma). This age distribution can be explained by a long lasting brittle deformation history with a minimum age of ˜360 Ma and a last clay minerals forming event at ˜220 Ma. Moreover, given the progression of apparent ages decreasing from coarse to fine size fractions (˜360-311 Ma for 2-1 μm grain size fraction, ˜326-286 Ma for 1-0.2 μm and ˜291-219 Ma of <0.2 μm), we modeled discrete deformation events at ˜417 Ma (ending of the Famatinian cycle), ˜317-326 Ma (end of Gondwanic orogeny), and ˜194-279 Ma (Early Permian - Jurassic deformation). According to our data, the Neogene reactivation would not have affected the K-Ar system neither generated a significant clay minerals crystallization in the fault gouge, although an exhumation of more than 2 Km is recorded in this period from stratigraphic data.

The action of water films at Å-scales in the Earth: Implications for the Nankai subduction system

NASA Astrophysics Data System (ADS)

Brown, Kevin M.; Poeppe, Dean; Josh, Matthew; Sample, James; Even, Emilie; Saffer, Demian; Tobin, Harold; Hirose, Takehiro; Kulongoski, J. T.; Toczko, Sean; Maeda, Lena; IODP Expedition 348 Shipboard Party

2017-04-01

Water properties change with confinement within nanofilms trapped between natural charged clay particles. We investigated nanofilm characteristics through high-stress laboratory compression tests in combination with analyses of expelled pore fluids. We utilized sediments obtained from deep drilling of the Nankai subduction zone at Site C0002 of the Integrated Ocean Drilling Program (IODP). We show that below 1-2 km, there should be widespread ultrafiltration of migrating fluids. Experiments to > ∼ 100 MPa normal compression collapse pores below a few ion monofilm thicknesses. A reduction towards a single condensing/dehydrating ion monofilm occurs as stresses rise >100-200 MPa and clay separations are reduced to <10-20 Å. Thus, porosity in high mineral surface area systems only consists of double and single monofilms at depths below a few km leaving little room for either bulk water or the deep biosphere. The resulting semipermeable properties result in variable segregation of ions and charged isotopes and water during active flow. The ultrafiltration and ion dehydration processes are coupled in that both require the partial immobilization of ions between the charged clay surfaces. The general effect is to increase salinities in residual pore fluids at depth and freshen fluids expelled during consolidation. Cessation of nanofilm collapse to a near constant ∼17 Å below 2 km depth at Nankai supports the contention for the onset of substantial geopressuring on the deeper seismogenic fault. The properties of monofilm water, thus, have considerable implications for the deep water properties of subduction zones generating major tremor and Mw 8+ earthquakes. Indeed, the combined effects of advective flow, ultrafiltration, diffusion, and diagenesis could provide a unifying explanation for the origins of overpressuring and pore water geochemical signals observed in many natural systems.

Organic Control of Dioctahedral and Trioctahedral Clay Formation in an Alkaline Soil System in the Pantanal Wetland of Nhecolândia, Brazil.

PubMed

Barbiero, Laurent; Berger, Gilles; Rezende Filho, Ary T; Meunier, Jean-François; Martins-Silva, Elisângela R; Furian, Sonia

2016-01-01

Recent studies have focused on the formation of authigenic clays in an alkaline soil system surrounding lakes of the Nhecolândia region, Pantanal wetland. The presence of trioctahedral Mg-smectites (stevensite and saponite types), which requires low Al and Fe contents in the soil solution for its formation, contrasts with the neoformation of dioctahedral Fe-mica (glauconite, and Fe-illite), which instead requires solutions relatively enriched in Al and Fe. This study aims to understand the conditions of co-existence of both, Mg-smectite and Fe-mica a common clay association in former or modern alkaline soil systems and sediments. The study was carried out along an alkaline soil catena representative of the region. The soil organization revealed that Mg-smectite occur in top soil close to the lake, whereas Fe-mica dominate in the clay fraction of deeper greenish horizons a few meters apart. We propose here that this spatial distribution is controlled by the lateral transfer of Fe and Al with organic ligands. Alkaline organic rich solutions (DOC up to 738 mg L-1) collected in the watertable were centrifuged and filtered through membranes of decreasing pore size (0.45 μm, 0.2 μm, 30 KDa, 10 KDa, 3 KDa) to separate colloidal and dissolved fractions. Fe, Al, Si, Mg and K were analysed for each fraction. Although the filtration had no influence on Si and K contents, almost 90% of Fe (up to 2.3 mg L-1) and Al (up to 7 mg L-1) are retained at the first cutoff threshold of 0.45μm. The treatment of the same solutions by oxygen peroxide before filtration shows that a large proportion of Fe and Al were bonded to organic colloids in alkaline soil solution at the immediate lake border, allowing Mg-smectite precipitation. The fast mineralization of the organic matter a few meters apart from the lake favors the release of Fe and Al necessary for Fe-mica neoformation. In comparison with chemical and mineralogical characteristics of alkaline environments described in the literature, the study suggests that the co-existence of trioctahedral Mg-smectite and dioctahedral Fe-mica should be regarded as a standard occurrence in alkaline soil systems with organic rich waters.

Roles of Nano- and Micro-Scale Subsurface Geochemical Reactions on Environmentally Sustainable Geologic Carbon Dioxide Sequestration

NASA Astrophysics Data System (ADS)

Hu, Yandi

Geologic CO2 sequestration (GCS) is a promising approach to reduce anthropogenic CO2 emissions into the atmosphere. At GCS sites, injected CO2 is kept in formation rock by an overlying low permeability caprock. During and after CO2 injection, geochemical reactions can affect the porosity, permeability, and pollutant transport in aquifers. Despite their importance, nano- and micro-scale subsurface geochemical reactions are far from well-understood. Clay mobilization has been reported to decrease aquifer permeability during water flooding, and clay minerals are abundant in caprock. Thus, we studied CO2-brine-clay interactions under varied conditions relevant to different GCS sites (at 35-95°C and under 35-120 atm CO2, in water, NaCl, MgCl2, or CaCl2 solutions). Biotite, Fe-bearing mica, was used as a model clay mineral. We observed numerous fibrous illite precipitates on mica after reaction for only 3 h, which had not been previously reported. A few hours later, the mica surface cracked and fibrous illite detached. The mobilization of fibrous illite can decrease the aquifer's permeability greatly and affect the safety and efficiency of GCS. Mechanisms related to ion exchange, mica swelling, and CO2 intercalation were explored. Oriented aggregation of illite nanoparticles forming the fibrous illite was directly observed, suggesting a new mechanism for fibrous illite formation. Interestingly, besides the pH effect, aqueous CO2 enhances mica cracking over N2. These findings can help to achieve safer subsurface operations. At GCS field sites, Fe concentration increased near the injection sites and originally adsorbed pollutants were released. As the brine flows, Fe re-precipitated because of pH increase. To better predict the fate and transport of aqueous pollutants, the nucleation and growth of Fe(III) (hydr)oxides were studied. New information about sizes and volumes of the Fe(III) (hydr)oxide nanoparticles precipitated in solution and on quartz, mica, and sapphire were provided using small angle X-ray scattering, in the presence of different ions (Al 3+, Cl-, NO3-, and SO 42-). Using complementary techniques, the controlling mechanisms related to surface charge, bond formation, and interfacial energies were explored. These new findings can help better predict pollutant transport in aquifers not only at GCS sites, but also in managed aquifer recharge and acid mine drainage sites.

Organic Control of Dioctahedral and Trioctahedral Clay Formation in an Alkaline Soil System in the Pantanal Wetland of Nhecolândia, Brazil

PubMed Central

Meunier, Jean-François; Martins-Silva, Elisângela R.; Furian, Sonia

2016-01-01

Recent studies have focused on the formation of authigenic clays in an alkaline soil system surrounding lakes of the Nhecolândia region, Pantanal wetland. The presence of trioctahedral Mg-smectites (stevensite and saponite types), which requires low Al and Fe contents in the soil solution for its formation, contrasts with the neoformation of dioctahedral Fe-mica (glauconite, and Fe-illite), which instead requires solutions relatively enriched in Al and Fe. This study aims to understand the conditions of co-existence of both, Mg-smectite and Fe-mica a common clay association in former or modern alkaline soil systems and sediments. The study was carried out along an alkaline soil catena representative of the region. The soil organization revealed that Mg-smectite occur in top soil close to the lake, whereas Fe-mica dominate in the clay fraction of deeper greenish horizons a few meters apart. We propose here that this spatial distribution is controlled by the lateral transfer of Fe and Al with organic ligands. Alkaline organic rich solutions (DOC up to 738 mg L-1) collected in the watertable were centrifuged and filtered through membranes of decreasing pore size (0.45 μm, 0.2 μm, 30 KDa, 10 KDa, 3 KDa) to separate colloidal and dissolved fractions. Fe, Al, Si, Mg and K were analysed for each fraction. Although the filtration had no influence on Si and K contents, almost 90% of Fe (up to 2.3 mg L-1) and Al (up to 7 mg L-1) are retained at the first cutoff threshold of 0.45μm. The treatment of the same solutions by oxygen peroxide before filtration shows that a large proportion of Fe and Al were bonded to organic colloids in alkaline soil solution at the immediate lake border, allowing Mg-smectite precipitation. The fast mineralization of the organic matter a few meters apart from the lake favors the release of Fe and Al necessary for Fe-mica neoformation. In comparison with chemical and mineralogical characteristics of alkaline environments described in the literature, the study suggests that the co-existence of trioctahedral Mg-smectite and dioctahedral Fe-mica should be regarded as a standard occurrence in alkaline soil systems with organic rich waters. PMID:27463379