Adsorption of poly(ethylene oxide) on smectite: Effect of layer charge.

PubMed

Su, Chia-Chi; Shen, Yun-Hwei

2009-04-01

The adsorption of polymers on clay is important in many applications. However the mechanisms of poly(ethylene oxide) (PEO) adsorption on smectite is not well elucidated at present. The aim of this study was to investigate the effect of layer charge density on the adsorption of PEO by smectite. The results indicated that both the hydrophobic interaction (between CH(2)CH(2) groups and siloxane surface) and the hydrogen bonding (between ether oxygen of PEO and structure OH of smectite) lead to PEO preferential adsorption on the surface of low-charge smectite. In addition, the delamination of low-charge smectite in water is enhanced upon PEO adsorption presumably due to the hydrophilic ether oxygen of adsorbed PEO.

Meta-analysis: Smectite in the treatment of acute infectious diarrhoea in children.

PubMed

Szajewska, H; Dziechciarz, P; Mrukowicz, J

2006-01-15

Although not currently recommended, dioctahedral smectite (smectite) is commonly used to treat acute infectious diarrhoea in many countries. To evaluate systematically the effectiveness of smectite in treating acute infectious diarrhoea in children. Using medical subject headings and free-language terms, the following electronic databases were searched for studies relevant to acute infectious diarrhoea and smectite: MEDLINE, EMBASE, CINAHL and The Cochrane Library; additional references were obtained from reviewed articles. Only randomized-controlled trials were included. Nine randomized-controlled trials (1238 participants) met the inclusion criteria. Combined data from six randomized-controlled trials showed that smectite significantly reduced the duration of diarrhoea compared with placebo. The pooled weighted mean difference was (-22.7 h, 95% CI: -24.8 to -20.6) with a fixed model and remained significant in a random effect model (-24.4 h, 95% CI: -29.8 to -19.1). The chance of cure on intervention day 3 was significantly increased in the smectite vs. the control group (RR 1.64, 95% CI: 1.36-1.98; number needed to treat 4, 95% CI: 3-5). Adverse effects were similar in both groups. Smectite may be a useful adjunct to rehydration therapy in treating acute paediatric gastroenteritis. However, the results of this meta-analysis should be interpreted with caution as most of the included studies had important limitations. Cost-effectiveness analyses should be undertaken before routine pharmacological therapy with smectite is recommended.

Formation of a bioconjugate composed of hemin, smectite, and quaternary ammonium chloride that is soluble and active in hydrophobic media.

PubMed

Kurosawa, Masaru; Itoh, Tetsuji; Kodera, Yoh; Matsushima, Ayako; Hiroto, Misao; Nishimura, Hiroyuki; Inada, Yuji

2002-01-01

Hemin (Fe(3+)) was adsorbed onto synthetic smectite (clay mineral) intercalated with a quaternary alkenylammonium compound, dioleyldimethylammonium chloride (DOA), to form a hemin-smectite-DOA conjugate. The hemin-smectite-DOA conjugate was soluble in organic solvents such as benzene and toluene to form a transparent colloidal solution with a light yellow color. Its absorption spectrum in benzene showed two bands, 600 and 568 nm, in the visible region and a sharp Soret band at 400 nm with the molar extinction coefficient of 7.5 x 10(4) M(-1) cm(-1). The formation of the conjugate of smectite and DOA was confirmed by X-ray diffraction analysis: the basal spacing, d(001), of hemin-smectite-DOA conjugate was 19 A which is an expansion of the interlayer space by 5 A based upon the basal spacing of smectite of 14 A. Hemin-smectite-DOA conjugate catalyzed the peroxidase-like reaction in organic solvents using benzoyl peroxide as the hydrogen acceptor and leucocrystal violet as the hydrogen donor. The temperature-dependent peroxidase-like activity of the conjugate was compared with peroxidase activity of horseradish peroxidase. The hemin-smectite-DOA conjugate exhibited higher activity as the temperature was increased from 30 to 70 degrees C, while horseradish peroxidase activity was reduced as the temperature was increased.

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.

Geochemical modulation of bioavailability and toxicity of nitroaromatic compounds to aquatic plants.

PubMed

Roberts, Michael G; Rugh, Clayton L; Li, Hui; Teppen, Brian J; Boyd, Stephen A

2007-03-01

Nitroaromatic compounds (NACs) are prominent soil and sediment contaminants that are strongly adsorbed by smectites at extents that depend on hydration properties of the exchangeable cation. Potassium smectites adsorb nitroaromatics much more strongly than calcium smectites, so that adjustment of K+ versus Ca2+ occupation on cation exchange sites in smectites can be used to modulate the retention and release of nitroaromatics. We suggest that this modulation can be used to advantageously manage the bioavailability and toxicity of NACs during bioremedation. We have measured the toxicity of 2,4-dinitrotoluene (2,4-DNT) to duckweed grown in smectite suspensions and utilized Ca2+/K+ exchange to retain or release 2,4-DNT. Retention by potassium smectite reduced bioavailability and hence toxicity to duckweed. Addition of Ca2+ to replace K+ by ion exchange released adsorbed 2,4-DNT, which is toxic to duckweed. So smectites can be used to sequester or release 2,4-DNT predictably and provide means to control bioavailability and environmental toxicity.

[HEALTH-IMPROVING REMEDIES ON THE BASIS OF SMECTITE®].

PubMed

Shirobokov, V; Yankovskii, D; Dyment, G

2015-01-01

The review is devoted to the issues of using smectites in medicine. Modern information concerning smectite composition, structure, physico-chemical properties and reasonability of using them with health-improving purposes is presented. Special attention is given to smectite sorbtional and ionic properties and their unique mineral composition. Characterization is given to modern preparation based on smectites, including developed in Ukraine dietary additives of the series Smectovit®.

Smectite formation in the presence of sulfuric acid: Implications for acidic smectite formation on early Mars

NASA Astrophysics Data System (ADS)

Peretyazhko, T. S.; Niles, P. B.; Sutter, B.; Morris, R. V.; Agresti, D. G.; Le, L.; Ming, D. W.

2018-01-01

The excess of orbital detection of smectite deposits compared to carbonate deposits on the martian surface presents an enigma because smectite and carbonate formations are both favored alteration products of basalt under neutral to alkaline conditions. We propose that Mars experienced acidic events caused by sulfuric acid (H2SO4) that permitted phyllosilicate, but inhibited carbonate, formation. To experimentally verify this hypothesis, we report the first synthesis of smectite from Mars-analogue glass-rich basalt simulant (66 wt% glass, 32 wt% olivine, 2 wt% chromite) in the presence of H2SO4 under hydrothermal conditions (∼200 °C). Smectites were analyzed by X-ray diffraction, Mössbauer spectroscopy, visible and near-infrared reflectance spectroscopy and electron microprobe to characterize mineralogy and chemical composition. Solution chemistry was determined by Inductively Coupled Plasma Mass Spectrometry. Basalt simulant suspensions in 11-42 mM H2SO4 were acidic with pH ≤ 2 at the beginning of incubation and varied from acidic (pH 1.8) to mildly alkaline (pH 8.4) at the end of incubation. Alteration of glass phase during reaction of the basalt simulant with H2SO4 led to formation of the dioctahedral smectite at final pH ∼3 and trioctahedral smectite saponite at final pH ∼4 and higher. Anhydrite and hematite formed in the final pH range from 1.8 to 8.4 while natroalunite was detected at pH 1.8. Hematite was precipitated as a result of oxidative dissolution of olivine present in Adirondack basalt simulant. Formation of secondary phases, including smectite, resulted in release of variable amounts of Si, Mg, Na and Ca while solubilization of Al and Fe was low. Comparison of mineralogical and solution chemistry data indicated that the type of smectite (i.e., dioctahedral vs trioctahedral) was likely controlled by Mg leaching from altering basalt and substantial Mg loss created favorable conditions for formation of dioctahedral smectite. We present a model for global-scale smectite formation on Mars via acid-sulfate conditions created by the volcanic outgassing of SO2 in the Noachian and early Hesperian.

Influence of layer charge and charge distribution of smectites on the flow behaviour and swelling of bentonites

USGS Publications Warehouse

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

2006-01-01

The influence of layer charge and charge distribution of dioctahedral smectites on the rheological and swelling properties of bentonites is examined. Layer charge and charge distribution were determined by XRD using the LayerCharge program [Christidis, G.E., Eberl, D.D., 2003. Determination of layer charge characteristics of smectites. Clays Clay Miner. 51, 644-655.]. The rheological properties were determined, after sodium exchange using the optimum amount of Na2CO3, from free swelling tests. Rheological properties were determined using 6.42% suspensions according to industrial practice. In smectites with layer charges of - 0.425 to - 0.470 per half formula unit (phfu), layer charge is inversely correlated with free swelling, viscosity, gel strength, yield strength and thixotropic behaviour. In these smectites, the rheological properties are directly associated with the proportion of low charge layers. By contrast, in low charge and high charge smectites there is no systematic relation between layer charge or the proportion of low charge layers and rheological properties. However, low charge smectites yield more viscous suspensions and swell more than high charge smectites. The rheological properties of bentonites also are affected by the proportion of tetrahedral charge (i.e. beidellitic charge), by the existence of fine-grained minerals having clay size, such as opal-CT and to a lesser degree by the ionic strength and the pH of the suspension. A new method for classification of smectites according to the layer charge based on the XRD characteristics of smecites is proposed, that also is consistent with variations in rheological properties. In this classification scheme the term smectites with intermediate layer charge is proposed. ?? 2006 Elsevier B.V. All rights reserved.

Characterization of a hybrid-smectite nanomaterial formed by immobilizing of N-pyridin-2-ylmethylsuccinamic acid onto (3-aminopropyl)triethoxysilane modified smectite and its potentiometric sensor application

NASA Astrophysics Data System (ADS)

Topcu, Cihan; Caglar, Sema; Caglar, Bulent; Coldur, Fatih; Cubuk, Osman; Sarp, Gokhan; Gedik, Kubra; Bozkurt Cirak, Burcu; Tabak, Ahmet

2016-09-01

A novel N-pyridin-2-ylmethylsuccinamic acid-functionalized smectite nanomaterial was synthesized by immobilizing of N-pyridin-2-ylmethylsuccinamic acid through chemical bonding onto (3-aminopropyl)triethoxysilane modified smectite. The structural, thermal, morphological and surface properties of raw, silane-grafted and the N-pyridin-2-ylmethylsuccinamic acid-functionalized smectites were investigated by various characterization techniques. The thermal analysis data showed the presence of peaks in the temperature range from 200 °C to 600 °C due to the presence of physically adsorbed silanes, intercalated silanes, surface grafted silanes and chemically grafted silane molecules between the smectite layers. The powder x-ray diffraction patterns clearly indicated that the aminopropyl molecules also intercalated into the smectite interlayers as bilayer arrangement whereas N-pyridin-2-ylmethylsuccinamic acid molecules were only attached to 3-aminopropyltriethoxysilane molecules on the external surface and edges of clay and they did not intercalate. Fourier transform infrared spectroscopy confirms N-pyridin-2-ylmethylsuccinamic acid molecules bonding through the amide bond between the amine group of aminopropyltriethoxysilane molecules and a carboxylic acid functional group of N-pyridin-2-ylmethylsuccinamic acid molecules. The guest molecules functionalized onto the smectite caused significant alterations in the textural and morphological parameters of the raw smectite. The anchoring of N-pyridin-2-ylmethylsuccinamic acid molecules led to positive electrophoretic mobility values when compared to starting materials. N-pyridin-2-ylmethylsuccinamic acid-functionalized smectite was employed as an electroactive ingredient in the structure of potentiometric PVC-membrane sensor. The sensor exhibited more selective potentiometric response towards chlorate ions compared to the other common anionic species.

Fe/Mg smectite formation under acidic conditions on early Mars

NASA Astrophysics Data System (ADS)

Peretyazhko, T. S.; Sutter, B.; Morris, R. V.; Agresti, D. G.; Le, L.; Ming, D. W.

2016-01-01

Phyllosilicates of the smectite group detected in Noachian and early Hesperian terrains on Mars have been hypothesized to form under neutral to alkaline conditions. These pH conditions would also be favorable for formation of widespread carbonate deposits which have not been detected on Mars. We propose that smectite deposits on Mars formed under moderately acidic conditions inhibiting carbonate formation. We report here the first synthesis of Fe/Mg smectite in an acidic hydrothermal system [200 °C, pHRT ∼ 4 (pH measured at room temperature) buffered with acetic acid] from Mars-analogue, glass-rich, basalt simulant with and without aqueous Mg or Fe(II) addition under N2-purged anoxic and ambient oxic redox conditions. Synthesized Fe/Mg smectite was examined by X-ray-diffraction, Mössbauer spectroscopy, visible and near-infrared reflectance spectroscopy, scanning electron microscopy and electron microprobe to characterize mineralogy, morphology and chemical composition. Alteration of the glass phase of basalt simulant resulted in formation of the Fe/Mg smectite mineral saponite with some mineralogical and chemical properties similar to the properties reported for Fe/Mg smectite on Mars. Our experiments are evidence that neutral to alkaline conditions on early Mars are not necessary for Fe/Mg smectite formation as previously inferred. Phyllosilicate minerals could instead have formed under mildly acidic pH conditions. Volcanic SO2 emanation and sulfuric acid formation is proposed as the major source of acidity for the alteration of basaltic materials and subsequent formation of Fe/Mg smectite.

Geochemical Identification in Sediment Provenance during Glacial/Interglacial Period: the Southern Drake Passage

NASA Astrophysics Data System (ADS)

Park, Y. K.; Jung, J.; Lee, J. I.; Yoo, K. C.; Kim, J. W.

2016-12-01

Clay mineralogy and crystal size distribution in marine sediment is used for the indication of a sediment provenance and climatic changes. Objective of this study is to trace the sediment provenances in the Southern Drake Passage with clay mineralogy, elemental composition and crystal size distributions (CSDs) of clay mineral. In the present study, X-Ray Diffractometer (XRD) measurements showed that smectite, illite and chlorite are dominant phases. The semi-quantitative analysis showed that the relatively proportion of smectite is 50 - 60% in interglacial stage, 30 - 39% in glacial stage. Comparing with REE data, sediments supply was influenced by Weddell sea current and Antarctic Circumpolar Current (ACC). Moreover, elemental composition and microscopic analysis of smectites were carried by Transmission Electron Microscopy (TEM) and energy dispersive spectroscopy (EDS). The composition of smectite clay minerals were plotted on the tertiary diagram indicating that Smectite in Drake Passage was transported from three provenances: South Shetland island, east and west side of Antarctic peninsula during glacial - interglacial period. The CSDs of smectite also indicate the various source of smectite. The variation in the values of α (mean thickness) and β2 (shape or uniformity of the distribution) of smectite grain size will be discussed in terms of the sediment provenance.

Smectite flocculation structure modified by Al13 macro-molecules--as revealed by the transmission X-ray microscopy (TXM).

PubMed

Zbik, Marek S; Martens, Wayde N; Frost, Ray L; Song, Yen-Fang; Chen, Yi-Ming; Chen, Jian-Hua

2010-05-01

The aggregate structure which occurs in aqueous smectitic suspensions is responsible for poor water clarification, difficulties in sludge dewatering and the unusual rheological behaviour of smectite rich soils. These macroscopic properties are dictated by the 3D structural arrangement of smectite finest fraction within flocculated aggregates. Here, we report results from a relatively new technique, transmission X-ray microscopy (TXM), which makes it possible to investigate the internal structure and 3D tomographic reconstruction of the smectite clay aggregates modified by Al(13) Keggin macro-molecule [Al(13)(O)(4)(OH)(24)(H(2)O)(12)](7+). Three different treatment methods were shown resulted in three different micro-structural environments of the resulting flocculation. In case of smectite sample prepared in Methods 1 and 3 particles fall into the primary minimum where Van der Waals forces act between FF oriented smectite flakes and aggregates become approach irreversible flocculation. In case of sample prepared using Method 2, particles contacting by edges (EE) and edge to face (EF) orientation fell into secondary minimum and weak flocculation resulted in severe gelation and formation of the micelle-like texture in fringe superstructure, which was first time observed in smectite based gel. Copyright 2010 Elsevier Inc. All rights reserved.

Adsorption, aggregation, and desorption of proteins on smectite particles.

PubMed

Kolman, Krzysztof; Makowski, Marcin M; Golriz, Ali A; Kappl, Michael; Pigłowski, Jacek; Butt, Hans-Jürgen; Kiersnowski, Adam

2014-10-07

We report on adsorption of lysozyme (LYS), ovalbumin (OVA), or ovotransferrin (OVT) on particles of a synthetic smectite (synthetic layered aluminosilicate). In our approach we used atomic force microscopy (AFM) and quartz crystal microbalance (QCM) to study the protein-smectite systems in water solutions at pH ranging from 4 to 9. The AFM provided insights into the adhesion forces of protein molecules to the smectite particles, while the QCM measurements yielded information about the amounts of the adsorbed proteins, changes in their structure, and conditions of desorption. The binding of the proteins to the smectite surface was driven mainly by electrostatic interactions, and hence properties of the adsorbed layers were controlled by pH. At high pH values a change in orientation of the adsorbed LYS molecules and a collapse or desorption of OVA layer were observed. Lowering pH to the value ≤ 4 caused LYS to desorb and swelling the adsorbed OVA. The stability of OVT-smectite complexes was found the lowest. OVT revealed a tendency to desorb from the smectite surface at all investigated pH. The minimum desorption rate was observed at pH close to the isoelectric point of the protein, which suggests that nonspecific interactions between OVT and smectite particles significantly contribute to the stability of these complexes.

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

NASA Technical Reports Server (NTRS)

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

2014-01-01

Phyllosilicates of the smectite group including Mg- and Fe-saponite and Fe(III)-rich nontronite have been identified on Mars. Smectites are believed to be formed under neutral to alkaline conditions that prevailed on early Mars. This hypothesis is supported by the observation of smectite and carbonate deposits in Noachian terrain on Mars. However, smectite may have formed under mildly acidic conditions. Abundant smectite formations have been detected as layered deposits hundreds of meters thick in intracrater depositional fans and plains sediments, while no large deposits of carbonates are found. Development of mildly acidic conditions at early Mars might allow formation of smectite but inhibit widespread carbonate precipitation. Little is known regarding the mechanisms of smectite formation from basaltic glass under acidic conditions. The objective of this study was to test a hypothesis that Mars-analogue basaltic glass alters to smectite minerals under acidic conditions (pH 4). The effects of Mg and Fe concentrations and temperature on smectite formation from basaltic glass were evaluated. Phyllosilicate synthesis was performed in batch reactors (Parr acid digestion vessel) under reducing hydrothermal conditions at 200 C and 100 C. Synthetic basaltic glass with a composition similar to that of the Gusev crater rock Adirondack (Ground surface APXS measurement) was used in these experiments. Basaltic glass was prepared by melting and quenching procedures. X-ray diffraction (XRD) analysis indicated that the synthesized glass was composed of olivine, magnetite and X-ray amorphous phase. Samples were prepared by mixing 250 mg Adirondack with 0.1 M acetic acid (final pH 4). In order to study influence of Mg concentration on smectite formation, experiments were performed with addition of 0, 1 and 10 mM MgCl2. After 1, 7 and 14 day incubations the solution composition was analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and the altered glass and formed phyllosilicates were examined by XRD analysis. Mineralogical changes were significant in Adirondack incubated with 10 mM MgCl2 at pH 4 and heated at 200 C. X-ray diffraction analysis revealed formation of phyllosilicate during 14 day incubation (Figure 1). Smectite was confirmed as the phyllosilicate after treatments with glycerol and KCl and heating to 550 C. The position of 02l (4.60 A) and 060 (1.54 A) diffraction bands were indicative of trioctahedral smectite such as saponite. Analysis of solution composition demonstrated that aqueous concentration of Mg decreased from 10 mM to approx.4 mM after 7 day incubation likely due to saponite formation. Smectite also formed in Adirondack incubated with 0 mM MgCl2 at pH 4 and heated at 200 C. However, diffraction peak positions of 02l (4.52 A) and 060 (1.51 A) suggested formation of dioctahedral nontronite. The 100degC Mg and Fe(II) treated basaltic glass experiments are ongoing and results will be presented.

Microbial reduction of structural Fe3+ in nontronite by a thermophilic bacterium and its role in promoting the smectite to illite reaction

USGS Publications Warehouse

Zhang, G.; Dong, H.; Kim, J.; Eberl, D.D.

2007-01-01

The illitization process of Fe-rich smectite (nontronite NAu-2) promoted by microbial reduction of structural Fe3+ was investigated by using a thermophilic metal-reducing bacterium, Thermoanaerobacter ethanolicus, isolated from the deep subsurface. T. ethanolicus was incubated with lactate as the sole electron donor and structural Fe3+ in nontronite as the sole electron acceptor, and anthraquinone-2, 6-disulfonate (AQDS) as an electron shuttle in a growth medium (pH 6.2 and 9.2, 65 ??C) with or without an external supply of Al and K sources. With an external supply of Al and K, the extent of reduction of Fe3+ in NAu-2 was 43.7 and 40.4% at pH 6.2 and 9.2, respectively. X-ray diffraction and scanning and transmission electron microscopy revealed formation of discrete illite at pH 9.2 with external Al and K sources, while mixed layers of illite/smectite or highly charged smectite were detected under other conditions. The morphology of biogenic illite evolved from lath and flake to pseudo-hexagonal shape. An external supply of Al and K under alkaline conditions enhances the smectite-illite reaction during microbial Fe3+ reduction of smectite. Biogenic SiO2 was observed as a result of bioreduction under all conditions. The microbially promoted smectite-illite reaction proceeds via dissolution of smectite and precipitation of illite. Thermophilic iron reducing bacteria have a significant role in promoting the smectite to illite reaction under conditions common in sedimentary basins.

The Formation of Fe/Mg Smectite Under Mildly Acidic Conditions on Early Mars

NASA Technical Reports Server (NTRS)

Sutter, B.; Golden, D. C.; Ming, Douglas W.; Niles, P. B.

2011-01-01

The detection of Fe/Mg smectites and carbonate in Noachian and early Hesperian terrain of Mars suggests that neutral to mildly alkaline conditions prevailed during the early history of Mars. If early Mars surface geochemical conditions were neutral to moderately alkaline with a denser CO2 atmosphere than today, then large carbonates deposits should be more widely detected in Noachian terrain. Why have so few carbonate deposits been detected compared to Fe/Mg smectites? Fe/Mg smectites on early Mars formed under mildly acidic conditions, which would preclude the extensive formation of carbonate deposits. The goal of the proposed work is to evaluate the formation of Fe/Mg smectites under mildly acidic conditions.

Analysis of Long Wave Infrared (LWIR) Soil Data to Predict Reflectance Response

DTIC Science & Technology

2009-08-01

Aridisol red-orange sandy soil 6% x 16% 61 12% smectite Aridisol grey calcareous silty soil x 19% 49 22% smectite ...trace 16% 59 20% smectite ; grain size analysis of fraction finer than 2 mm indicates 35% finer than 20 micrometer (12% finer than 5 micrometer...Entisol red-orange sandy loam/alluvium see comment 8% x 10% 72 7% smectite ; 47% finer than 20 μm (22% finer than 5 μm) Entisol sandy

Rapid and extensive debromination of decabromodiphenyl ether by smectite clay-templated subnanoscale zero-valent iron.

PubMed

Yu, Kai; Gu, Cheng; Boyd, Stephen A; Liu, Cun; Sun, Cheng; Teppen, Brian J; Li, Hui

2012-08-21

Subnanoscale zerovalent iron (ZVI) synthesized using smectite clay as a template was utilized to investigate reduction of decabromodiphenyl ether (DBDE). The results revealed that DBDE was rapidly debrominated by the prepared smectite-templated ZVI with a reaction rate 10 times greater than that by conventionally prepared nanoscale ZVI. This enhanced reduction is plausibly attributed to the smaller-sized smectite-templated ZVI clusters (∼0.5 nm) vs that of the conventional nanoscale ZVI (∼40 nm). The degradation of DBDE occurred in a stepwise debromination manner. Pentabromodiphenyl ethers were the terminal products in an alkaline suspension (pH 9.6) of smectite-templated ZVI, whereas di-, tri-, and tetrabromodiphenyl ethers formed at the neutral pH. The presence of tetrahydrofuran (THF) as a cosolvent at large volume fractions (e.g., >70%) in water reduced the debromination rates due to enhanced aggregation of clay particles and/or diminished adsorption of DBDE to smectite surfaces. Modification of clay surfaces with tetramethylammonium (TMA) attenuated the colsovent effect on the aggregation of clay particles, resulting in enhanced debromination rates. Smectite clay provides an ideal template to form subnanoscale ZVI, which demonstrated superior debromination reactivity with DBDE compared with other known forms of ZVIs. The ability to modify the nature of smectite clay surface by cation exchange reaction utilizing organic cations can be harnessed to create surface properties compatible with various contaminated sites.

Dynamic weakening of smectite-rich faults at intermediate to high velocities

NASA Astrophysics Data System (ADS)

Oohashi, K.; Hirose, T.; Takahashi, M.

2013-12-01

Smectite, one of the hydrous clay mineral, is ubiquitous in incoming sediments to subduction zones and is thought to weaken and stabilize subduction thrust faults. However, frictional properties of smectite alone cannot explain the nucleation and propagation of earthquake slip at the shallow plate boundary thrust which potentially causes the devastating tsunamis. Here, we investigate for the first time the effect of smectite fraction in smectite-quartz mixtures on friction at 30 μm/s to 1.3 m/s, to shed a light on the frictional response for the intermediate to high slip rates where the conventional friction experiments have not been explored. In the low slip rate of 30 μm/s, the steady-state coefficient of friction decreases non-linearly increasing smectite fraction: it drops rapidly at moderate fraction of 30-50 vol%. On the other hand, at the faster slip rates of ≥ 150 μm/s the friction lowers from 10-20 vol% fraction since drastic slip weakening appears for the mixtures of ~20 vol % smectite. Hence the fault suddenly loses the strength by adding only 20 % of smectite. The weakening seems to be associated with an excess pore pressure invoked by shear compaction and thermal pressurization during the experiments. This property weakens the fault strength and accelerates the fault slip, even if clay content is small (c.a. 15-35 %), leading to the large stress drop. In contrast, the faults rich in smectite (≥ 50 %) may cause small stress drop during the faulting owing to low friction coefficient of smectite at any slip rates. The results highlight that smectite content significantly affects frictional properties of faults and may generates the diversity in the subduction zone earthquakes. ACKNOLEDGEMENTS We thank Kyuichi Kanagawa, Masaya Suzuki, Osamu Tadai, and Hiroko Kitajima for constructive discussions and technical help. This work was supported by a JSPS Grant-in-Aid for JSPS fellows (25-04960) to KO, a JSPS Grant-in-Aid for Young Scientists (B) (20740264) to TH, and MEXT KANAME grant #21107004.

Influence of smectite hydration and swelling on atrazine sorption behavior.

PubMed

Chappell, Mark A; Laird, David A; Thompson, Michael L; Li, Hui; Teppen, Brian J; Aggarwal, Vaneet; Johnston, Cliff T; Boyd, Stephen A

2005-05-01

Smectites, clay minerals commonly found in soils and sediments, vary widely in their ability to adsorb organic chemicals. Recent research has demonstrated the importance of surface charge density and properties of exchangeable cations in controlling the affinity of smectites for organic molecules. In this study, we induced hysteresis in the crystalline swelling of smectites to test the hypothesis that the extent of crystalline swelling (or interlayer hydration status) has a large influence on the ability of smectites to adsorb atrazine from aqueous systems. Air-dried K-saturated Panther Creek (PC) smectite swelled less (d(001) = 1.38 nm) than never-dried K-PC (d(001) = 1.7 nm) when rehydrated in 20 mM KCl. Correspondingly, the air-dried-rehydrated K-PC had an order of magnitude greater affinity for atrazine relative to the never-dried K-PC. Both air-dried-rehydrated and never-dried Ca-PC expanded to approximately 2.0 nm in 10 mM CaCl2 and both samples had similar affinities for atrazine that were slightly lower than that of never-dried K-PC. The importance of interlayer hydration status in controlling sorption affinity was confirmed by molecular modeling, which revealed much greater interaction between interlayer water molecules and atrazine in a three-layer hydrate relative to a one-layer hydrate. The entropy change on moving atrazine from a fully hydrated state in the bulk solution to a partially hydrated state in the smectite interlayers is believed to be a major factor influencing sorption affinity. In an application test, choice of background solution (20 mM KCl versus 10 mM CaCl2) and air-drying treatments significantly affected atrazine sorption affinities for three-smectitic soils; however, the trends were not consistent with those observed for the reference smectite. Further, extending the initial rehydration time from 24 to 240 h (prior to adding atrazine) significantly decreased the soil's sorption affinity for atrazine. We conclude that interlayer hydration status has a large influence on the affinity of smectites for atrazine and that air-drying treatments have the potential to modify the sorption affinity of smectitic soils for organic molecules such as atrazine.

H2O Adsorption Kinetics on Smectites

NASA Technical Reports Server (NTRS)

Zent, Aaron P.; Quinn, Richard C.; Howard, Jeanie; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

The adsorptive equilibration of H2O a with montomorillonite, a smectite clay has been measured. At low temperatures and pressures, equilibration can require many hours, effectively preventing smectites at the martian surface from responding rapidly to diurnal pressure and temperature variations.

A new illite geothermometer

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

Ballantyne, Judith M.; Moore, Joseph N.

1988-01-01

Sericite, either as illite or illite/smectite, is ubiquitous in geothermal systems. Theoretical Ca- and Na-smectite contents of non-expanding geothermal sericites have been calculated from published electron microprobe analyses. Geothermal sericites can be modeled as solid solutions of muscovite and smectite. For those sericites that fit the model, the amount of smectite in solid solution is related to temperature by the expression TºC = 1000/(0.45LogX{sub smectite} + 2.38) – 273. The temperature dependence of illite interlayer chemistry suggests a related temperature dependence of the K, Na and Ca content of geothermal fluids. The original data used by Fournier and Truesdell (1973)more » to derive the empirical Na-K-Ca geothermometer for geothermal fluids can be modeled equally well by an equation incorporating the equilibrium constant for the reaction of smectite to illite: T ºC = 1.145*10{sup 3}/([0.35LogNa + 0.175LogCa – 0.75LogK] + 1.51) – 273, where the concentration units are molalities. This supports the hypothesis that illite and illite/smectite are important controls on the concentrations of Na, K and Ca in geothermal fluids.« less

Formation and Restacking of Disordered Smectite Osmotic Hydrates

DOE PAGES

Gilbert, Benjamin; Comolli, Luis R.; Tinnacher, Ruth M.; ...

2015-12-01

Clay swelling, an important phenomenon in natural systems, can dramatically affect the properties of soils and sediments. Something of particular interest in low-salinity, saturated systems are osmotic hydrates, forms of smectite in which the layer separation greatly exceeds the thickness of a single smectite layer due to the intercalation of water. In situ X-ray diffraction (XRD) studies have shown a strong link between ionic strength and average interlayer spacing in osmotic hydrates but also indicate the presence of structural disorder that has not been fully described. In the present study the structural state of expanded smectite in sodium chloride solutionsmore » was investigated by combining very low electron dose, high-resolution cryogenic-transmission electron microscopy observations with XRD experiments. Wyoming smectite (SWy-2) was embedded in vitreous ice to evaluate clay structure in aqua. Lattice-fringe images showed that smectite equilibrated in aqueous, low-ionic-strength solutions, exists as individual smectite layers, osmotic hydrates composed of parallel layers, as well as disordered layer conformations. There was no evidence found here for edge-to-sheet attractions, but significant variability in interlayer spacing was observed. Whether this variation could be explained by a dependence of the magnitude of long-range cohesive (van der Waals) forces on the number of layers in a smectite particle was investigated here. Calculations of the Hamaker constant for layer-layer interactions showed that van der Waals forces may span at least five layers plus the intervening water and confirmed that forces vary with layer number. The drying of the disordered osmotic hydrates induced re-aggregation of the smectite to form particles that exhibited coherent scattering domains. Clay disaggregation and restacking may be considered as an example of oriented attachment, with the unusual distinction that it may be cycled repeatedly by changing solution conditions.« less

Lactobacillus GG (LGG) and smectite versus LGG alone for acute gastroenteritis: a double-blind, randomized controlled trial.

PubMed

Pieścik-Lech, Małgorzata; Urbańska, Magdalena; Szajewska, Hania

2013-02-01

Diarrhea treatment with either Lactobacillus GG (LGG) or smectite as an adjuvant to standard rehydration therapy has proven efficacy. In countries where both LGG and smectite are available, concomitant use is frequently practiced. We investigated whether LGG plus smectite is superior to LGG alone in the management of children with acute gastroenteritis (AGE). A double-blind, placebo-controlled, randomized trial was performed. Children aged 4 to 60 months with AGE received LGG 6 × 10(9) colony forming units/day plus randomly either smectite (3 g) or placebo as an adjuvant to the standard rehydration therapy. Of the 88 children randomized, 81 (92 %) were available for intention-to-treat analysis. The duration of diarrhea in the LGG/smectite group (n = 44) compared with the LGG/placebo group (n = 37) was similar (P = 0.43). There were no significant differences between the study groups for the secondary outcomes, with three exceptions. On day 4, in the LGG/placebo group compared to the LGG/smectite group, there was significantly reduced stool frequency (P = 0.03). While there was a significant (P = 0.05) difference in stool consistency on the Bristol Stool Form Scale on day 4, it was not of clinical relevance. Finally, in the LGG/smectite group compared to the LGG/placebo group, there was a significantly shorter duration of intravenous therapy after randomization (P = 0.02). No adverse events were observed in the study groups. LGG plus smectite and LGG alone are equally effective for treating young children with AGE. Combined use of the two interventions is not justified.

Formation and Restacking of Disordered Smectite Osmotic Hydrates

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

Gilbert, Benjamin; Comolli, Luis R.; Tinnacher, Ruth M.

Clay swelling, an important phenomenon in natural systems, can dramatically affect the properties of soils and sediments. Something of particular interest in low-salinity, saturated systems are osmotic hydrates, forms of smectite in which the layer separation greatly exceeds the thickness of a single smectite layer due to the intercalation of water. In situ X-ray diffraction (XRD) studies have shown a strong link between ionic strength and average interlayer spacing in osmotic hydrates but also indicate the presence of structural disorder that has not been fully described. In the present study the structural state of expanded smectite in sodium chloride solutionsmore » was investigated by combining very low electron dose, high-resolution cryogenic-transmission electron microscopy observations with XRD experiments. Wyoming smectite (SWy-2) was embedded in vitreous ice to evaluate clay structure in aqua. Lattice-fringe images showed that smectite equilibrated in aqueous, low-ionic-strength solutions, exists as individual smectite layers, osmotic hydrates composed of parallel layers, as well as disordered layer conformations. There was no evidence found here for edge-to-sheet attractions, but significant variability in interlayer spacing was observed. Whether this variation could be explained by a dependence of the magnitude of long-range cohesive (van der Waals) forces on the number of layers in a smectite particle was investigated here. Calculations of the Hamaker constant for layer-layer interactions showed that van der Waals forces may span at least five layers plus the intervening water and confirmed that forces vary with layer number. The drying of the disordered osmotic hydrates induced re-aggregation of the smectite to form particles that exhibited coherent scattering domains. Clay disaggregation and restacking may be considered as an example of oriented attachment, with the unusual distinction that it may be cycled repeatedly by changing solution conditions.« less

Transformation of adsorbed aflatoxin B1 on smectite at elevated temperatures

USDA-ARS?s Scientific Manuscript database

Aflatoxins cause liver damage and suppress immunity. Smectites can be used to reduce the bioavailability of aflatoxins through adsorption. To further reduce the toxicity of aflatoxins and to eliminate the treatments of aflatoxin-loaded smectites, degrading the adsorbed aflatoxin to nontoxic or less ...

Smectite Formation in Acid Sulfate Environments on Mars

NASA Technical Reports Server (NTRS)

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

2017-01-01

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

Mineralogical, chemical and K-Ar isotopic changes in Kreyenhagen Shale whole rocks and <2 µm clay fractions during natural burial and hydrous-pyrolysis experimental maturation

USGS Publications Warehouse

Clauer, Norbert; Lewan, Michael D.; Dolan, Michael P.; Chaudhuri, Sambhudas; Curtis, John B.

2014-01-01

Large amounts of smectite layers in the illite–smectite mixed layers of the pyrolyzed outcrop <2 μm fraction remain during thermal experiments, especially above 310 °C. With no illitization detected above 310 °C, smectite appears to have inhibited rather than promoted generation of expelled oil from decomposition of bitumen. This hindrance is interpreted to result from bitumen impregnating the smectite interlayer sites and rock matrix. Bitumen remains in the <2 μm fraction despite leaching with H2O2. Its presence in the smectite interlayers is apparent by the inability of the clay fraction to fully expand or collapse once bitumen generation from the thermal decomposition of the kerogen is completed, and by almost invariable K–Ar ages confirming for the lack of any K supply and/or radiogenic 40Ar removal. This suggests that once bitumen impregnates the porosity of a progressively maturing source rock, the pore system is no longer wetted by water and smectite to illite conversion ceases. Experimental attempts to evaluate the smectite conversion to illite should preferentially use low-TOC rocks to avoid inhibition of the reaction by bitumen impregnation.

Temperature-dependent residual shear strength characteristics of smectite-bearing landslide soils

NASA Astrophysics Data System (ADS)

Shibasaki, Tatsuya; Matsuura, Sumio; Hasegawa, Yoichi

2017-02-01

This paper presents experimental investigations regarding the effect of temperature on the residual strength of landslide soils at slow-to-moderate shearing velocities. We performed ring-shear tests on 23 soil samples at temperatures of 6-29°C. The test results show that the shear strength of smectite-rich soils decreased when temperatures were relatively low. These positive temperature effects (strength losses at lower temperatures) observed for smectite-bearing soils are typical under relatively slow shearing rates. In contrast, under relatively high shearing rates, strength was gained as temperature decreased. As rheological properties of smectite suspensions are sensitive to environmental factors, such as temperature, pH, and dissolved ions, we inferred that temperature-dependent residual strengths of smectitic soils are also attributed to their specific rheological properties. Visual and scanning electron microscope observations of Ca-bentonite suggest that slickensided shear surfaces at slow shearing rates are very shiny and smooth, whereas those at moderate shearing rates are not glossy and are slightly turbulent, indicating that platy smectite particles are strongly orientated at slow velocities. The positive temperature effect is probably due to temperature-dependent microfriction that is mobilized in the parallel directions of the sheet structure of hydrous smectite particles. On the contrary, the influence of microviscous resistance, which appears in the vertical directions of the lamination, is assumed to increase at faster velocities. Our results imply that if slip-surface soils contain high fractions of smectite, decreases in ground temperature can lead to lowered shear resistance of the slip surface and trigger slow landslide movement.

Interaction between tetracycline and smectite in aqueous solution.

PubMed

Li, Zhaohui; Chang, Po-Hsiang; Jean, Jiin-Shuh; Jiang, Wei-Teh; Wang, Chih-Jen

2010-01-15

The fate and transport of commonly used antibiotics in soil and groundwater have attracted renewed studies due to increased sensitivities of analytical instruments and thus frequent detections of these compounds even in treated wastewater. Smectite, an important soil component, has large surface area and high cation exchange capacity, while tetracycline (TC) can exist in different forms and charges under different pH conditions. Thus, the interaction between smectite and TC in aqueous systems is of great importance. This research focused on elucidating the mechanisms of TC uptake by smectite, in terms of TC adsorption, cation desorption, and pH changes associated with TC adsorption by smectite and intercalation in smectite. TC adsorption onto smectite was a relatively fast process even though most of the adsorption sites were in the interlayer position involved in intercalation as confirmed by the expansion of d(001) spacing. The TC adsorption capacity was equivalent to 0.74-1.11 times the cation exchange capacity for three of the four smectite minerals studied. Accompanying TC adsorption was simultaneous adsorption of H(+), resulting in protonation of TC on the dimethylamine group. At higher TC input concentrations further adsorption of H(+) resulted in the ratio of H(+) adsorbed to TC adsorbed greater than one, suggesting that additionally adsorbed H(+) could serve as counterions to partially offset the negative charges on the tricarbonyl or phenolic diketone functional groups. The positive correlations between cations desorbed and TC adsorbed, as well as TC adsorbed and H(+) adsorbed, provided a first time evidence to confirm cation exchange as the main mechanism of TC uptake, even under neutral pH conditions.

The Formation of Fe/Mg Smectite Under Mildly Acidic Conditions on Early Mars

NASA Technical Reports Server (NTRS)

Sutter, Brad; Golden, D. C.; Ming, Douglas W.; Niles, P. B.

2011-01-01

The detection of Fe/Mg smectites and carbonate in Noachian and early Hesperian terrain of Mars has been used to suggest that neutral to mildly alkaline conditions prevailed during the early history of Mars. However, if early Mars was neutral to moderately alkaline with a denser CO2 atmosphere than today, then large carbonates deposits should be more widely detected in Noachian terrain. The critical question is: Why have so few carbonate deposits been detected compared to Fe/Mg smectites? We suggest that Fe/Mg smectites on early Mars formed under mildly acidic conditions, which would inhibit the extensive formation of carbonate deposits. The goal of this work is to evaluate the formation of Fe/Mg smectites under mildly acidic conditions. The stability of smectites under mildly acidic conditions is attributed to elevated Fe/Mg activities that inhibit smectite dissolution. Beidelite and saponite have been shown to form from hydrothermal alteration of basaltic glass at pH 3.5-4.0 in seawater solutions. Nontronite is also known to be stable in mildly acidic systems associated with mafic and ultramafic rock. Nontronite was shown to form in acid sulfate soils in the Bangkok Plain, Thailand due to oxidation of Fe-sulfides that transformed saponite to nontronite. Smectite is known to transform to kaolinite in naturally acid soils due to selective leaching of Mg. However, if Mg removal is limited, then based on equilibrium relationships, the dissolution of smectite should be minimized. If Fe and Mg solution activities are sufficiently high, such as might be found in a low water/rock ratio system that is poorly drained, smectite could form and remain stable under mildly acidic conditions on Mars. The sources of mild acidity on early Mars includes elevated atmospheric CO2 levels, Fe-hydrolysis reactions, and the presence of volcanic SO2 aerosols. Equilibrium calculations dictate that water equilibrated with an early Mars CO2 atmosphere at 1 to 4 bar yields a pH of 3.6 to 3.9. Fe hydrolysis reactions on Mars is another source of protons that would have contributed to acidity. The presence of SO2 from volcanic processes could also have contributed to geochemical acidification. These sources of acidity competed with base-forming cations that resulted in mildly acidic solutions that were not favorable for carbonate formation but may have allowed for Fe/Mg smectite formation. Noachian to early Hesperian Mars could have been mildly acidic, allowing Fe/Mg smectite formation but preventing widespread carbonate deposition. This paradigm shift from an early Mars that was neutral-alkaline to mildly acidic may possibly explain why there is a disparity between the occurrence of carbonate and Fe/Mg smectites. Potential microbiological activity would not be eliminated under a mildly acidic Mars; however, there could be tighter constraints as to the type and species of microbiology that could exist.

Application of an alkylammonium method for characterization of phyllosilicates in CI chondrites

NASA Technical Reports Server (NTRS)

Golden, D. C.; Ming, D. W.; Zolensky, M. E.; Yang, S. V.

1994-01-01

Many meteorites and interplanetary dust particles (IDP's) with primitive compositions contain significant amounts of phyllosilicates, which are generally interpreted as evidence of protoplanetary aqueous alteration at an early period in the solar system. These meteorites are chondrites of the carbonaceous and ordinary varieties. Characterization of phyllosilicates in these materials is important because of the important physico-chemical information they hold, e.g., from well characterized phyllosilicates, thermodynamic stability relations and hence the conditions of formation of phyllosilicates in the parent body of the meteorite can be predicted. Although we are at a rudimentary level of understanding of the minerals resulting from the aqueous alteration in the early solar nebula, we know that the most common phyllosilicates present in chondritic extraterrestrial materials are serpentines, smectites, chlorites, and micas. The characterization of fine grained minerals in meteorites and IDP's rely heavily on electron beam instruments, especially transmission electron microscopy (TEM). Typically, phyllosilicates are identified by a combination of high resolution imaging of basal spacings, electron diffraction analysis, and chemical analysis. Smectites can be difficult to differentiate from micas because the smectites loose their interlayer water and the interlayers collapse to the same basal spacing as mica in the high vacuum of the TEM. In high-resolution TEM (HRTEM) images, smectite basal spacings vary from 1 nm up to 1.5 nm, while micas show 1 or 2 nm basal spacings. Not only is it difficult to differentiate smectites from micas, but there is no way of identifying different classes of smectites in meteorites and IDP's. To differentiate smectites from micas and also to recognize the charge differences among smectites, an alkylammonium method can be employed because the basal spacings of alkylammonium saturated smectites expand as a function of alkylamine chain length and the layer-charge density of the 2:1 expanding phyllosilicate, and the final product is significantly more stable under electron beam examination. Such a method was tested on standard clays and several meteorite samples using four alkylammonium salts.

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

NASA Technical Reports Server (NTRS)

Treiman, Allan H; Morris, Richard V.; Bristow, Thomas; Ming, Douglas W.; Achillies, Cherie; Bish, David L.; Blake, David; Vaniman, David; Chipera, Steve

2013-01-01

Sediments of the Sheepbed unit, Gale Crater, were analyzed by the CheMin X-ray diffraction instrument on the Curiosity Rover. The sediments consist of typical basalt minerals (Fe-forsterite, augite, pigeonite, plagioclase), as well as Fe oxide/hydroxides, Fesulfides, amorphous material, and a phyllosilicate. The phyllosilicate has a broad 001 peak at approx 1.0 nm, consistent with a poorly ordered smectite. However, in the absence of diagnostic tests possible on Earth, its identity is not clear. The position of the 06L diffraction band is generally used to distinguish dioctahedral from trioctahedral smectite, but it is beyond CheMin's range of 2 Theta. The measured position of the 02L diffraction band (approx 22.5deg 2 Theta by CheMin), implies that the smectite is trioctahedral. The exact position and shape of the 02L band is determined by the cations in the 'M' sites of the smectite; to constrain those cations, we sought analogs among terrestrial smectites, emphasizing those developed from basaltic precursors. A potential analog for the Sheepbed smectite is 'griffithite,' a variety of trioctahedral smectite in altered basalt of the Topanga formation, Griffith Park, Los Angeles. 'Griffithite' has an 02L diffraction band that is close in position and shape to that of the Sheepbed smectite, although 'griffithite' has a very sharp 001 peak, indicating a high degree of layer ordering not seen in the Sheepbed smectite. A typical chemical formula for 'griffithite,' determined by electron microprobe, is (Ca0.59 Na0.03) (Mg4.28 Fe1.83) (Si6.64 Al1.36) O20 (OH)4, normalized to Si+Al=8. This formula is consistent with a fully trioctahedral Fe-Mg smectite with Ca and Na as interlayer cations. In the Topanga basalt, four types of 'griffithite' are present: fine-grained, filling cracks and vesicles; coarse-grained, filling vesicles; coarse-grained, replacing olivine phenocrysts; and coarse-grained, replacing glassy mesostasis. The fine-grained 'griffithite' formed first, and the last three varieties may be contemporaneous. One sample shows agate (alpha- quartz) that was precipitated between the episodes of deposition of the fine-grained and coarse-grained 'griffithite.' 'Griffithite' is not unique as a possible terrestrial analog - some clay minerals from the Doushantou formation, China, have similar 02L diffraction bands, and many basalts contain smectites in vesicles and as replacements after olivine. Similar trioctahedral smectites occur also in the nakhlite martian meteorites - as veinlets and replacements of olivine. By understanding the formation of these terrestrial clays, we hope to constrain the nature and mechanism of formation of the Sheepbed clay mineral.

Dehydrochlorination of 1,1,1-trichloroethane and pentachloroethane by microbially reduced ferruginous smectite.

PubMed

Cervini-Silva, Javiera; Kostka, Joel E; Larson, Richard A; Stucki, Joseph W; Wu, Jun

2003-05-01

Reduction of structural Fe(III) in smectite clay minerals has been identified as a means to promote dechlorination of polychlorinated ethanes, but its environmental significance has yet to be fully assessed because Fe reduction has normally been achieved by agents uncommon in the environment (e.g., dithionite). This study reports the dehydrochlorination of pentachloroethane and 1,1,1-trichloroethane in the presence of ferruginous smectite reduced by two cultures of microorganisms, Shewanella oneidensis strain MR-1 (MR-R) and an enrichment culture from rice paddy soils (PS-R), in aqueous suspension under anoxic conditions. Microbially reduced ferruginous smectite facilitated dehydrochlorination of 1,1,1-trichloroethane to 1,1-dichloroethene with up to 60% conversion within 3 h of incubation time. In contrast, no formation of 1,1-dichloroethene was observed after incubation of 1,1,1-trichloroethane with chemically reduced ferruginous smectite for 24 h. Microbially reduced ferruginous smectite by MR-R and PS-R promoted the dehydrochlorination of pentachloroethane to tetrachloroethene by 80 and 15%, respectively, after 3 h of incubation time. The conversion of pentachloroethane to tetrachloroethene in the presence of chemically reduced ferruginous smectite after 24 h was 65%. These results indicate that structural Fe(II) in clay minerals has the potential to be an important reductant controlling the fate of organic chemicals in contaminated sediments.

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.

Effects of Kapton Sample Cell Windows on the Detection Limit of Smectite: Implications for CheMin on the Mars Science Laboratory Mission

NASA Technical Reports Server (NTRS)

Achilles, C. N.; Ming, Douglas W.; Morris, R. V.; Blake, D. F.

2012-01-01

The CheMin instrument on the Mars Science Laboratory (MSL) rover Curiosity is an X-ray diffraction (XRD) and X-ray fluorescence (XRF) instrument capable of providing the mineralogical and chemical compositions of rocks and soils on the surface of Mars. CheMin uses a microfocus X-ray tube with a Co target, transmission geometry, and an energy-discriminating X-ray sensitive CCD to produce simultaneous 2-D XRD patterns and energy-dispersive X-ray histograms from powdered samples. CheMin has two different window materials used for sample cells -- Mylar and Kapton. Instrument details are provided elsewhere. Fe/Mg-smectite (e.g., nontronite) has been identified in Gale Crater, the MSL future landing site, by CRISM spectra. While large quantities of phyllosilicate minerals will be easily detected by CheMin, it is important to establish detection limits of such phases to understand capabilities and limitations of the instrument. A previous study indicated that the (001) peak of smectite at 15 Ang was detectable in a mixture of 1 wt.% smectite with olivine when Mylar is the window material for the sample cell. Complications arise when Kapton is the window material because Kapton itself also has a diffraction peak near 15 Ang (6.8 deg 2 Theta). This study presents results of mineral mixtures of smectite and olivine to determine smectite detection limits for Kapton sample cells. Because the intensity and position of the smectite (001) peak depends on the hydration state, we also analyzed mixtures with "hydrated" and "dehydrated"h smectite to examine the effects of hydration state on detection limits.

Simulation of Viking biology experiments suggests smectites not palagonites, as martian soil analogues

NASA Technical Reports Server (NTRS)

Banin, A.; Margulies, L.

1983-01-01

An experimental comparison of palagonites and a smectite (montmorillonite) was performed in a simulation of the Viking Biology Labelled Release (LR) experiment in order to judge which mineral is a better Mars soil analog material (MarSAM). Samples of palagonite were obtained from cold weathering environments and volcanic soil, and the smectite was extracted from Wyoming Bentonite and converted to H or Fe types. Decomposition reaction kinetics were examined in the LR simulation, which on the Lander involved interaction of the martian soil with organic compounds. Reflectance spectroscopy indicated that smectites bearing Fe(III) in well-crystallized sites are not good MarSAMS. The palagonites did not cause the formate decomposition and C-14 emission detected in the LR, indicating that palagonites are also not good MarSAMS. Smectites, however, may be responsible for ion exchange, molecular adsorption, and catalysis in martian soil.

HYDROTHERMAL MINERALOGY OF RESEARCH DRILL HOLE Y-3, YELLOWSTONE NATIONAL PARK, WYOMING.

USGS Publications Warehouse

Bargar, Keith E.; Beeson, Melvin H.

1984-01-01

The approximate paragenetic sequence of hydrothermal minerals in the Y-3 U. S. Geological Survey research diamond-drill hole in Lower Geyser Basin, Yellowstone National Park, Wyoming, is: hydrothermal chalcedony, hematite, pyrite, quartz, clay minerals (smectite and mixed-layer illite-smectite), calcite, chlorite, fluorite, pyrite, quartz, zeolite minerals (analcime, dachiardite, laumontite, stilbite, and yugawaralite), and clay minerals (smectite and mixed-layer illite-smectite). A few hydrothermal minerals that were identified in drill core Y-3 (lepidolite, aegirine, pectolite, and truscottite) are rarely found in modern geothermal areas. The alteration minerals occur primarily as vug and fracture fillings that were deposited from cooling thermal water. Refs.

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

NASA Technical Reports Server (NTRS)

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

1991-01-01

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

Importance of dust storms in the diagenesis of sandstones: a case study, Entrada sandstone in the Ghost Ranch area, New Mexico, USA

NASA Astrophysics Data System (ADS)

Orhan, Hükmü

1992-04-01

The importance of dust storms on geological processes has only been studied recently. Case-hardening, desert-varnish formation, duricrust development, reddening and cementation of sediments and caliche formation, are some important geological processes related to dust storms. Dust storms can also be a major source for cements in aeolian sandstones. The Jurassic aeolian Entrada Formation in the Ghost Ranch area is composed of quartz with minor amounts of feldspar and rock fragments, and is cemented with smectite as grain coatings and calcite and kaolinite as pore fillings. Smectite shows a crinkly and honeycomb-like morphology which points to an authigenic origin. The absence of smectite as framework grains and the presence of partially dissolved grains, coated with smectite and smectite egg-shells, indicate an external source. Clay and fine silt-size particles are believed to be the major source for cements, smectite and calcite in the Entrada Formation. The common association of kaolinite with altered feldspar, and the absence of kaolinite in spots heavily cemented with calcite, lead to the conclusions that the kaolinite formation postdates carbonates and that framework feldspar grains were the source of kaolinite.

[Mechanism Study of the Smectite-OR-SH Compound for Reducing Cadmium Uptake by Plants in Contaminated Soils].

PubMed

Zeng, Yan-jun; Zhou, Zhi-jun; Zhao, Qiu-xiang

2015-06-01

Adsorption and desorption experiments, pot experiments and characterization test were performed to investigate the immobilization effect and mechanism of the smectite-OR-SH compound for reducing cadmium uptake by plants in contaminated soils. The results showed that the saturated adsorption capacity for the adsorption of Cd2+ on smectite raised distinctly after functionalized. The adsorption of Cd2+ on smectite-OR-SH compound was very stable and it was difficult for Cd2+ to be desorbed from it. Crop yields promoted differently in original soil, Cd 3 mg x kg(-1) soil and Cd 10 mg x kg(-1) soil after adding the smectite-OR-SH compound. And the cadmium content of the cabbage reduced 61.00%, 62.10% and 83.73% respectively compare with the control. Characterization test analysis showed that Cd was adsorbed by the compound successfully and ligand interaction occurred between Cd and the thiol group. Floc amount on the compound surface increased correspondingly. In addition to electrostatic adsorption, ion exchange and hydroxyl ligand adsorption, the reaction mechanism of smectite-OR-SH compound with Cd was mainly sulfhydryl ligand adsorption.

Siderophore-promoted dissolution of smectite by fluorescent Pseudomonas.

PubMed

Ferret, Claire; Sterckeman, Thibault; Cornu, Jean-Yves; Gangloff, Sophie; Schalk, Isabelle J; Geoffroy, Valérie A

2014-10-01

Siderophores are organic chelators produced by microorganisms to fulfil their iron requirements. Siderophore-promoted dissolution of iron-bearing minerals has been clearly documented for some siderophores, but few studies have addressed metabolizing siderophore-producing bacteria. We investigated iron acquisition from clays by fluorescent Pseudomonads, bacteria that are ubiquitous in the environment. We focused on the interactions between smectite and Pseudomonas aeruginosa, a bacterium producing two structurally different siderophores: pyoverdine and pyochelin. The presence of smectite in iron-limited growth media promoted planktonic growth of P. aeruginosa and biofilm surrounding the smectite aggregates. Chemical analysis of the culture media indicated increases in the dissolved silicon, iron and aluminium concentrations following smectite supplementation. The use of P. aeruginosa mutants unable to produce either one or both of the two siderophores indicated that pyoverdine, the siderophore with the higher affinity for iron, was involved in iron and aluminium solubilization by the wild-type strain. However, in the absence of pyoverdine, pyochelin was also able to solubilize iron but with a twofold lower efficiency. In conclusion, pyoverdine and pyochelin, two structurally different siderophores, can solubilize structural iron from smectite and thereby make it available for bacterial growth.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Stable hydrogen production from ethanol through steam reforming reaction over nickel-containing smectite-derived catalyst.

PubMed

Yoshida, Hiroshi; Yamaoka, Ryohei; Arai, Masahiko

2014-12-25

Hydrogen production through steam reforming of ethanol was investigated with conventional supported nickel catalysts and a Ni-containing smectite-derived catalyst. The former is initially active, but significant catalyst deactivation occurs during the reaction due to carbon deposition. Side reactions of the decomposition of CO and CH4 are the main reason for the catalyst deactivation, and these reactions can relatively be suppressed by the use of the Ni-containing smectite. The Ni-containing smectite-derived catalyst contains, after H2 reduction, stable and active Ni nanocrystallites, and as a result, it shows a stable and high catalytic performance for the steam reforming of ethanol, producing H2.

Stable Hydrogen Production from Ethanol through Steam Reforming Reaction over Nickel-Containing Smectite-Derived Catalyst

PubMed Central

Yoshida, Hiroshi; Yamaoka, Ryohei; Arai, Masahiko

2014-01-01

Hydrogen production through steam reforming of ethanol was investigated with conventional supported nickel catalysts and a Ni-containing smectite-derived catalyst. The former is initially active, but significant catalyst deactivation occurs during the reaction due to carbon deposition. Side reactions of the decomposition of CO and CH4 are the main reason for the catalyst deactivation, and these reactions can relatively be suppressed by the use of the Ni-containing smectite. The Ni-containing smectite-derived catalyst contains, after H2 reduction, stable and active Ni nanocrystallites, and as a result, it shows a stable and high catalytic performance for the steam reforming of ethanol, producing H2. PMID:25547495

Sorption characteristics of organic compounds on hexadecyltrimethylammonium-smectite

USGS Publications Warehouse

Boyd, Stephen A.; Mortland, Max M.; Chiou, Cary T.

1988-01-01

When hexadedyltrimethylammonium (HDTMA) ion is exchanged for metal cations like calcium in smectite, the sorptive properties of the clay are greatly modified. The resultant HDTMA-smectite complex behaves as a dual sorbent, in the sorption of organic compounds, in which the mineral fraction functions as a solid adsorbent and the organic (HDTMA) phase as a partition medium. Capacities of mineral adsorption and partition uptake by HDTMA in the HDTMA-smectites are illustrated by sorption of benzene, trichloroethene (TCE), and water as vapors on the dry sample and by sorption of benzene and TCE from water. The exchanged HDTMA in clay is found to be a much more powerful partition medium than ordinary soil organic matter in the uptake of benzene and TCE. Based on this finding, HDTMA-smectite appears to be an effective sorbent for removing organic contaminants from water. It is suggested that such sorptive organo-clay complexes could be used to enhance the containment capabilities of clay landfill liners and bentonite slurry walls.

Precipitation of Secondary Phases from the Dissolution of Silicate Glasses

NASA Technical Reports Server (NTRS)

Ming, Douglas W.; Golden, D. C.

2004-01-01

Basaltic and anorthositic glasses were subjected to aqueous weathering conditions in the laboratory where the variables were pH, temperature, glass composition, solution composition, and time. Leached layers formed at the surfaces of glasses followed by the precipitation of X-ray amorphous iron and titanium oxides in acidic and neutral solutions at 25 C over time. Glass under oxidative hydrothermal treatments at 150 C yielded a three-layered surface; which included an outer smectite layer, a Fe-Ti oxide layer and an innermost thin leached layer. The introduction of Mg into solutions facilitated the formation of phyllosilicates. Aqueous hydrothermal treatment of anorthositic glasses (high Ca, low Ti) at 200 C readily formed smectite, whereas, the basaltic glasses (high Ti) were more resistant to alteration and smectite was not observed. Alkaline hydrothermal treatment at 2000e produced zeolites and smectites; only smectites formed at 200 C in neutral solutions. These mineralogical changes, although observed under controlled conditions, have direct applications in interpreting planetary (e.g., meteorite parent bodies) and terrestrial aqueous alteration processes.

In situ immobilisation of toxic metals in soil using Maifan stone and illite/smectite clay.

PubMed

Ou, Jieyong; Li, Hong; Yan, Zengguang; Zhou, Youya; Bai, Liping; Zhang, Chaoyan; Wang, Xuedong; Chen, Guikui

2018-03-15

Clay minerals have been proposed as amendments for remediating metal-contaminated soils owing to their abundant reserves, high performance, simplicity of use and low cost. Two novel clay minerals, Maifan stone and illite/smectite clay, were examined in the in situ immobilisation of soil metals. The application of 0.5% Maifan stone or illite/smectite clay to field soils significantly decreased the fractions of diethylenetriaminepentaacetic acid (DTPA)-extractable Cd, Ni, Cr, Zn, Cu and Pb. Furthermore, reductions of 35.4% and 7.0% in the DTPA-extractable fraction of Cd were obtained with the Maifan stone and illite/smectite clay treatments, respectively, which also significantly reduced the uptake of Cd, Ni, Cr, Zn, Cu and Pb in the edible parts of Brassica rapa subspecies pekinensis, Brassica campestris and Spinacia oleracea. Quantitatively, the Maifan stone treatment reduced the metal uptake in B. rapa ssp. Pekinensis, B. campestris and S. oleracea from 11.6% to 62.2%, 4.6% to 41.8% and 11.3% to 58.2%, respectively, whereas illite/smectite clay produced reductions of 8.5% to 62.8% and 4.2% to 37.6% in the metal uptake in B. rapa ssp. Pekinensis and B. campestris, respectively. Therefore, both Maifan stone and illite/smectite clay are promising amendments for contaminated soil remediation.

Analysis of the improvement of selenite retention in smectite by adding alumina nanoparticles.

PubMed

Mayordomo, Natalia; Alonso, Ursula; Missana, Tiziana

2016-12-01

Smectite clay is used as barrier for hazardous waste retention and confinement. It is a powerful material to retain cations, but less effective for retaining anionic species like selenite. This study shows that the addition of a small percentage of γ-Al 2 O 3 nanoparticles to smectite significantly improves selenite sorption. γ-Al 2 O 3 nanoparticles provide high surface area and positively charged surface sites within a wide range of pH, since their point of zero charge is at pH8-9. An addition of 20wt% of γ-Al 2 O 3 to smectite is sufficient to approach the sorption capacity of pure alumina. To analyze the sorption behavior of the smectite/oxide mixtures, a nonelectrostatic surface complexation model was considered, accounting for the surface complexation of HSeO 3 - and SeO 3 2- , the anion competition, and the formation of surface ternary complexes with major cations present in the solution. Selenite sorption in mixtures was satisfactorily described with the surface parameters and complexation constants defined for the pure systems, accounting only for the mixture weight fractions. Sorption in mixtures was additive despite the particle heteroaggregation observed in previous stability studies carried out on smectite/γ-Al 2 O 3 mixtures. Copyright © 2016 Elsevier B.V. All rights reserved.

Prediction of Intrinsic Cesium Desorption from Na-Smectite in Mixed Cation Solutions.

PubMed

Fukushi, Keisuke; Fukiage, Tomo

2015-09-01

Quantitative understanding of the stability of sorbed radionuclides in smectite is necessary to assess the performance of engineering barriers used for nuclear waste disposal. Our previous study demonstrated that the spatial organization of the smectite platelets triggered by the divalent cations led to the apparent fixation of intrinsic Cs in smectite, because some Cs is retained inside the formed tactoids. Natural water is usually a mixture of Na(+) and divalent cations (Ca(2+) and Mg(2+)). This study therefore investigated the desorption behavior of intrinsic Cs in Na-smecite in mixed Na(+)-divalent cation solutions under widely various cation concentrations using batch experiments, grain size measurements, and cation exchange modeling (CEM). Results show that increased Na(+) concentrations facilitate Cs desorption because Na(+) serves as the dispersion agent. A linear relation was obtained between the logarithm of the Na(+) fraction and the accessible Cs fraction in smectite. That relation enables the prediction of accessible Cs fraction as a function of solution cationic compositions. The corrected CEM considering the effects of the spatial organization suggests that the stability of intrinsic Cs in the smectite is governed by the Na(+) concentration, and suggests that it is almost independent of the concentrations of divalent cations in natural water.

Discovery of Ni-smectite-rich saprolite at Loma Ortega, Falcondo mining district (Dominican Republic): geochemistry and mineralogy of an unusual case of "hybrid hydrous Mg silicate - clay silicate" type Ni-laterite

NASA Astrophysics Data System (ADS)

Tauler, Esperança; Lewis, John F.; Villanova-de-Benavent, Cristina; Aiglsperger, Thomas; Proenza, Joaquín A.; Domènech, Cristina; Gallardo, Tamara; Longo, Francisco; Galí, Salvador

2017-10-01

Hydrous Mg silicate-type Ni-laterite deposits, like those in the Falcondo district, Dominican Republic, are dominated by Ni-enriched serpentine and garnierite. Recently, abundant Ni-smectite in the saprolite zone have been discovered in Loma Ortega, one of the nine Ni-laterite deposits in Falcondo. A first detailed study on these Ni-smectites has been performed (μXRD, SEM, EPMA), in addition to a geochemical and mineralogical characterisation of the Loma Ortega profile (XRF, ICP-MS, XRD). Unlike other smectite occurrences in laterite profiles worldwide, the Loma Ortega smectites are trioctahedral and exhibit high Ni contents never reported before. These Ni-smectites may be formed from weathering of pyroxene and olivine, and their composition can be explained by the mineralogy and the composition of the Al-depleted, olivine-rich parent ultramafic rock. Our study shows that Ni-laterites are mineralogically complex, and that a hydrous Mg silicate ore and a clay silicate ore can be confined to the same horizon in the weathering profile, which has significant implications from a recovery perspective. In accordance, the classification of "hybrid hydrous Mg silicate - clay silicate" type Ni-laterite deposit for Loma Ortega would be more appropriate.

Interlamellar adsorption of carbon dioxide by smectites

USGS Publications Warehouse

Fripiat, J.J.; Cruz, M.I.; Bohor, B.F.; Thomas, J.

1974-01-01

The adsorption of CO2 at low temperature (∼ −70°C) on thin films of homoionic smectites was studied by X-ray diffraction and by i.r. absorption. An increase in the d001 spacings of these clay films upon adsorption of CO2 was observed. In addition, a dichroic effect was readily discernible by comparing the i.r. spectra at two different orientations of the smectite films; i.e. with the film normal and tilted 35° with respect to the i.r. beam. The CO2 stretching vibration at 2350 cm−1 was used for the i.r. study. These observations conclusively show that CO2 intercalates the smectite structure rather than being adsorbed only in pores between clay tactoids—the limiting process proposed by other investigators.Adsorption isotherm data from earlier surface area studies are re-examined here through application of the Dubinin equation. Again, intercalation is demonstrated by convergence of the plotted experimental data for smectites containing large monovalent interlayer cations toward a pore volume that is near the calculated theoretical value for a monolayer of intercalated CO2.Scanning electron photomicrographs of Li- and Cs- smectites provide additional evidence that aggregation differences are not responsible for the large observed difference in BET surface areas obtained for these smectites with CO2 as the adsorbate. At low magnification, visual differences in macro-aggregates are apparent, but at high magnification no significant differences are observed in the micro-structure of individual aggregates where the major amount of gas adsorption really occurs.

Efficacy of Probiotics and Smectite in Rats with Non-Alcoholic Fatty Liver Disease.

PubMed

Kobyliak, Nazarii; Abenavoli, Ludovico; Falalyeyeva, Tetyana; Beregova, Tetyana

2018-01-01

Today probiotics have been suggested as a treatment for the prevention of non-alcoholic fatty liver disease (NAFLD). Smectite is a natural silicate that binds to digestive mucous and has the ability to bind endo- and exotoxins. The present study was designed to determine whether probiotics plus smectite is superior to probiotic alone on the monosodium glutamate (MSG) induced NAFLD model in rats. We included 60 rats divided into 4 groups 15 animals in each. Rats of group I were intact. Newborns rats of groups II-IV were injected with MSG. The III (Symbiter) group received 2.5 ml/kg of multiprobiotic "Symbiter" containing concentrated biomass of 14 probiotic bacteria genera. The IV (Symbiter+Smectite) groups received "Symbiter Forte" combination of probiotic biomass with smectite gel (250 mg). In both interventional groups reduction of total NAS score as compared to MSG-obesity was observed. Indeed similar values of steatosis score (0.93 ± 0.22 vs. 0.87 ± 0.16) in both treatment groups, we observed that lower total score for Symbiter+ Smectite are associated with more pronounced reduction of lobular inflammation (0.13 ± 0.09 vs. 0.33 ± 0.15) as compared to administration of probiotic alone. This data accompanied with significant reduction of IL-1 and restoration of IL-10 between these 2 groups. Additional to alive probiotic administration of smectite gel due to his absorbent activity and mucus layer stabilization properties can impact on synergistic enhancement of single effect which manifested with reduction of lobular inflammation and at list partly steatohepatitis prevention.

Amorphization and Frictional Processes in Smectite-Quartz Gouge Mixtures Sheared from Sub-seismic to Seismic Slip Rates

NASA Astrophysics Data System (ADS)

Aretusini, S.; Mittempergher, S.; Spagnuolo, E.; Di Toro, G.; Gualtieri, A.; Plümper, O.

2015-12-01

Slipping zones in shallow sections of megathrusts and large landslides are often made of smectite and quartz gouge mixtures. Experiments aimed at investigating the frictional processes operating at high slip rates (>1 m/s) may unravel the mechanics of these natural phenomena. Here we present a new dataset obtained with two rotary shear apparatus (ROSA, Padua University; SHIVA, INGV-Rome). Experiments were performed at room humidity and temperature on four mixtures of smectite (Ca-Montmorillonite) and quartz with 68, 50, 25, 0 wt% of smectite. The gouges were slid for 3 m at normal stress of 5 MPa and slip rate V from 300 µm/s to 1.5 m/s. Temperature during the experiments was monitored with four thermocouples and modeled with COMSOL Multiphysics. In smectite-rich mixtures, the friction coefficient µ evolved with slip according to three slip rate regimes: in regime 1 (V<0.1 m/s) initial slip-weakening was followed by slip-strengthening; in regime 2 (0.10.3 m/s) µ had strong slip-weakening behavior. Instead, in quartz-rich mixtures the gouge had a monotonic slip-weakening behavior, independently of V. Temperature modelling showed that the fraction of work rate converted into heat decreased with increasing smectite content and slip rate. Quantitative X-ray powder diffraction (Rietveld method) indicates that the production of amorphous material from smectite breakdown increased with frictional work but was independent of work rate. Scanning Electron Microscopy investigation evidenced strain localization and presence of dehydrated clays for V≥0.3 m/s; instead, for V<0.3 m/s, strain was distributed and the gouge layer pervasively foliated. In conclusion, amorphization of the sheared gouges was not responsible of the measured frictional weakening. Instead, slip-weakening was concomitant to strain localization and possible vaporization of water adsorbed on smectite grain surfaces.

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

NASA Astrophysics Data System (ADS)

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

2015-06-01

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

An experimental flow-through assessment of acidic Fe/Mg smectite formation on early Mars

NASA Astrophysics Data System (ADS)

Sutter, B.; Peretyazhko, T.; Garcia, A. H.; Ming, D. W.

2017-12-01

Orbital observations have detected the phyllosilicate smectite in layered material hundreds of meters thick, intracrater depositional fans, and plains sediments on Mars; however, the detection of carbonate deposits is limited. Instead of neutral/alkaline conditions during the Noachian, early Mars may have experienced mildly acidic conditions derived from volcanic acid-sulfate solutions that allowed Fe/Mg smectite formation but prevented widespread carbonate formation. The detection of acid sulfates (e.g., jarosite) associated with smectite in Mawrth Vallis supports this hypothesis. Previous work demonstrated smectite (saponite) formation in closed hydrologic systems (batch reactor) from basaltic glass at pH 4 and 200°C (Peretyazhko et al., 2016 GCA). This work presents results from alteration of basaltic glass from alkaline to acidic conditions in open hydrologic systems (flow-through reactor). Preliminary experiments exposed basaltic glass to deionized water at 190°C at 0.25 ml/min where solution pH equilibrated to 9.5. These initial high pH experiments were conducted to evaluate the flow-through reactor system before working with lower pHs. Smectite at this pH was not produced and instead X-ray diffraction results consistent with serpentine was detected. Experiments are in progress exposing basaltic glass from pH 8 down to pH 3 to determine what range of pHs could allow for smectite formation in this experimental open-system. The production of smectite under an experimental open-system at low pHs if successful, would support a significant paradigm shift regarding the geochemical evolution of early Mars: Early Mars geochemical solutions were mildly acidic, not neutral/alkaline. This could have profound implications regarding early martain microbiology where acid conditions instead of neutral/alkaline conditions will require further research in terrestrial analogs to address the potential for biosignature preservation on Mars (Johnson et al., 2016, LPSC).

ROLE OF PRESSURE IN SMECTITE DEHYDRATION - EFFECTS ON GEOPRESSURE AND SMECTITE-TO-ILLITE TRANSFORMATION.

USGS Publications Warehouse

Colten-Bradley, Virginia

1987-01-01

Evaluation of the effects of pressure on the temperature of interlayer water loss (dehydration) by smectites under diagenetic conditions indicates that smectites are stable as hydrated phases in the deep subsurface. Hydraulic and differential pressure conditions affect dehydration differently. The temperature of dehydration increase with pore fluid pressure and interlayer water density. The temperatures of dehydration increase with pore fluid pressure and interlayer water density. The temperatures of dehydration under differential-presssure conditions are inversely related to pressure and interlayer water density. The model presented assumes the effects of pore fluid composition and 2:1 layer reactivity to be negligible. Agreement between theoretical and experimental results validate this assumption. Additional aspects of the subject are discussed.

Effects of smectite on the oil-expulsion efficiency of the Kreyenhagen Shale, San Joaquin Basin, California, based on hydrous-pyrolysis experiments

USGS Publications Warehouse

Lewan, Michael D.; Dolan, Michael P.; Curtis, John B.

2014-01-01

The amount of oil that maturing source rocks expel is expressed as their expulsion efficiency, which is usually stated in milligrams of expelled oil per gram of original total organic carbon (TOCO). Oil-expulsion efficiency can be determined by heating thermally immature source rocks in the presence of liquid water (i.e., hydrous pyrolysis) at temperatures between 350°C and 365°C for 72 hr. This pyrolysis method generates oil that is compositionally similar to natural crude oil and expels it by processes operative in the subsurface. Consequently, hydrous pyrolysis provides a means to determine oil-expulsion efficiencies and the rock properties that influence them. Smectite in source rocks has previously been considered to promote oil generation and expulsion and is the focus of this hydrous-pyrolysis study involving a representative sample of smectite-rich source rock from the Eocene Kreyenhagen Shale in the San Joaquin Basin of California. Smectite is the major clay mineral (31 wt. %) in this thermally immature sample, which contains 9.4 wt. % total organic carbon (TOC) comprised of type II kerogen. Compared to other immature source rocks that lack smectite as their major clay mineral, the expulsion efficiency of the Kreyenhagen Shale was significantly lower. The expulsion efficiency of the Kreyenhagen whole rock was reduced 88% compared to that of its isolated kerogen. This significant reduction is attributed to bitumen impregnating the smectite interlayers in addition to the rock matrix. Within the interlayers, much of the bitumen is converted to pyrobitumen through crosslinking instead of oil through thermal cracking. As a result, smectite does not promote oil generation but inhibits it. Bitumen impregnation of the rock matrix and smectite interlayers results in the rock pore system changing from water wet to bitumen wet. This change prevents potassium ion (K+) transfer and dissolution and precipitation reactions needed for the conversion of smectite to illite. As a result, illitization only reaches 35% to 40% at 310°C for 72 hr and remains unchanged to 365°C for 72 hr. Bitumen generation before or during early illitization in these experiments emphasizes the importance of knowing when and to what degree illitization occurs in natural maturation of a smectite-rich source rock to determine its expulsion efficiency. Complete illitization prior to bitumen generation is common for Paleozoic source rocks (e.g., Woodford Shale and Retort Phosphatic Shale Member of the Phosphoria Formation), and expulsion efficiencies can be determined on immature samples by hydrous pyrolysis. Conversely, smectite is more common in Cenozoic source rocks like the Kreyenhagen Shale, and expulsion efficiencies determined by hydrous pyrolysis need to be made on samples that reflect the level of illitization at or near bitumen generation in the subsurface.

Shallow Water Propagation

DTIC Science & Technology

2013-09-30

HPMM. For these minerals, kaolinite and smectite , the corresponding shear speed estimates are 13 m/s and 0.25 m/s. The third and fourth columns of...representative value for each parameter in two clay minerals, kaolinite and smectite , which are the most common types in marine mud. These values produce...13 m/s for kaolinite and 0.25 m/s for smectite . The third column shows typical ranges of values for h, L, and χ in the two clay types. The fourth

Escherichia coli challenge and one type of smectite alter intestinal barrier of pigs

PubMed Central

2013-01-01

An experiment was conducted to determine how an E. coli challenge and dietary clays affect the intestinal barrier of pigs. Two groups of 32 pigs (initial BW: 6.9 ± 1.0 kg) were distributed in a 2 × 4 factorial arrangement of a randomized complete block design (2 challenge treatments: sham or E. coli, and 4 dietary treatments: control, 0.3% smectite A, 0.3% smectite B and 0.3% zeolite), with 8 replicates total. Diarrhea score, growth performance, goblet cell size and number, bacterial translocation from intestinal lumen to lymph nodes, intestinal morphology, and relative amounts of sulfo and sialo mucins were measured. The E. coli challenge reduced performance, increased goblet cell size and number in the ileum, increased bacterial translocation from the intestinal lumen to the lymph nodes, and increased ileal crypt depth. One of the clays (smectite A) tended to increase goblet cell size in ileum, which may indicate enhanced protection. In conclusion, E. coli infection degrades intestinal barrier integrity but smectite A may enhance it. PMID:24359581

Escherichia coli challenge and one type of smectite alter intestinal barrier of pigs.

PubMed

Almeida, Juliana Abranches Soares; Liu, Yanhong; Song, Minho; Lee, Jeong Jae; Gaskins, H Rex; Maddox, Carol Wolfgang; Osuna, Orlando; Pettigrew, James Eugene

2013-12-20

An experiment was conducted to determine how an E. coli challenge and dietary clays affect the intestinal barrier of pigs. Two groups of 32 pigs (initial BW: 6.9 ± 1.0 kg) were distributed in a 2 × 4 factorial arrangement of a randomized complete block design (2 challenge treatments: sham or E. coli, and 4 dietary treatments: control, 0.3% smectite A, 0.3% smectite B and 0.3% zeolite), with 8 replicates total. Diarrhea score, growth performance, goblet cell size and number, bacterial translocation from intestinal lumen to lymph nodes, intestinal morphology, and relative amounts of sulfo and sialo mucins were measured. The E. coli challenge reduced performance, increased goblet cell size and number in the ileum, increased bacterial translocation from the intestinal lumen to the lymph nodes, and increased ileal crypt depth. One of the clays (smectite A) tended to increase goblet cell size in ileum, which may indicate enhanced protection. In conclusion, E. coli infection degrades intestinal barrier integrity but smectite A may enhance it.

Mineralogy of a mudstone at Yellowknife Bay, Gale crater, Mars.

PubMed

Vaniman, D T; Bish, D L; Ming, D W; Bristow, T F; Morris, R V; Blake, D F; Chipera, S J; Morrison, S M; Treiman, A H; Rampe, E B; Rice, M; Achilles, C N; Grotzinger, J P; McLennan, S M; Williams, J; Bell, J F; Newsom, H E; Downs, R T; Maurice, S; Sarrazin, P; Yen, A S; Morookian, J M; Farmer, J D; Stack, K; Milliken, R E; Ehlmann, B L; Sumner, D Y; Berger, G; Crisp, J A; Hurowitz, J A; Anderson, R; Des Marais, D J; Stolper, E M; Edgett, K S; Gupta, S; Spanovich, N

2014-01-24

Sedimentary rocks at Yellowknife Bay (Gale crater) on Mars include mudstone sampled by the Curiosity rover. The samples, John Klein and Cumberland, contain detrital basaltic minerals, calcium sulfates, iron oxide or hydroxides, iron sulfides, amorphous material, and trioctahedral smectites. The John Klein smectite has basal spacing of ~10 angstroms, indicating little interlayer hydration. The Cumberland smectite has basal spacing at both ~13.2 and ~10 angstroms. The larger spacing suggests a partially chloritized interlayer or interlayer magnesium or calcium facilitating H2O retention. Basaltic minerals in the mudstone are similar to those in nearby eolian deposits. However, the mudstone has far less Fe-forsterite, possibly lost with formation of smectite plus magnetite. Late Noachian/Early Hesperian or younger age indicates that clay mineral formation on Mars extended beyond Noachian time.

Effects of lactic acid bacteria and smectite after aflatoxin B1 challenge on the growth performance, nutrient digestibility and blood parameters of broilers.

PubMed

Liu, N; Ding, K; Wang, J; Deng, Q; Gu, K; Wang, J

2018-04-11

This study aimed to investigate the effect of lactic acid bacteria (LAB) and smectite on the growth performance, nutrient digestibility and blood parameters of broilers that were fed diets contaminated with aflatoxin B 1 (AFB 1 ). A total of 480 newly hatched male Arbor Acres broilers were randomly allocated into four groups with six replicates of 20 chicks each. The broilers were fed diets with the AFB 1 (40 μg/kg) challenge or without (control) it and supplemented with smectite (3.0 g/kg) or LAB (4.0 × 10 10  CFU/kg) based on the AFB 1 diet. The trial lasted for 42 days. The results showed that during days 1-42 of AFB 1 challenge, the feed intake (FI) and body weight gain (BWG) were depressed (p < .05). The inclusion of LAB and smectite increased (p < .05) the BWG by 71.58 and 41.89 g/bird, respectively, which reached the level of the control diet (p ≥ .05), but there were no differences (p ≥ .05) in performance between LAB and smectite. LAB and smectite also increased (p < .05) the apparent total tract digestibility of the crude protein. Regarding the blood parameters, AFB 1 decreased (p < .05) the levels of red blood cell count, haematocrit, mean corpuscular volume, haemoglobin, albumin and total protein. In the meantime, the AFB 1 increased (p < .05) leucocyte counts, urea nitrogen, cholesterol, total bilirubin, creatinine, glutamic-pyruvic transaminase, glutamic oxaloacetic transaminase and alkaline phosphatase. By contrast, LAB and smectite affected (p < .05) these parameters in the opposite direction. It can be concluded that after the AFB 1 challenge, LAB and smectite have similar effects on the growth and health of the broilers, suggesting that LAB could be an alternative against AFB 1 in commercial animal feeds. © 2018 Blackwell Verlag GmbH.

Growth of thermophilic and hyperthermophilic Fe(III)-reducing microorganisms on a ferruginous smectite as the sole electron acceptor.

PubMed

Kashefi, Kazem; Shelobolina, Evgenya S; Elliott, W Crawford; Lovley, Derek R

2008-01-01

Recent studies have suggested that the structural Fe(III) within phyllosilicate minerals, including smectite and illite, is an important electron acceptor for Fe(III)-reducing microorganisms in sedimentary environments at moderate temperatures. The reduction of structural Fe(III) by thermophiles, however, has not previously been described. A wide range of thermophilic and hyperthermophilic Archaea and Bacteria from marine and freshwater environments that are known to reduce poorly crystalline Fe(III) oxides were tested for their ability to reduce structural (octahedrally coordinated) Fe(III) in smectite (SWa-1) as the sole electron acceptor. Two out of the 10 organisms tested, Geoglobus ahangari and Geothermobacterium ferrireducens, were not able to conserve energy to support growth by reduction of Fe(III) in SWa-1 despite the fact that both organisms were originally isolated with solid-phase Fe(III) as the electron acceptor. The other organisms tested were able to grow on SWa-1 and reduced 6.3 to 15.1% of the Fe(III). This is 20 to 50% less than the reported amounts of Fe(III) reduced in the same smectite (SWa-1) by mesophilic Fe(III) reducers. Two organisms, Geothermobacter ehrlichii and archaeal strain 140, produced copious amounts of an exopolysaccharide material, which may have played an active role in the dissolution of the structural iron in SWa-1 smectite. The reduction of structural Fe(III) in SWa-1 by archaeal strain 140 was studied in detail. Microbial Fe(III) reduction was accompanied by an increase in interlayer and octahedral charges and some incorporation of potassium and magnesium into the smectite structure. However, these changes in the major element chemistry of SWa-1 smectite did not result in the formation of an illite-like structure, as reported for a mesophilic Fe(III) reducer. These results suggest that thermophilic Fe(III)-reducing organisms differ in their ability to reduce and solubilize structural Fe(III) in SWa-1 smectite and that SWa-1 is not easily transformed to illite by these organisms.

Growth of Thermophilic and Hyperthermophilic Fe(III)-Reducing Microorganisms on a Ferruginous Smectite as the Sole Electron Acceptor▿

PubMed Central

Kashefi, Kazem; Shelobolina, Evgenya S.; Elliott, W. Crawford; Lovley, Derek R.

2008-01-01

Recent studies have suggested that the structural Fe(III) within phyllosilicate minerals, including smectite and illite, is an important electron acceptor for Fe(III)-reducing microorganisms in sedimentary environments at moderate temperatures. The reduction of structural Fe(III) by thermophiles, however, has not previously been described. A wide range of thermophilic and hyperthermophilic Archaea and Bacteria from marine and freshwater environments that are known to reduce poorly crystalline Fe(III) oxides were tested for their ability to reduce structural (octahedrally coordinated) Fe(III) in smectite (SWa-1) as the sole electron acceptor. Two out of the 10 organisms tested, Geoglobus ahangari and Geothermobacterium ferrireducens, were not able to conserve energy to support growth by reduction of Fe(III) in SWa-1 despite the fact that both organisms were originally isolated with solid-phase Fe(III) as the electron acceptor. The other organisms tested were able to grow on SWa-1 and reduced 6.3 to 15.1% of the Fe(III). This is 20 to 50% less than the reported amounts of Fe(III) reduced in the same smectite (SWa-1) by mesophilic Fe(III) reducers. Two organisms, Geothermobacter ehrlichii and archaeal strain 140, produced copious amounts of an exopolysaccharide material, which may have played an active role in the dissolution of the structural iron in SWa-1 smectite. The reduction of structural Fe(III) in SWa-1 by archaeal strain 140 was studied in detail. Microbial Fe(III) reduction was accompanied by an increase in interlayer and octahedral charges and some incorporation of potassium and magnesium into the smectite structure. However, these changes in the major element chemistry of SWa-1 smectite did not result in the formation of an illite-like structure, as reported for a mesophilic Fe(III) reducer. These results suggest that thermophilic Fe(III)-reducing organisms differ in their ability to reduce and solubilize structural Fe(III) in SWa-1 smectite and that SWa-1 is not easily transformed to illite by these organisms. PMID:17981937

Hydrothermal synthesis of ammonium illite

USGS Publications Warehouse

Šucha, Vladimír; Elsass, F.; Eberl, D.D.; Kuchta, L'.; Madejova, J.; Gates, W.P.; Komadel, P.

1998-01-01

Synthetic gel and glass of illitic composition, natural kaolinite, and mixed-layer illite-smectite were used as starting materials for hydrothermal synthesis of ammonium illite. Ammonium illite was prepared from synthetic gel by hydrothermal treatment at 300??C. The onset of crystallization began within 3 h, and well-crystallized ammonium illite appeared at 24 h. Increasing reaction time (up to four weeks) led to many illite layers per crystal. In the presence of equivalent proportions of potassium and ammonium, the gel was transformed to illite with equimolar contents of K and NH4. In contrast, synthesis using glass under the same conditions resulted in a mixture of mixed-layer ammonium illite-smectite with large expandability and discrete illite. Hydrothermal treatments of the fine fractions of natural kaolinite and illite-smectite produced ammonium illite from kaolinite but the illite-smectite remained unchanged.

The XRD Amorphous Component in John Klein Drill Fines at Yellowknife Bay, Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Morris, Richard V.; Ming,, Douglas W.; Blake, David; Vaniman, David; Bish, David L; Chipera, Steve; Downs, Robert; Morrison, Shaunna; Gellert, Ralf; Campbell, Iain;

The Effects of Punctuated Warm and Wet Environments on Phyllosilicate Formation - or How Long was Early Mars Wet?

NASA Astrophysics Data System (ADS)

Bishop, J. L.; Baker, L.; Rampe, E. B.; Velbel, M. A.

2016-12-01

Abundant phyllosilicates and aqueous minerals are observed nearly everywhere we can see the ancient rocks on Mars [1,2]. Most bountiful among these is Fe/Mg-smectite. So, what can these smectite clays tell us about the early Martian environment? Studies of smectite formation [3,4] indicate that they form faster at elevated (>100 °C) temperatures. There is a trade-off between temperature and time such that lower temperatures require more time for smectite formation. We postulate that short-term warm and wet environments could have enabled formation of the observed smectite occurrences on Mars without requiring long-term bodies of water on the planet. Smectites form in weathering environments by transformation from primary silicates or by neoformation from allophane and related amorphous materials [3,5]. The highest smectite abundances are observed in low rainfall climates (<50 cm/yr), while kaolins and vermiculites require significantly higher rainfall levels [3]. Smectites formed in low temperature (<100 °C) waters are typically mixed with amorphous aluminosilicates [4], which implies incomplete reaction. Allophane and imogolite form in near neutral waters in well-drained environments as Al and Si are leached from volcanic ash and tephra [6]. In dry environments allophane and related nanophase materials can persist long-term. Allophane and imogolite have been identified in Martian surface material from orbit [7,8] and amorphous components have been found at Gale crater [9]. Because amorphous phases such as opal, ferrihydrite, allophane and imogolite are highly reactive and mobile in aqueous environments, finding these on the surface of Mars and in martian meteorites [10] suggests that the planet has been dry since their formation. In fact, Bishop & Rampe [7] suggest that the transition from smectite to allophane on Mars marks a change in climate. References: [1] Carter J. et al. (2015) Icarus, 248, 373. [2] Murchie S.L. et al. (2009) JGR, 114. [3] Eberl D.D. et al. (1984) PTRS London A, 311, 241. [4] Kloprogge J.T. et al. (1999) CCM, 47, 529. [5] Velbel M.A. & W.W. Barker (2008) CCM, 56, 111. [6] Parfitt R. L. (2009) ClayMiner. 44, 135. [7] Bishop J.L. & E.B. Rampe (2016) EPSL, 448, 42. [8] Rampe E. B. et al. (2012) Geol., 40. [9] Bish D.L. et al. (2013) Science, 341, 1238932. [10] Lee M. R. et al. (2015) MAPS, 50, 1362.

Intercalation and retention of carbon dioxide in a smectite clay promoted by interlayer cations.

PubMed

Michels, L; Fossum, J O; Rozynek, Z; Hemmen, H; Rustenberg, K; Sobas, P A; Kalantzopoulos, G N; Knudsen, K D; Janek, M; Plivelic, T S; da Silva, G J

2015-03-05

A good material for CO2 capture should possess some specific properties: (i) a large effective surface area with good adsorption capacity, (ii) selectivity for CO2, (iii) regeneration capacity with minimum energy input, allowing reutilization of the material for CO2 adsorption, and (iv) low cost and high environmental friendliness. Smectite clays are layered nanoporous materials that may be good candidates in this context. Here we report experiments which show that gaseous CO2 intercalates into the interlayer nano-space of smectite clay (synthetic fluorohectorite) at conditions close to ambient. The rate of intercalation, as well as the retention ability of CO2 was found to be strongly dependent on the type of the interlayer cation, which in the present case is Li(+), Na(+) or Ni(2+). Interestingly, we observe that the smectite Li-fluorohectorite is able to retain CO2 up to a temperature of 35°C at ambient pressure, and that the captured CO2 can be released by heating above this temperature. Our estimates indicate that smectite clays, even with the standard cations analyzed here, can capture an amount of CO2 comparable to other materials studied in this context.

Di-tri-octahedral smectite for the prevention of post-operative diarrhea in equids with surgical disease of the large intestine: results of a randomized clinical trial.

PubMed

Hassel, Diana M; Smith, Phoebe A; Nieto, Jorge E; Beldomenico, Pablo; Spier, Sharon J

2009-11-01

The aim of this study was to evaluate the effects of a commercially available di-tri-octahedral (DTO) smectite product on clinical signs and prevalence of post-operative diarrhea in horses with colic associated with disease of the large intestine. Sixty-seven horses with surgical disease of the large intestine were randomly assigned to be treated with DTO smectite (n=37; 0.5 kg via nasogastric intubation every 24 h for 3 days post-operatively) or a placebo (n=30). The effect of treatment on fecal scores and clinical and hematological parameters, including heart rate, mucous membrane color, temperature, total white blood cell count, total neutrophil count and total plasma protein values, were determined. Horses treated with DTO smectite had a significant reduction in the prevalence of post-operative diarrhea (10.8%), compared with controls (41.4%). A significant improvement in mucous membrane color was observed 72 h post-operatively in horses receiving treatment, compared with placebo. Administration of DTO smectite to colic patients with disease of the large intestine reduced the occurrence of diarrhea in the early post-operative period.

Smectite Formation from Basaltic Glass Under Acidic Conditions on Mars

NASA Technical Reports Server (NTRS)

Peretyazhko, T. S.; Sutter, B.; Morris, R. V.; Agresti, D. G.; Le, L.; Ming, D. W.

2015-01-01

Massive deposits of phyllosilicates of the smectite group, including Mg/Fe-smectite, have been identified in Mars's ancient Noachian terrain. The observed smectite is hypothesized to form through aqueous alteration of basaltic crust under neutral to alkaline pH conditions. These pH conditions and the presence of a CO2-rich atmosphere suggested for ancient Mars were favorable for the formation of large carbonate deposits. However, the detection of large-scale carbonate deposits is limited on Mars. We hypothesized that smectite deposits may have formed under acidic conditions that prevented carbonate precipitation. In this work we investigated formation of saponite at a pH of approximately 4 from Mars-analogue synthetic Adirondack basaltic glass of composition similar to Adirondack class rocks located at Gusev crater. Hydrothermal (200º Centigrade) 14 day experiments were performed with and without 10 millimoles Fe(II) or Mg under anoxic condition [hereafter denoted as anoxic_Fe, anoxic_Mg and anoxic (no addition of Fe(II) or Mg)] and under oxic condition [hereafter denoted as oxic (no addition of Fe(II) or Mg)]. Characterization and formation conditions of the synthesized saponite provided insight into the possible geochemical conditions required for saponite formation on Mars.

Intercalation and Retention of Carbon Dioxide in a Smectite Clay promoted by Interlayer Cations

PubMed Central

Michels, L.; Fossum, J. O.; Rozynek, Z.; Hemmen, H.; Rustenberg, K.; Sobas, P. A.; Kalantzopoulos, G. N.; Knudsen, K. D.; Janek, M.; Plivelic, T. S.; da Silva, G. J.

2015-01-01

A good material for CO2 capture should possess some specific properties: (i) a large effective surface area with good adsorption capacity, (ii) selectivity for CO2, (iii) regeneration capacity with minimum energy input, allowing reutilization of the material for CO2 adsorption, and (iv) low cost and high environmental friendliness. Smectite clays are layered nanoporous materials that may be good candidates in this context. Here we report experiments which show that gaseous CO2 intercalates into the interlayer nano-space of smectite clay (synthetic fluorohectorite) at conditions close to ambient. The rate of intercalation, as well as the retention ability of CO2 was found to be strongly dependent on the type of the interlayer cation, which in the present case is Li+, Na+ or Ni2+. Interestingly, we observe that the smectite Li-fluorohectorite is able to retain CO2 up to a temperature of 35°C at ambient pressure, and that the captured CO2 can be released by heating above this temperature. Our estimates indicate that smectite clays, even with the standard cations analyzed here, can capture an amount of CO2 comparable to other materials studied in this context. PMID:25739522

Role of microbes in the smectite-to-illite reaction

NASA Technical Reports Server (NTRS)

Kim, Jinwook; Dong, Hailiang; Seabaugh, Jennifer; Newell, Steven W.; Eberl, Dennis D.

2004-01-01

Temperature, pressure, and time have been thought to control the smectite-to-illite (S-I) reaction, an important diagenetic process used for petroleum exploration. We demonstrated that microorganisms can promote the S-I reaction by dissolving smectite through reduction of structural Fe(III) at room temperature and 1 atmosphere within 14 days. This reaction typically requires conditions of 300 degrees to 350 degrees C, 100 megapascals, and 4 to 5 months in the absence of microbial activity. These results challenge the conventional concept of the S-I reaction and of reaction kinetic models.

Isotopic studies of epigenetic features in metalliferous sediment, Atlantis II Deep, Red Sea

USGS Publications Warehouse

Zierenberg, Robert A.; Shanks, Wayne C.

1988-01-01

The unique depositional environment of the Atlantis II Deep brine pool in the Red Sea produces a stratiform metalliferous deposit of greater areal extent than deposits formed by buoyant-plume systems typical of the midocean ridges because of much more efficient metal entrapment. Isotopic analyses of strontium, sulfur, carbon, and oxygen from the metalliferous sediments indicate that three major sources contribute dissolved components to the hydrothermal system: seawater, Miocene evaporites, and rift-zone basalt. An areally restricted magnetite-hematite-pyroxene assemblage formed at high temperatures, possibly in response to hydrothermal convection initiated by intrusion of basalt into the metalliferous sediment. A correlation between smectite Fe/(Fe+Mg) ratios and oxygen isotope temperatures suggests that smectite is a potentially important chemical geothermometer, and confirms geochemical calculations indicating that Mg-rich smectite is more stable than Fe-rich smectite at elevated temperatures.

Water and Sediment Quality in the Yukon River Basin, Alaska, During Water Year 2005

DTIC Science & Technology

2007-01-01

Disordered Kaolinite 0.6 0.5 0.4 0.7 0.6 1.0 0.4 Ferruginous smectite 7.4 9.5 6.1 4.9 9.4 10.6 12.4 Illite + Smectite 6.8 4.8 5.2 6.6 6.6 5.5 4.9...64.7 Clays: Goethite 0.1 0.1 0.3 0.1 0.1 0.3 0.1 Disordered Kaolinite 0.6 0.9 0.3 0.7 0.9 0.6 0.7 Ferruginous smectite 7.0 6.8 7.1...7.9 7.6 16.4 15.7 Illite + Smectite 10.2 7.7 8.1 7.9 6.8 1.2 3.2 Chlorite 8.0 9.5 9.6 9.4 10.7 10.8 12.2 Muscovite (2M1) 4.1 6.0 5.2 4.8 4.1 4.8

Organofunctionalized Amazon smectite for dye removal from aqueous medium--kinetic and thermodynamic adsorption investigations.

PubMed

Guerra, Denis L; Silva, Weber L L; Oliveira, Helen C P; Viana, Rúbia R; Airoldi, Claudio

2011-02-15

The objective of this study is to examine the adsorption behavior of Sumifix Brilliant Orange 3R textile dye from aqueous solution on smectite sample, an abundant Amazon clay. The original smectite clay mineral has been collected from Amazon region, Brazil. The compound 2-aminomethylpyridine was anchored onto smectite surface by heterogeneous route. The ability of these materials to remove the Sumifix Brilliant Orange 3R textile dye from aqueous solution was followed by a series of adsorption isotherms, using a batchwise process. The maximum number of moles adsorbed was determined to be 1.26 and 2.07 mmol g(-1) for natural and modified clay samples, respectively. The energetic effects caused by dye cations adsorption were determined through calorimetric titrations. Thermodynamics indicated the existence of favorable conditions for such dye-nitrogen interactions. Copyright © 2010. Published by Elsevier B.V.

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

USGS Publications Warehouse

Glanzman, Richard K.; Rytuba, James J.

1979-01-01

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

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.

Redox properties of structural Fe in clay minerals: 3. Relationships between smectite redox and structural properties.

PubMed

Gorski, Christopher A; Klüpfel, Laura E; Voegelin, Andreas; Sander, Michael; Hofstetter, Thomas B

2013-01-01

Structural Fe in clay minerals is an important redox-active species in many pristine and contaminated environments as well as in engineered systems. Understanding the extent and kinetics of redox reactions involving Fe-bearing clay minerals has been challenging due to the inability to relate structural Fe(2+)/Fe(total) fractions to fundamental redox properties, such as reduction potentials (EH). Here, we overcame this challenge by using mediated electrochemical reduction (MER) and oxidation (MEO) to characterize the fraction of redox-active structural Fe (Fe(2+)/Fe(total)) in smectites over a wide range of applied EH-values (-0.6 V to +0.6 V). We examined Fe(2+)/Fe(total )- EH relationships of four natural Fe-bearing smectites (SWy-2, SWa-1, NAu-1, NAu-2) in their native, reduced, and reoxidized states and compared our measurements with spectroscopic observations and a suite of mineralogical properties. All smectites exhibited unique Fe(2+)/Fe(total) - EH relationships, were redox active over wide EH ranges, and underwent irreversible electron transfer induced structural changes that were observable with X-ray absorption spectroscopy. Variations among the smectite Fe(2+)/Fe(total) - EH relationships correlated well with both bulk and molecular-scale properties, including Fe(total) content, layer charge, and quadrupole splitting values, suggesting that multiple structural parameters determined the redox properties of smectites. The Fe(2+)/Fe(total) - EH relationships developed for these four commonly studied clay minerals may be applied to future studies interested in relating the extent of structural Fe reduction or oxidation to EH-values.

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

Role of interlayer hydration in lincomycin sorption by smectite clays.

PubMed

Wang, Cuiping; Ding, Yunjie; Teppen, Brian J; Boyd, Stephen A; Song, Cunyi; Li, Hui

2009-08-15

Lincomycin, an antibiotic widely administered as a veterinary medicine, is frequently detected in water. Little is known about the soil-water distribution of lincomycin despite the fact that this is a major determinant of its environmental fate and potential for exposure. Cation exchange was found to be the primary mechanism responsible for lincomycin sorption by soil clay minerals. This was evidenced by pH-dependent sorption, and competition with inorganic cations for sorptive sites. As solution pH increased, lincomycin sorption decreased. The extent of reduction was consistent with the decrease in cationic lincomycin species in solution. The presence of Ca2+ in solution diminished lincomycin sorption. Clay interlayer hydration status strongly influenced lincomycin adsorption. Smectites with the charge deficit from isomorphic substitution in tetrahedral layers (i.e., saponite) manifest a less hydrated interlayer environment resulting in greater sorption than that by octahedrally substituted clays (i.e., montmorillonite). Strongly hydrated exchangeable cations resulted in a more hydrated clay interlayer environment reducing sorption in the order of Ca- < K- < Cs-smectite. X-ray diffraction revealed that lincomycin was intercalated in smectite clay interlayers. Sorption capacity was limited by clay surface area rather than by cation exchange capacity. Smectite interlayer hydration was shown to be a major, yet previously unrecognized, factor influencing the cation exchange process of lincomycin on aluminosilicate mineral surfaces.

Organo-modified anionic clays into polymer compared to smectite-type nanofiller: potential applications of the nanocomposites.

PubMed

Leroux, Fabrice

2006-02-01

The scope of the article is to provide the state of the art concerning the utilization of Layered Double Hydroxide (LDH) materials in polymer nanocomposite and to enlight their potential application and even advantage in comparison to smectite-type materials. A particular attention is paid on the synthetic procedures for the elaboration of polymer nanocomposite taking poly(styrene), poly(imide), poly(methylmethacrylate) and epoxy resin as examples. Lipophilization of the inorganic platelets used to decrease the surface polarity may be achieved either with a surfactant molecule or a surfactant monomer molecule, giving rise to reactive hybrid filler. The state of dispersion of the inorganic platelets, i.e., intercalated versus exfoliated structure is discussed. LDH-based nanocomposites present mechanical properties, such as the tensile modulus and elongation at break, always greater in comparison to virgin polymer, but also compete well with smectite-type filler. For epoxy nanocomposite, the relative gain using LDH nanofiller is superior to smectite-type filler. In both types of nanocomposites using either LDH or smectite-type nanofiller, mixed intercalated-exfoliated structure is generally met. Dispersion of LDH nanoplatelets should emerge well as flame-retardant materials and as polymer electrolyte, but may also find application in topical domains such as in sun radiation absorption.

Coupled deformation and dehydration processes in smectite-rich sediments constrained by laboratory experiments

NASA Astrophysics Data System (ADS)

Huepers, Andre; Kopf, Achim J.

2013-04-01

Subduction zones play a central role in the geological activity of the earth which is expressed as devastating events such as earthquakes, tsunamis and explosive volcanism. Many processes that lead to such catastrophic behavior are driven by fluids, which in turn affect the rock mechanical behavior. The kinetic reaction of hydrous smectite to illite is widely accepted as a fluid source in subduction zone forearcs that also affects the mechanical state of subduction zone sediments. The released fluids are characterized by low-chlorinity and high volatile content. Also, previous workers demonstrated in uniaxial deformation tests that smectite partially dehydrates with increasing effective stress. To shed light on this process we performed uniaxial deformation experiments on smectite-rich samples from the Nankai and Costa Rica subduction zones. Experiments were conducted at temperatures of up to 100°C under constant rate of strain and effective stresses of up to ~100MPa. Fluids expelled during the experiments were analyzed for major and minor element content. The fluids are characterized by fluid-freshening and increasing volatile content that starts at ~1.3MPa effective stress. During the course of the experiments the smectite interlayer water content decreases from 27 wt-% to 20 wt-%. The released interlayer water comprises up to 17% of the total fluid volume released from the consolidating sediment. The onset of fluid freshening is characterized by a change in deformation behavior of the samples. The porosity decrease with increasing effective stress is smaller at effective stresses greater 1.3MPa. We propose that dehydration of the low permeable smectite leads to excess pore pressures in the sample, which causes a load transfer from the solid phase to the pore fluid.

Role of water in the smectite-to-illite reaction

USGS Publications Warehouse

Whitney, Gene

1990-01-01

A series of hydrothermal experiments was performed to determine the effect of fluid abundance on the reaction of smectite to illite. Experiments were conducted on K-saturated montmorillonite (<0.1-µm fraction) in a closed system at 250° to 400°C using run times of 1, 7, 14, 30, and 60 days at 100 MPa (1 kbar) pressure. In fluid-deficient systems (pore spaces not saturated), the rate and extent of illitization was significantly inhibited. A rock:water ratio of 20:1 (mass:mass) produced an R0 illite/smectite (I/S) having 82% smectite layers after 60 days at 250°C, whereas a rock:water ratio of 1:1 produced an I/S having 57% smectite layers under the same conditions. The effect became less pronounced at higher temperatures, with the 20:1 and the 1:1 experimental products differing by only 11% expandability at 400°C after 60 days. In addition, the low-fluid experiments produced fewer crystalline byproducts (quartz, cristobalite, chlorite) than did the fluid-rich runs, and the I/S was more difficult to disperse and orient in the fluid-deficient samples, suggesting enhanced cementation at grain contacts or the production of particle morphologies that did not lend themselves to orientation. The difference in reactivity of the smectite and I/S as a function of water content appears to be attributable to the reduced capacity for low volumes of water to mediate the dissolution, solute transport, and precipitation reactions that make up the series of reactions collectively termed illitization. Of these variables, solute transport is likely to be affected most by reduction of fluid.

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.

Influence of pH, layer charge location and crystal thickness distribution on U(VI) sorption onto heterogeneous dioctahedral smectite.

PubMed

Guimarães, Vanessa; Rodríguez-Castellón, Enrique; Algarra, Manuel; Rocha, Fernando; Bobos, Iuliu

2016-11-05

The UO2(2+) adsorption on smectite (samples BA1, PS2 and PS3) with a heterogeneous structure was investigated at pH 4 (I=0.02M) and pH 6 (I=0.2M) in batch experiments, with the aim to evaluate the influence of pH, layer charge location and crystal thickness distribution. Mean crystal thickness distribution of smectite crystallite used in sorption experiments range from 4.8nm (sample PS2), to 5.1nm (sample PS3) and, to 7.4nm (sample BA1). Smaller crystallites have higher total surface area and sorption capacity. Octahedral charge location favor higher sorption capacity. The sorption isotherms of Freundlich, Langmuir and SIPS were used to model the sorption experiments. The surface complexation and cation exchange reactions were modeled using PHREEQC-code to describe the UO2(2+) sorption on smectite. The amount of UO2(2+) adsorbed on smectite samples decreased significantly at pH 6 and higher ionic strength, where the sorption mechanism was restricted to the edge sites of smectite. Two binding energy components at 380.8±0.3 and 382.2±0.3eV, assigned to hydrated UO2(2+) adsorbed by cation exchange and by inner-sphere complexation on the external sites at pH 4, were identified after the U4f7/2 peak deconvolution by X-photoelectron spectroscopy. Also, two new binding energy components at 380.3±0.3 and 381.8±0.3eV assigned to AlOUO2(+) and SiOUO2(+) surface species were observed at pH 6. Copyright © 2016 Elsevier B.V. All rights reserved.

Evaluation of in vitro properties of di-tri-octahedral smectite on clostridial toxins and growth.

PubMed

Weese, J S; Cote, N M; deGannes, R V G

2003-11-01

Clostridial colitis and endotoxaemia of intestinal origin are significant causes of morbidity and mortality in horses. Intestinal adsorbents are available for treatment of these conditions; however, little information exists supporting their use. To evaluate the ability of di-tri-octahedral smectite to bind to Clostridium difficile toxins A and B, C. perfringens enterotoxin and endotoxin, inhibit clostridial growth and the actions of metronidazole in vitro. Clostridium difficile toxins, C. perfringens enterotoxin and endotoxin were mixed with serial dilutions of di-tri-octahedral smectite, then tested for the presence of clostridial toxins or endotoxin using commercial tests. Serial dilutions of smectite were tested for the ability to inhibit growth of C. perfringens in culture broth, and to interfere with the effect of metronidazole on growth of C. perfringens in culture broth. Clostridium difficile toxins A and B, and C. perfringens enterotoxin were completely bound at dilutions of 1:2 to 1:16. Partial binding of C. difficile toxins occurred at dilutions up to 1:256 while partial binding of C. perfringens enterotoxin occurred up to a dilution of 1:128. Greater than 99% binding of endotoxin occurred with dilutions 1:2 to 1:32. No inhibition of growth of C. difficile or C. perfringens was present at any dilution, and there was no effect on the action of metronidazole. Di-tri-octahedral smectite possesses the ability to bind C. difficile toxins A and B, C. perfringens enterotoxin and endotoxin in vivo while having no effect on bacterial growth or the action of metronidazole. In vivo studies are required to determine whether di-tri-octahedral smectite might be a useful adjunctive treatment of clostridial colitis and endotoxaemia in horses.

Thermal Transport in Self-Assembled Nanostructures

DTIC Science & Technology

2011-01-01

2:1 smectite clay family which can be exfoliated into large aspect ratio (>1000:1) ~1 nm thick sheets (Figure 4a). Each montmorillonite sheet...measurements. While it was suggested earlier that study of the thermal transport properties of similarly modified smectite clays other than montmorillonite

H2O Adsorption on Smectites: Application to the Diurnal Variation of H2O in the Martian Atmosphere

NASA Technical Reports Server (NTRS)

Zent, Aaron P.; Howard, J.; Quinn, R. C.

2000-01-01

Observations of the Martian planetary boundary layer lead to interpretations that are baffling and contradictory. In this paper, we specifically address the question of whether or not water vapor finds a substantial diurnal reservoir in the Martian regolith. To address this issue, we have measured H2O adsorption kinetics on SWy-1, a Na-rich montmorillonite from Wyoming. The highest-temperature (273 K) data equilibrates rapidly. Data gathered at realistic H2O partial pressures and temperatures appropriate to early morning show two phenomena that preclude a significant role for smectites in diurnally exchanging a large column abundance. First, the equilibration timescale is longer than a sol. Second, the equilibrium abundances are a small fraction of that predicted by earlier adsorption isotherms. The explanation for this phenomenon is that smectite clay actually increases its surface area as a function of adsorptive coverage. At Mars-like conditions, we show that the interlayer sites of smectites are likely to be unavailable.

Links between clay transformation and earthquakes along the Costa Rican subduction margin

NASA Astrophysics Data System (ADS)

Lauer, Rachel M.; Saffer, Demian M.; Harris, Robert N.

2017-08-01

We investigate the depth distribution of smectite clay transformation and its along-strike variability at the Middle America Trench offshore Costa Rica. We take advantage of recent well-constrained thermal models that refine our understanding of the margin's thermal structure and which capture significant along-strike variability. Using these thermal models, together with sediment compositions defined by drilling, we compute the distribution of smectite transformation and associated fluid production. We show that the hypocenters of large (M > 6.9) well-located megathrust earthquakes lie consistently downdip of peak fluid production. We suggest that silica cementation associated with smectite transformation promotes lithification and slip-weakening behavior that, in combination with declining fluid pressures, facilitate the initiation of unstable slip. The earthquake ruptures extend updip into the region of peak reaction, possibly due to excess pore pressures that facilitate their propagation. These results are consistent with the hypothesis that smectite transformation contributes to the onset of stick-slip behavior and acts as an important control on earthquake nucleation and propagation.

Analyte-Size-Dependent Ionization and Quantification of Monosaccharides in Human Plasma Using Cation-Exchanged Smectite Layers.

PubMed

Ding, Yuqi; Kawakita, Kento; Xu, Jiawei; Akiyama, Kazuhiko; Fujino, Tatsuya

2015-08-04

Smectite, a synthetic inorganic polymer with a saponite structure, was subjected to matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS). Typical organic matrix molecules 2,4,6-trihydroxyacetophenone (THAP) and 2,5-dihydroxybenzoic acid (DHBA) were intercalated into the layer spacing of cation-exchanged smectite, and the complex was used as a new matrix for laser desorption/ionization mass spectrometry. Because of layer spacing limitations, only a small analyte that could enter the layer and bind to THAP or DHBA could be ionized. This was confirmed by examining different analyte/matrix preparation methods and by measuring saccharides with different molecular sizes. Because of the homogeneous distribution of THAP molecules in the smectite layer spacing, high reproducibility of the analyte peak intensity was achieved. By using isotope-labeled (13)C6-d-glucose as the internal standard, quantitative analysis of monosaccharides in pretreated human plasma sample was performed, and the value of 8.6 ± 0.3 μg/mg was estimated.

Lithologic Control on Secondary Clay Mineral Formation in the Valles Caldera, New Mexico

NASA Astrophysics Data System (ADS)

Caylor, E.; Rasmussen, C.; Dhakal, P.

2015-12-01

Understanding the transformation of rock to soil is central to landscape evolution and ecosystem function. The objective of this study was to examine controls on secondary mineral formation in a forested catchment in the Catalina-Jemez CZO. We hypothesized landscape position controls the type of secondary minerals formed in that well-drained hillslopes favor Si-poor secondary phases such as kaolinite, whereas poorly drained portions of the landscape that collect solutes from surrounding areas favor formation of Si-rich secondary phases such as smectite. The study focused on a catchment in Valles Caldera in northern New Mexico where soils are derived from a mix of rhyolitic volcanic material, vegetation includes a mixed conifer forest, and climate is characterized by a mean annual precipitation of ~800 mm yr-1 and mean annual temperature of 4.5°C. Soils were collected at the soil-saprolite boundary from three landscape positions, classified as well drained hillslope, poorly drained convergent area, and poorly drained hill slope. Clay fractions were isolated and analyzed using a combination of quantitative and qualitative x-ray diffraction (XRD) analyses and thermal analysis. Quantitative XRD of random powder mounts indicated the presence of both primary phases such as quartz, and alkali and plagioclase feldspars, and secondary phases that include illite, Fe-oxyhydroxides including both goethite and hematite, kaolinite, and smectite. The clay fractions were dominated by smectite ranging from 36-42%, illite ranging from 21-35%, and kaolinite ranging from 1-8%. Qualitative XRD of oriented mounts confirmed the presence of smectite in all samples, with varying degrees of interlayering and interstratification. In contrast to our hypothesis, results indicated that secondary mineral assemblage was not strongly controlled by landscape position, but rather varied with underlying variation in lithology. The catchment is underlain by a combination of porphorytic rhyolite and hydrothermally altered rhyolitic tuff, with an intrusion of Paleozoic sandstone. Smectite content was generally greater in areas underlain by the tuff and likely represent a combination of both diagenic smectite formed by hydrothermal alteration of volcanic glass and authigenic smectites formed in the soils via chemical weathering.

Comparison of the Composition of the Tempel 1 Ejecta to the Dust in Comet C/Hale-Bopp 1995 O1 and YSO HD 100546

DTIC Science & Technology

2007-01-01

niningerits.Blue phyllosililcates (near the sulfldes), represented here by the smectite nontronite. (b) Spectrum after subtraction of the best-fit silicate...1.70 Smectite nontrmite 0.14 2.3 496 0.07 340 3.76 Nasn3Fe2(Si.AjMO 0j(OH)2-3H20 Carbonats Mageuile (MgC0 3 ) 0.030 3.1 84 0.11 340 1.30 Siderite...any other comet, was optically thick near the nucleus due to its Phyllosilicates (as represented by the smectite nontron- huge rate of emission of

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

EPA Science Inventory

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

Exchangeable cations-mediated photodegradation of polycyclic aromatic hydrocarbons (PAHs) on smectite surface under visible light.

PubMed

Jia, Hanzhong; Li, Li; Chen, Hongxia; Zhao, Yue; Li, Xiyou; Wang, Chuanyi

2015-04-28

Clay minerals saturated with different exchangeable cations are expected to play various roles in photodegradation of polycyclic aromatic hydrocarbons (PAHs) via direct and/or indirect pathways on clay surfaces. In the present study, anthracene and phenanthrene were selected as molecule probes to investigate the roles of exchangeable cations on their photodegradation under visible light irradiation. For five types of cation-modified smectite clays, the photodegradation rate of anthracene and phenanthrene follows the order: Fe(3+)>Al(3+)>Cu(2+)>Ca(2+)>K(+)>Na(+), which is consistent with the binding energy of cation-π interactions between PAHs and exchangeable cations. The result suggests that PAHs photolysis rate depends on cation-π interactions on clay surfaces. Meanwhile, the deposition of anthracene at the Na(+)-smectite and K(+)-smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe(3+), Al(3+), and Cu(2+) are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O2(-) , which initiate the transformation of PAHs. The present work provides valuable insights into understanding the transformation and fate of PAHs in the natural soil environment and sheds light on the development of technologies for contaminated land remediation. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Composition, structure, and properties of iron-rich nontronites of different origins

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

Palchik, N. A., E-mail: nadezhda@igm.nsc.ru; Grigorieva, T. N.; Moroz, T. N.

2013-03-15

The composition, structure, and properties of smectites of different origins have been studied by X-ray diffraction, IR spectroscopy, scanning electron microscopy, and microprobe analysis. The results showed that nontronites of different origins differ in composition, properties, morphology, and IR spectroscopic characteristics. Depending on the degree of structural order and the negative charge of iron-silicate layers in nontronites, the shift of the 001 reflection to smaller angles as a result of impregnation with ethylene glycol (this shift is characteristic of the smectite group) occurs differently. The calculated values of the parameter b (from 9.11 to 9.14A) are valid for the extrememore » terms of dioctahedral smectite representatives: nontronites.« less

Distribution and origin of authigenic smectite clays in Cape Roberts Project Core 3, Victoria Land Basin, Antarctica

USGS Publications Warehouse

Priestas, A.W.; Wise, S.W.

2007-01-01

Of some 800 m of lower Oligocene marine sediments cored continuously from the seafloor in the Victoria Land Basin of Antarctica at Cape Roberts Site CRP-3, the lower 500 m exhibit authigenic smectite clay coats on shallow-water sandstone grains. A scanning electron microscope/EDS study of 46 fracture sections confirms that the distribution of the clay coats through the unit is not uniform or evenly distributed, but rather varies with depth, original porosity, and the kinds and abundance of source materials. Our results suggest that smectite emplacement resulted from in-situ, low-temperature burial diagenesis rather than hydrothermal or fault-focused thermobaric fluids.

Changes in particle morphology during illitization: An experimental study

USGS Publications Warehouse

Whitney, Gene; Velde, Bruce

1993-01-01

Smectite was reacted at several temperatures between 200°C and 500°C to produce interstratified illite/smectite (I/S) with different proportions of expandable layers. Dispersed and sedimented products were examined using a transmission electron microscope. Particle size and aspect ratio showed no systematic change as a function of reaction extent during R0 illitization. However, particles exhibited rounded edges during the early stages of the reaction, suggesting some dissolution of primary smectite. Additionally, increasing particle contrast in the electron beam suggests thickening of particles with increasing reaction extent. The thickening of particles is thought to be produced by the nucleation and precipitation of secondary illite layers on primary smectite layers. In the most extensively reacted I/S, particles have become aggregated into clumps or quasicrystals by lateral growth of illite layers. Internal uniformity of crystallographic alignment of individual growing crystals within each aggregate was reflected in the increasing frequency of 60° and 120° interfacial angles within each aggregate. In highly illitic I/S, these aggregates took on an overall euhedral form and became crystallographically contiguous, producing single crystal electron diffraction patterns.

Smectite diagenesis, pore-water freshening, and fluid flow at the toe of the Nankai wedge

USGS Publications Warehouse

Brown, K.M.; Saffer, D.M.; Bekins, B.A.

2001-01-01

The presence of low-chloride fluids in the lowermost sediments drilled at Ocean Drilling Program Site 808, at the Nankai accretionary wedge, has been considered as prime evidence for long-distance, lateral fluid flow from depth. Here, we re-evaluate the potential role of in situ reaction of smectite (S) to illite (I) in the genesis of this low chloride anomaly. This reaction is known to be occurring at Site 808, with both the S content and S to I ratio in the mixed layer clays decreasing substantially with depth. We show that the bulk of the chloride anomaly can generate by in situ clay dehydration, particularly if pre-reaction smectite abundances (Ai) approach ?? 10-15% of the bulk sediment. The Ai values, however, are not well constrained. At Ai values < 10-15%, an additional source of low-Cl fluid centered close to the de??collement could be required. Thus, there remains the important possibility that the observed low-Cl anomaly is a compound effect of both lateral flow and in situ smectite dehydration. ?? 2001 Elsevier Science B.V. All rights reserved.

Connecting the molecular scale to the continuum scale for diffusion processes in smectite-rich porous media.

PubMed

Bourg, Ian C; Sposito, Garrison

2010-03-15

In this paper, we address the manner in which the continuum-scale diffusive properties of smectite-rich porous media arise from their molecular- and pore-scale features. Our starting point is a successful model of the continuum-scale apparent diffusion coefficient for water tracers and cations, which decomposes it as a sum of pore-scale terms describing diffusion in macropore and interlayer "compartments." We then apply molecular dynamics (MD) simulations to determine molecular-scale diffusion coefficients D(interlayer) of water tracers and representative cations (Na(+), Cs(+), Sr(2+)) in Na-smectite interlayers. We find that a remarkably simple expression relates D(interlayer) to the pore-scale parameter δ(nanopore) ≤ 1, a constrictivity factor that accounts for the lower mobility in interlayers as compared to macropores: δ(nanopore) = D(interlayer)/D(0), where D(0) is the diffusion coefficient in bulk liquid water. Using this scaling expression, we can accurately predict the apparent diffusion coefficients of tracers H(2)0, Na(+), Sr(2+), and Cs(+) in compacted Na-smectite-rich materials.

Smectite clay--inorganic nanoparticle mixed suspensions: phase behaviour and rheology.

PubMed

Bailey, Louise; Lekkerkerker, Henk N W; Maitland, Geoffrey C

2015-01-14

Smectite clay minerals and their suspensions have long been of both great scientific and applications interest and continue to display a remarkable range of new and interesting behaviour. Recently there has been an increasing interest in the properties of mixed suspensions of such clays with nanoparticles of different size, shape and charge. This review aims to summarize the current status of research in this area focusing on phase behaviour and rheological properties. We will emphasize the rich range of data that has emerged for these systems and the challenges they present for future investigations. The review starts with a brief overview of the behaviour and current understanding of pure smectite clays and their suspensions. We then cover the work on smectite clay-inorganic nanoparticle mixed suspensions according to the shape and charge of the nanoparticles - spheres, rods and plates either positively or negatively charged. We conclude with a summary of the overarching trends that emerge from these studies and indicate where gaps in our understanding need further research for better understanding the underlying chemistry and physics.

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.

Diagenetic contrast of sandstones in hydrocarbon prospective Mesozoic rift basins (Ethiopia, UK, USA)

NASA Astrophysics Data System (ADS)

Wolela, A.

2014-11-01

Diagenetic studied in hydrocarbon-prospective Mesozoic rift basins were carried out in the Blue Nile Basin (Ethiopia), Ulster Basin (United Kingdom) and Hartford Basin (United States of America). Alluvial fan, single and amalgamated multistorey meandering and braided river, deep and shallow perennial lake, shallow ephemeral lake, aeolian and playa mud-flat are the prominent depositional environments. The studied sandstones exhibit red bed diagenesis. Source area geology, depositional environments, pore-water chemistry and circulation, tectonic setting and burial history controlled the diagenetic evolution. The diagenetic minerals include: facies-related minerals (calcrete and dolocrete), grain-coating clay minerals and/or hematite, quartz and feldspar overgrowths, carbonate cements, hematite, kaolinite, illite-smectite, smectite, illite, chlorite, actinolite, laumontite, pyrite and apatite. Diversity of diagenetic minerals and sequence of diagenetic alteration can be directly related to depositional environment and burial history of the basins. Variation in infiltrated clays, carbonate cements and clay minerals observed in the studied sandstones. The alluvial fan and fluviatile sandstones are dominated by kaolinite, illite calcite and ferroan calcite, whereas the playa and lacustrine sandstones are dominated by illite-smectite, smectite-chlorite, smectite, chlorite, dolomite ferroan dolomite and ankerite. Albite, pyrite and apatite are predominantly precipitated in lacustrine sandstones. Basaltic eruption in the basins modified mechanically infiltrated clays to authigenic clays. In all the studied sandstones, secondary porosity predominates over primary porosity. The oil emplacement inhabited clay authigenesis and generation of secondary porosity, whereas authigenesis of quartz, pyrite and apatite continued after oil emplacement.

Hydrated mineral stratigraphy of Ius Chasma, Valles Marineris

USGS Publications Warehouse

Roach, L.H.; Mustard, J.F.; Swayze, G.; Milliken, R.E.; Bishop, J.L.; Murchie, S.L.; Lichtenberg, K.

2010-01-01

New high-resolution spectral and morphologic imaging of deposits on walls and floor of Ius Chasma extend previous geomorphic mapping, and permit a new interpretation of aqueous processes that occurred during the development of Valles Marineris. We identify hydrated mineralogy based on visible-near infrared (VNIR) absorptions. We map the extents of these units with CRISM spectral data as well as morphologies in CTX and HiRISE imagery. Three cross-sections across Ius Chasma illustrate the interpreted mineral stratigraphy. Multiple episodes formed and transported hydrated minerals within Ius Chasma. Polyhydrated sulfate and kieserite are found within a closed basin at the lowest elevations in the chasma. They may have been precipitates in a closed basin or diagenetically altered after deposition. Fluvial or aeolian processes then deposited layered Fe/Mg smectite and hydrated silicate on the chasma floor, postdating the sulfates. The smectite apparently was weathered out of Noachian-age wallrock and transported to the depositional sites. The overlying hydrated silicate is interpreted to be an acid-leached phyllosilicate transformed from the underlying smectite unit, or a smectite/jarosite mixture. The finely layered smectite and massive hydrated silicate units have an erosional unconformity between them, that marks a change in surface water chemistry. Landslides transported large blocks of wallrock, some altered to contain Fe/Mg smectite, to the chasma floor. After the last episode of normal faulting and subsequent landslides, opal was transported short distances into the chasma from a few m-thick light-toned layer near the top of the wallrock, by sapping channels in Louros Valles. Alternatively, the material was transported into the chasma and then altered to opal. The superposition of different types of hydrated minerals and the different fluvial morphologies of the units containing them indicate sequential, distinct aqueous environments, characterized by alkaline, then circum-neutral, and finally very acidic surface or groundwater chemistry. ?? 2009 Elsevier Inc. All rights reserved.

Formation of Fe/mg Smectite Under Acidic Conditions from Synthetic Adirondack Basaltic Glass: an Analog to Fe/mg Smectite Formation on Mars

NASA Technical Reports Server (NTRS)

Sutter, B.; Peretyazhko, T.; Morris, R. V.; Ming, D. W.

2014-01-01

Smectite has been detected as layered material hundreds of meters thick, in intracrater depositional fans, in plains sediments, and deposits at depth on Mars. If early Mars hosted a dense CO2 atmosphere, then extensive carbonate should have formed in the neutral/alkaline conditions expected for smectite formation. However, large carbonate deposits on Mars have not been discovered. Instead of neutral to moderately alkaline conditions, early Mars may have experienced mildly acidic conditions that allowed for Fe/Mg smectite formation but prevented widespread carbonate formation. The objective of this work is to demonstrate that Fe(II)/Mg saponite and nontronite can form in mildly acidic solutions (e.g., pH 4). Synthetic basaltic glass (< 53 microns) of Adirondack rock class composition was exposed to pH 4 (acetic acid buffer) and N2 purged (anoxic) solutions amended with 0 and 10 mM Mg or Fe(II). Basaltic glass in these solutions was heated to 200 C in batch reactors for 1, 7, and 14 days. X-ray diffraction analysis of reacted materials detected the presence of phyllosilicates as indicated by a approx. 15.03-15.23Angstroms (001) peak. Smectite was confirmed as the phyllosilicate after treatments with glycerol and KCl and heating to 550 C. Trioctahedral saponite was confirmed by the presence of a 4.58 to 4.63 Angstroms (02l) and 1.54Angstroms (060) peaks. Saponite concentration was highest, as indicated by XRD peak intensity, in the 10 mM Mg treatment followed by the 0 mM and then 10 mM Fe(II) treatments. This order of sapontite concentration suggests that Fe(II) additions may have a role in slowing the kinetics of saponite formation relative to the other treatments. Nontronite synthesis was attempted by exposing Adirondack basaltic glass to pH 4 oxic solutions (without N2 purge) at 200 C for 14 days. X-ray diffraction analysis indicated that mixtures of trioctahedral (saponite) and dioctahedral (nontronite) may have formed in these experiments based on the 02l and 060 peaks. Moessbauer analysis coupled with future experiments are planned to verify if nontronite can be formed under mildly acidic and oxic conditions. Results of this work demonstrate that acidic conditions could have occurred on an early Mars, which allowed for smectite formation but inhibited carbonate formation.

Intensity and duration of chemical weathering: An example from soil clays of the southeastern Koolau Mountains, Oahu, Hawaii

USGS Publications Warehouse

Johnsson, Mark J.; Ellen, Stephen D.; McKittrick, Mary Anne

1993-01-01

Orographic precipitation on the southern flank of the southeastern Koolau Mountains produces a pronounced precipitation gradient. The corresponding gradient in the intensity of the chemical weathering environment provides an opportunity to address the effects of varying chemical weathering intensity on the composition of clay-size weathering products in soils developed on basalt. In addition, little-modified remnants of the constructional surface of the Koolau Volcano, isolated by stream dissection, remain as facets on the southern ends of the parallel ridges of the study area. By comparing clay mineralogy of soils developed on these older geomorphic surfaces with those developed on the younger sharp-crested ridges and steep side slopes, the effects of weathering duration on clay mineralogy can also be addressed.Soil clays in this part of the Koolau Mountains are mineralogically complex; principal phases include smectite, kaolinite, and halloysite, but pure end member phases are uncommon. Rather, most phases contain some amount of mixed layering. Smectite may contain small (<5%) amounts of randomly interstratified halloysite. Similarly, kaolinite commonly contains a small proportion of halloysite interlayers. A complex halloysitic phase shows evidence of interstratification with both smectite and kaolinite. Nonphyllosilicates found in the clay fraction include gibbsite, goethite, rare quartz, and perhaps cristobalite.The gradient in precipitation is reflected in soil clay mineralogy by varying proportions of dominantly smectitic, kaolinitic, and halloysitic phases. In regions of relatively low precipitation (<2,000 mm/yr), soils are dominated by the smectitic and halloysitic phases. With increased precipitation (as much as ∼4,000 mm/yr), kaolinitic and halloysitic phases become the dominant clay minerals, and goethite and gibbsite become increasingly abundant.Older soils developed on geomorphic surfaces representing the original constructional surface of Koolau Volcano are markedly more leached than those from younger landscapes in the same precipitation regime. Although smectite may be present, kaolinite is the dominant phase, and accumulations of Fe and Ti occur in the uppermost soil levels. Enrichment of Zr and Ti in these soils, as compared to concentrations in the original basaltic parent material, indicates that as much as 75% of the parent material has been lost. Thus weathering duration may affect soil clay composition in the same way as weathering intensity.Because smectite and halloysite are expandable clay minerals, their presence in soils may decrease slope stability and influence the nature of slope processes. Soil avalanches occur on steep slopes throughout the study area, whereas slow-moving landslides appear to be restricted to gentler slopes in drier parts of the study area where smectite is abundant. The clay mineralogy of soils thus appears to influence the nature of slope processes in the southeastern Koolau Mountains.

MASS SPECTROMETRIC IDENTIFICATION OF AN AZOBENZENE DERIVATIVE PRODUCED BY SMECTITE-CATALYZED CONVERSION OF 3-AMINO-4-HYDROXPHENYLARSONIC ACID

EPA Science Inventory

We report here the first evidence of a possible mechanism for the formation of an azobenzene arsonic acid compound in the environment The compound was formed when 3-amino-4-hydroxyphenylarsonic acid (3-amino-HPAA) was added to aqueous suspensions of smectite clay The 3-amino-HPAA...

Smectite deposits in Marathon Valley, Endeavour Crater, Mars, identified using CRISM hyperspectral reflectance data

NASA Astrophysics Data System (ADS)

Fox, V. K.; Arvidson, R. E.; Guinness, E. A.; McLennan, S. M.; Catalano, J. G.; Murchie, S. L.; Powell, K. E.

2016-05-01

The ~100 m wide Marathon Valley crosscuts the Cape Tribulation rim segment of the 22 km diameter, Noachian-age Endeavour impact crater on Mars. Single-scattering albedo spectra retrieved from three Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) Full-Resolution Targeted (FRT, regularized to 18 m/pixel) and two Along Track Oversampled (ATO, regularized to 12 m/pixel) observations indicate the presence of Fe3+-Mg2+ smectite exposures located in Marathon Valley with combination vibration metal-OH absorption strength comparable to smectite spectral signatures in Mawrth Vallis. The Opportunity rover was directed to the exposures and documented the presence of Shoemaker formation impact breccias that have been isochemically altered, likely by fracture-controlled aqueous fluids.

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.

Intercalated theophylline-smectite hybrid for pH-mediated delivery.

PubMed

Trivedi, Vivek; Nandi, Uttom; Maniruzzaman, Mohammed; Coleman, Nichola J

2018-01-23

On the basis of their large specific surface areas, high adsorption and cation exchange capacities, swelling potential and low toxicity, natural smectite clays are attractive substrates for the gastric protection of neutral and cationic drugs. Theophylline is an amphoteric xanthine derivative that is widely used as a bronchodilator in the treatment of asthma and chronic obstructive pulmonary disease. This study considers the in vitro uptake and release characteristics of the binary theophylline-smectite system. The cationic form of theophylline was readily ion exchanged into smectite clay at pH 1.2 with a maximum uptake of 67 ± 2 mg g -1 . Characterisation of the drug-clay hybrid system by powder X-ray diffraction analysis, Fourier transform infrared spectroscopy, differential scanning calorimetry and scanning electron microscopy confirmed that the theophylline had been exclusively intercalated into the clay system in an amorphous form. The drug remained bound within the clay under simulated gastric conditions at pH 1.2; and the prolonged release of approximately 40% of the drug was observed in simulated intestinal fluid at pH 6.8 and 7.4 within a 2-h timeframe. The incomplete reversibility of the intercalation process was attributed to chemisorption of the drug within the clay lattice. These findings indicate that smectite clay is a potentially suitable vehicle for the safe passage of theophylline into the duodenum. Protection from absorption in the stomach and subsequent prolonged release in the small intestine are advantageous in reducing fluctuations in serum concentration which may impact therapeutic effect and toxicity.

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

DOE PAGES

Cygan, Randall T.; Daemen, Luke L.; Ilgen, Anastasia G.; ...

2015-11-16

The study of mineral–water interfaces is of great importance to a variety of applications including oil and gas extraction, gas subsurface storage, environmental contaminant treatment, and nuclear waste repositories. Understanding the fundamentals of that interface is key to the success of those applications. Confinement of water in the interlayer of smectite clay minerals provides a unique environment to examine the interactions among water molecules, interlayer cations, and clay mineral surfaces. Smectite minerals are characterized by a relatively low layer charge that allows the clay to swell with increasing water content. Montmorillonite and beidellite varieties of smectite were investigated to comparemore » the impact of the location of layer charge on the interlayer structure and dynamics. Inelastic neutron scattering of hydrated and dehydrated cation-exchanged smectites was used to probe the dynamics of the interlayer water (200–900 cm –1 spectral region) and identify the shift in the librational edge as a function of the interlayer cation. Molecular dynamics simulations of equivalent phases and power spectra, derived from the resulting molecular trajectories, indicate a general shift in the librational behavior with interlayer cation that is generally consistent with the neutron scattering results for the monolayer hydrates. Both neutron scattering and power spectra exhibit librational structures affected by the location of layer charge and by the charge of the interlayer cation. Furthermore, divalent cations (Ba 2+ and Mg 2+) characterized by large hydration enthalpies typically exhibit multiple broad librational peaks compared to monovalent cations (Cs + and Na +), which have relatively small hydration enthalpies.« less

The Crystal Structure of Illite/Smectite.

DTIC Science & Technology

1988-04-04

summarized from Tellier and Reynolds (1987). Figure 3 shows a comparison between experimental and calculated diffraction patterns for the ethylene glycol...PUBLICATIONS Tellier . K. and Reynolds, R. C. (1987) Calculation of one-dimensional X-ray diffraction profiles of interstratified illite/smectite as...Abst.) 24th Annual fMeet Clay Min. Soc., Socorro, N. M., p. 115 PARTICIPATING SCIENTIFIC PERSONNEL Kathleen Tellier : Dept. of Earth Sciences

Effect of radiation-induced amorphization on smectite dissolution.

PubMed

Fourdrin, C; Allard, T; Monnet, I; Menguy, N; Benedetti, M; Calas, G

2010-04-01

Effects of radiation-induced amorphization of smectite were investigated using artificial irradiation. Beams of 925 MeV Xenon ions with radiation dose reaching 73 MGy were used to simulate the effects generated by alpha recoil nuclei or fission products in the context of high level nuclear waste repository. Amorphization was controlled by X-ray diffraction, transmission electron microscopy, and Fourier transform infrared spectroscopy. An important coalescence of the smectite sheets was observed which lead to a loss of interparticle porosity. The amorphization is revealed by a loss of long-range structure and accompanied by dehydroxylation. The dissolution rate far-from-equilibrium shows that the amount of silica in solution is two times larger in the amorphous sample than in the reference clay, a value which may be enhanced by orders of magnitude when considering the relative surface area of the samples. Irradiation-induced amorphization thus facilitates dissolution of the clay-derived material. This has to be taken into account for the safety assessment of high level nuclear waste repository, particularly in a scenario of leakage of the waste package which would deliver alpha emitters able to amorphize smectite after a limited period of time.

Evidence for Smectite Clays from MSL SAM Analyses of Mudstone at Yellowknife Bay, Gale Crater, Mars

NASA Technical Reports Server (NTRS)

McAdam, Amy; Franz, Heather; Mahaffy, Paul R.; Eigenbrode, Jennifer L.; Stern, Jennifer C.; Brunner, Anna; Archer, Paul Douglas; Ming, Douglas W.; Morris, Richard V.; Atreya, Sushil K.

2013-01-01

Drilled samples of mudstone from the Sheepbed unit at Yellowknife Bay were analyzed by MSL instruments including the Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments in MSL's Analytical Laboratory. CheMin analyses revealed the first in situ X-ray diffraction based evidence of clay minerals on Mars, which are likely trioctahedral smectites (e.g., saponite) and comprise approx 20% of the mudstone sample (e.g., Bristow et al., this meeting). SAM analyses, which heated the mudstone samples to 1000 C and monitored volatiles evolved to perform in situ evolved gas analysis mass spectrometry (EGA-MS), resulted in a H2O trace exhibiting a wide evolution at temperatures < 500 C, and an evolution peak at higher temperatures near approx 750 C. The low temperature H2O evolution has many potential contributors, including adsorbed H2O, smectite interlayer H2O, and structural H2O/OH from bassanite and akaganeite (identified by CheMin) and H2O/OH from amorphous phases in the sample. The high temperature H2O is consistent with the evolution of H2O from the dehydroxylation of the smectite clay mineral. Comparison to EGA-MS data collected under SAM-like conditions on a variety of clay mineral reference materials indicate that a trioctahedral smectite, such as saponite, is most consistent with the high temperature H2O evolution observed. There may also be SAM EGA-MS evidence for a small high temperature H2O evolution from scoop samples from the Yellowknife Bay Rocknest sand shadow bedform. As in the mudstone samples, this evolution may indicate the detection of smectite clays, and the idea that minor clays may be present in Rocknest materials that could be expected to be at least partially derived from local sources is reasonable. But, because smectite clays were not definitively observed in CheMin analyses of Rocknest materials, they must be present at much lower abundances than the approx 20% observed in the mudstone samples. This potential detection underscores the complementary nature of the MSL CheMin and SAM instruments for investigations of martian sample mineralogy. Information on the nature of Yellowknife Bay clay minerals may also be available from the detection of H2 evolved during SAM EGA-MS at high temperature. A likely source of at least some of this H2 is H2O evolved from the smectite clays at high temperature, and it is possible these evolutions can be used in a similar fashion to high temperature H2O releases to provide constraints on the clay minerals in a sample. In addition, the D/H of this high temperature H2, as well as the H2O, can be derived from SAM MS and Tunable Laser Spectrometer (TLS) data, respectively. These D/H values may help to inform the provenance of high and low temperature water evolved from martian samples

Formation of Fe/Mg Smectite under acidic conditions from synthetic Adirondack Basaltic Glass: An Analog to Fe/Mg Smectite Formation on Mars.

NASA Astrophysics Data System (ADS)

Sutter, B.; Peretyazhko, T.; Morris, R. V.; Ming, D. W.

2014-12-01

Smectite has been detected as layered material hundreds of meters thick, in intracrater depositional fans, in plains sediments, and deposits at depth on Mars. If early Mars hosted a dense CO2 atmosphere, then extensive carbonate should have formed in the neutral/alkaline conditions expected for smectite formation. However, large carbonate deposits on Mars have not been discovered. Instead of neutral to moderately alkaline conditions, early Mars may have experienced mildly acidic conditions that allowed for Fe/Mg smectite formation but prevented widespread carbonate formation. The objective of this work is to demonstrate that Fe(II)/Mg-saponite and nontronite can form in mildly acidic solutions (e.g., pH 4). Synthetic basaltic glass (< 53 μm) of Adirondack rock class composition was exposed to pH 4 (acetic acid buffer) and N2 purged (anoxic) solutions amended with 0 and 10 mM Mg or Fe(II). Basaltic glass in these solutions was heated to 200ºC in batch reactors for 1, 7, and 14 days. X-ray diffraction analysis of reacted materials detected the presence of phyllosilicates as indicated by a ~15.03-15.23Ǻ (001) peak. Smectite was confirmed as the phyllosilicate after treatments with glycerol and KCl and heating to 550°C. Trioctahedral saponite was confirmed by the presence of a 4.58 to 4.63 Ǻ (02l) and 1.54Ǻ (060) peaks. Saponite concentration was highest, as indicated by XRD peak intensity, in the 10 mM Mg treatment followed by the 0 mM and then 10 mM Fe(II) treatments. This order of sapontite concentration suggests that Fe(II) additions may have a role in slowing the kinetics of saponite formation relative to the other treatments. Nontronite synthesis was attempted by exposing Adirondack basaltic glass to pH 4 oxic solutions (without N2 purge) at 200ºC for 14 days. X-ray diffraction analysis indicated that mixtures of trioctahedral (saponite) and dioctahedral (nontronite) may have formed in these experiments based on the 02l and 060 peaks. Mössbauer analysis coupled with future experiments are planned to verify if nontronite can be formed under mildly acidic and oxic conditions. Results of this work demonstrate that acidic conditions could have occurred on an early Mars, which allowed for smectite formation but inhibited carbonate formation.

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.

The effect of iron on montmorillonite stability. (II) Experimental investigation

NASA Astrophysics Data System (ADS)

Wilson, James; Cressey, Gordon; Cressey, Barbara; Cuadros, Javier; Ragnarsdottir, K. Vala; Savage, David; Shibata, Masahiro

2006-01-01

Several designs proposed for high-level nuclear waste (HLW) repositories include steel waste canisters surrounded by montmorillonite clay. This work investigates montmorillonite stability in the presence of native Fe, magnetite and aqueous solutions under hydrothermal conditions. Two series of experiments were conducted. In the first, mixtures of Na-montmorillonite, magnetite, native Fe, calcite, and NaCl solutions were reacted at 250 °C, Psat for between 93 and 114 days. In the second series, the starting mixtures included Na-montmorillonite, native Fe and solutions of FeCl 2 which were reacted at temperatures of 80, 150, and 250 °C, Psat, for 90-92 days. Experiments were analysed using XRD, FT-IR, TEM, ICP-AES, and ICP-MS. In the first series of experiments, native Fe oxidised to produce magnetite and the starting montmorillonite material was transformed to Fe-rich smectite only when the Fe was added predominantly as Fe metal rather than Fe oxide (magnetite). The Fe-rich smectite was initially Fe(II)-rich, which oxidised to produce an Fe(III)-rich form on exposure to air. The expansion of this material on ethylene glycol solvation was much reduced compared to the montmorillonite starting material. TEM imaging shows that partial loss of tetrahedral sheets occurred during transformation of the montmorillonite, resulting in adjacent layers becoming H-bonded with a 7 Å repeat. The reduced swelling property of the Fe-smectite product may be due predominantly to the structural disruption of smectite layers and the formation of H-bonds. Solute activities corresponded to the approximate stability field calculated for hypothetical Fe(II)-saponite. In the second series of experiments, significant smectite alteration was only observed at 250 °C and the product contained a small proportion of a 7 Å repeat structure, observable by XRD. In these experiments, solute activities coincide with berthierine. The experiments indicate that although bentonite is still a desirable choice of backfill material for HLW repositories, some loss of expandability may result if montmorillonite is altered to Fe-rich smectite at the interface between steel canisters and bentonite.

Reflectance and Mossbauer spectroscopy of ferrihydrite-montmorillonite assemblages as Mars soil analog materials

NASA Technical Reports Server (NTRS)

Bishop, J. L.; Pieters, C. M.; Burns, R. G.; Chang, S. (Principal Investigator)

1993-01-01

Spectroscopic analyses show that Fe(3+)-doped smectites prepared in the laboratory exhibit important similarities to the soils on Mars. Ferrihydrite has been identified as the interlayer ferric component in Fe(3+)-doped smectites by a low quadrupole splitting and magnetic field strength of approximately 48 tesla in Mossbauer spectra measured at 4.2 K, as well as a crystal field transition at 0.92 micrometer. Ferrihydrite in these smectites explains features in the visible-near infrared region that resemble the energies and band strengths of features in reflectance spectra observed for several bright regions on Mars. Clay silicates have met resistance in the past as Mars soil analogs because terrestrial clay silicates exhibit prominent hydrous spectral features at 1.4, 1.9, and 2.2 micrometers; and these are observed weakly, if at all, in reflectance spectra of Mars. However, several mechanisms can weaken or compress these features, including desiccation under low-humidity conditions. The hydration properties of the interlayer cations also effect band strengths, such that a ferrihydrite-bearing smectite in the Martian environment would exhibit a 1.9 micrometers H2O absorption that is even weaker than the 2.2 micrometers structural OH absorption. Mixing experiments demonstrate that infrared spectral features of clays can be significantly suppressed and that the reflectance can be significantly darkened by mixing with only a few percent of a strongly absorbing opaque material. Therefore, the absolute reflectance of a soil on Mars may be disproportionately sensitive to a minor component. For this reason, the shape and position of spectral features and the chemical composition of potential analogs are of utmost importance in assessing the composition of the soil on Mars. Given the remarkable similarity between visible-infrared reflectance spectra of soils in bright regions on Mars and Fe(3+)-doped montmorillonites, coupled with recent observations of smectites in SNC meteorites and a weak 2.2 micrometers absorption in some Mars soils, ferrihydrite-bearing smectites warrant serious consideration as a Mars soil analog.

Surface reactions of iron - enriched smectites: adsorption and transformation of hydroxy fatty acids and phenolic acids

NASA Astrophysics Data System (ADS)

Polubesova, Tamara; Olshansky, Yaniv; Eldad, Shay; Chefetz, Benny

2014-05-01

Iron-enriched smectites play an important role in adsorption and transformation of soil organic components. Soil organo-clay complexes, and in particular humin contain hydroxy fatty acids, which are derived from plant biopolymer cutin. Phenolic acids belong to another major group of organic acids detected in soil. They participate in various soil processes, and are of concern due to their allelopathic activity. We studied the reactivity of iron-enriched smectites (Fe(III)-montmorillonite and nontronite) toward both groups of acids. We used fatty acids- 9(10),16-dihydroxypalmitic acid (diHPA), isolated from curtin, and 9,10,16-trihydroxypalmitic acid (triHPA); the following phenolic acids were used: ferulic, p-coumaric, syringic, and vanillic. Adsorption of both groups of acids was measured. The FTIR spectra of fatty acid-mineral complexes indicated inner-sphere complexation of fatty acids with iron-enriched smectites (versus outer-sphere complexation with Ca(II)-montmorillonite). The LC-MS results demonstrated enhanced esterification of fatty acids on the iron-enriched smectite surfaces (as compared to Ca(II)-montmorillonite). This study suggests that fatty acids can be esterified on the iron-enriched smectite surfaces, which results in the formation of stable organo-mineral complexes. These complexes may serve as a model for the study of natural soil organo-clay complexes and humin. The reaction of phenolic acids with Fe(III)-montmorillonite demonstrated their oxidative transformation by the mineral surfaces, which was affected by molecular structure of acids. The following order of their transformation was obtained: ferulic >syringic >p-coumaric >vanillic. The LC-MS analysis demonstrated the presence of dimers, trimers, and tetramers of ferulic acid on the surface of Fe(III)-montmorillonite. Oxidation and transformation of ferulic acid were more intense on the surface of Fe(III)-montmorillonite as compared to Fe(III) in solution due to stronger complexation on the Fe(III)-motnomrillonite surface. Our study demonstrate the importance of iron-enriched minerals for the abiotic formation of humic materials and for the transformation of aromatic (phenolic) pollutants.

Spectroscopic study of carbaryl sorption on smectite from aqueous suspension.

PubMed

de Oliveira, Maurilio Fernandes; Johnston, Cliff T; Premachandra, G S; Teppen, Brian J; Li, Hui; Laird, David A; Zhu, Dongqiang; Boyd, Stephen A

2005-12-01

Sorption of carbaryl (1-naphthyl-N-methyl-carbamate) from aqueous suspension to smectite was studied using Fourier transform infrared (FTIR), high-performance liquid chromatography (HPLC) (for batch sorption), and quantum chemical methods. The amount of carbaryl sorbed was strongly dependent on the surface-charge density of the smectite with more sorption occurring on the two "low" surface-charge density smectites (SHCa-1 and SWy-2) compared to that of the high surface-charge SAz-1 smectite. In addition, the amount of carbaryl sorbed was strongly dependent on the nature of the exchangeable cation and followed the order of Ba approximately Cs approximately Ca > Mg approximately K > Na approximately Li for SWy-2. A similartrend was found for hectorite (SHCa-1) of Cs > Ba > Ca > K approximately Mg > Na approximately Li. Using the shift of the carbonyl stretching band as an indicator of the strength of interaction between carbaryl and the exchangeable cation, the observed order was Mg > Ca > Ba approximately K > Na > Cs. The position of the carbonyl stretching band shifted to lower wavenumbers with increasing ionic potential of the exchangeable cation. Density functional theory predicted a cation-induced lengthening of the C=O bond, resulting from the carbonyl group interacting directly with the exchangeable cation in support of the spectroscopic observations. Further evidence was provided by a concomitant shift in the opposite direction by several vibrational bands in the 1355-1375 cm(-1) region assigned to stretching bands of the carbamate N-Ccarbonyl and Oether-Ccarbonyl bonds. These data indicate that carbaryl sorption is due, in part, to site-specific interactions between the carbamate functional group and exchangeable cations, as evidenced by the FTIR data. However, these data suggest that hydrophobic interactions also contribute to the overall amount of carbaryl sorbed. For example, the FTIR data indicated thatthe weakest interaction occurred when Cs+ was the exchangeable cation. In contrast, the highest amount of carbaryl sorption was observed on Cs-exchanged smectite. Of all the cations studied, Cs has the lowest enthalpy of hydration. It is suggested that this low hydration energy provides the carbaryl with greater access to the hydrophobic regions of the siloxane surface.

Kinetic Study of Denatonium Sorption to Smectite Clay Minerals.

PubMed

Crosson, Garry S; Sandmann, Emily

2013-06-01

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

An AEM-TEM study of weathering and diagenesis, Abert Lake, Oregon: II. Diagenetic modification of the sedimentary assemblage

USGS Publications Warehouse

Banfield, J.F.; Jones, B.F.; Veblen, D.R.

1991-01-01

This paper compares the mineralogy and chemistry of clay minerals in sediments from various depths and positions in Abert Lake and surrounding playa with those of the weathered materials entering the lake in order to reveal the nature and extent of post-depositional mineralogical modification. Analytical electron microscope (AEM) data from individual clay particles reveal that each sample is comprised of a highly inhomogeneous smectite assemblage. The thin clay flakes (commonly less than 10 nm wide) display a complete range in octahedral sheet compositions from nearly dioctahedral to nearly trioctahedral. The very abundant Mg-rich lake smectites with an estimated composition K0.29(Al0.23-Mg2.16Fe0.30)Si3.80Al0.20O10(OH)2 are not formed by weathering. This confirms the importance of diagenetic Mg uptake. Lattice-fringe imaging failed to reveal distinct brucite-like or vermiculite-like layers, suggesting that interstratifications of this type are rare or absent. Siliceous coatings on clay particles (identified by silica excess in smectite analyses) seem to favor topotactic overgrowth of stevensite rather than addition of brucite-like layers to the dioctahedral nuclei. The growth of K-stevensite dilutes the Al content of the crystal, and thus the increasing diagenetic modification reduces rather than supplements its illite component. Smectite compositions within individual samples were highly variable, yet source-related characteristics such as the abundance of Fe-rich smectite were apparent. Little evidence for systematic K or Mg enrichment with depth was identified in samples from depths of down to 16 feet below the sediment-water interface. The most magnesian assemblages are associated both with weathering sources of Mg-rich smectite and playa environments subjected to repeated wetting and drying cycles. Thus, the observations suggest that clay compositions primarily reflect changes in lake levels, brine composition, and source characteristics, rather than time and depth/compaction effects. Other diagenetic reactions in the sediment include recrystallization of Na-rich silica gel and diatom fragments. Abundant, submicron-sized, untwinned, euhedral crystals of K-feldspar are interpreted to be authigenic in origin. ?? 1991.

Kinetic Study of Denatonium Sorption to Smectite Clay Minerals

PubMed Central

Crosson, Garry S.; Sandmann, Emily

2013-01-01

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

Illitization of Potassium, Cesium, and Ammonium Exchanged Smectite

NASA Astrophysics Data System (ADS)

Mills, M. M.; Wang, Y.; Payne, C.; Sanchez, A. C.; Boisvert, L.; Matteo, E. N.

2017-12-01

Bentonite clay is a primary choice for engineered barrier systems within geologic repositories for disposal of radioactive wastes due to its low permeability at saturated states, warranting diffusion as the dominant transport mechanism, and large swelling pressures that promote sealing. In order to predict how well the barrier will function over time at repository relevant temperatures, it is important to understand thermal alteration effects on montmorillonite, better known as smectite, a main constituent of bentonite. One type of thermal alteration is the conversion to illite, when exposed to elevated temperatures and a sufficient amount of potassium ions, thereby weakening barrier functions. To facilitate the conversion of smectite to illite and examine the influence of interlayer cations, illitization experiments on cation exchanged smectite were performed within hydrothermal reaction vessels over one week timescales. The <2um fraction of a Na-rich smectite clay was first exchanged with 1M Cs, K, and NH4 salt solutions and further exposed to hydrous pyrolysis using a 1M KCl solution with various solid to liquid ratios at 200°C. Multiple analysis techniques were used to characterize the altered clay and identify extent of conversion, such as XRD, cation exchange capacity, and morphology changes by SEM. The pore-water chemistry was also analyzed by ICP-OES to detect any dissolved products and silica content. Results suggest the conversion rate is relatively fast, occurring within days, and is dependent on not only the amount of K, but also dissolved silica concentration related to total solid in solution. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia LLC, a wholly owned subsidiary of Honeywell International Inc. for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525. SAND2017-7856A

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.

Mechanisms for the adsorption of substituted nitrobenzenes by smectite clays.

PubMed

Boyd, S A; Sheng, G; Teppen, B J; Johnston, C T

2001-11-01

To more fully understand the potential for transport of nitroaromatic compounds in soils and subsoils,the adsorption of a series of para- and meta-substituted nitrobenzenes (SNBs) by K-smectite clay was measured. Adsorption isotherms were fit to the Freundlich equation, and the resultant Freundlich adsorption coefficients (log(Kf) were positively correlated with the Hammett substituent constant (r2 = 0.80). This relationship and a positive reaction constant (p = 1.15) indicate that the adsorption reaction is favored by electron-withdrawing substituents. These results are consistent with an electron donor (smectite)-acceptor (substituted nitrobenzene) mechanism offered previously. However, quantum calculations did not reveal any systematic relationship between the Hammett constant and the electron density on the aromatic ring, which would explain a donor-acceptor relationship. Rather, electron density donated by a second substituent on nitrobenzene appears to be appropriated by the nitro group leaving ring electron density unchanged. Fourier transform infrared spectroscopy revealed shifts in the -NO2 vibrational modes of 1,3,5-trinitrobenzene (TNB) upon adsorption to K+-smectite that were consistent with the complexation of K+ by -NO2 groups. Such TNB vibrational shifts were not observed for SWy-1 saturated with more strongly hydrated cations (i.e., Na+, Mg2+, Ca2+, and Ba2+). The simultaneous interaction of multiple -NO2 groups with exchangeable K+ was indicated by molecular dynamic simulations. Adsorption of SNBs by smectite clays appears to result from the additive interactions of -NO2 groups and secondary substituents with interlayer K+ ions. Adsorption occurs to a greater or lesser extent depending on the abilities of substituents to complex additional interlayer cations and the water solubilities of SNBs. We conclude that the adsorption trends of SNBs on K-SAz-1 can be explained without recourse to hypothetical electron donor-acceptor complexes.

Interactions among K+-Ca2+ exchange, sorption of m-dinitrobenzene, and smectite quasicrystal dynamics.

PubMed

Chatterjee, Ritushree; Laird, David A; Thompson, Michael L

2008-12-15

The fate of organic contaminants in soils and sediments is influenced by sorption of the compounds to surfaces of soil materials. We investigated the interaction among sorption of an organic compound, cation exchange reactions, and both the size and swelling of smectite quasicrystals. Two reference smectites that vary in location and amount of layer charge, SPV (a Wyoming bentonite) and SAz-1 were initially Ca- and K-saturated and then equilibrated with mixed 0.01 M KCl and 0.005 M CaCl2 salt solutions both with and without the presence of 200 mg L(-1) m-dinitrobenzene (m-DNB). In general, sorption of m-DNB increased with the amount of K+ in the system for both clays, and the SPV sorbed more m-DNB than the SAz-1. Sorption of m-DNB increased the preference of Ca-SPV for K+ relative to Ca2+ but had little effect on K+-Ca2+ selectivity for K-SPV. Selectivity for K+ relative to Ca2+ was slightly higher for both K-SAz-1 and Ca-SAz-1 in the presence of m-DNB than in its absence. Distinct hysteresis loops were observed for the K+-Ca2+ cation exchange reactions for both clays, and the legacy of having been initially Ca- or K-saturated influenced sorption of m-DNB by SPV but had little effect for SAz-1. Suspension X-ray diffraction was used to measure changes in d-spacing and the relative thickness of smectite quasicrystals during the cation exchange and m-DNB sorption reactions. The results suggest that interactions among cation exchange and organic sorption reactions are controlled byan inherently hysteretic complex feedback process that is regulated by changes in the size and extent of swelling of smectite quasicrystals.

Probing the microscopic hydrophobicity of smectite surfaces. A vibrational spectroscopic study of dibenzo-p-dioxin sorption to smectite.

PubMed

Rana, Kiran; Boyd, Stephen A; Teppen, Brian J; Li, Hui; Liu, Cun; Johnston, Cliff T

2009-04-28

The interaction of dibenzo-p-dioxin (DD), from aqueous suspension, with smectite was investigated using in situ vibrational spectroscopy (FTIR and Raman), structural and batch sorption techniques. Batch sorption isotherms were integrated with in situ attenuated total reflectance (ATR)-FTIR and Raman spectroscopy and X-ray diffraction. Sorption isotherms revealed that the affinity of DD for smectite in aqueous suspension was strongly influenced both by the type of smectite and by the nature of the exchangeable cation. Cs-saponite showed a much higher affinity over Rb-, K- and Na-exchange saponites. In addition, DD sorption was found to depend on clay type with DD showing a high affinity for the tetrahedrally substituted trioctahedral saponite over SWy-2 and Upton montmorillonites. A structural model is introduced to account for the influence of clay type. Raman and FTIR data provided complementary molecular-level insight into the sorption mechanisms. In the case of Cs-saponite, the selection rules of DD based on D(2h) symmetry were broken indicating a site-specific interaction between DD and intercalated Cs(+) ions in the interlayer of the clay. Polarized in situ ATR-FTIR spectra revealed that the molecular plane of sorbed DD was tilted with respect to the clay surface which was consistent with a d-spacing of 1.49 nm. Finally, cation-induced changes in both the skeletal ring vibrations and the asymmetric C-O-C stretching vibrations provided evidence for site specific interactions between the DD and exchangeable cations in the clay interlayer. Together, the combined macroscopic and spectroscopic data show a surprising link between a hydrophilic material and a planar hydrophobic aromatic hydrocarbon.

Anatomy of a metabentonite: nucleation and growth of illite crystals and their colescence into mixed-layer illite/smectite

USGS Publications Warehouse

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

2011-01-01

The illite layer content of mixed-layer illite/smectite (I/S) in a 2.5 m thick, zoned, metabentonite bed from Montana decreases regularly from the edges to the center of the bed. Traditional X-ray diffraction (XRD) pattern modeling using Markovian statistics indicated that this zonation results from a mixing in different proportions of smectite-rich R0 I/S and illite-rich R1 I/S, with each phase having a relatively constant illite layer content. However, a new method for modeling XRD patterns of I/S indicates that R0 and R1 I/S in these samples are not separate phases (in the mineralogical sense of the word), but that the samples are composed of illite crystals that have continuous distributions of crystal thicknesses, and of 1 nm thick smectite crystals. The shapes of these distributions indicate that the crystals were formed by simultaneous nucleation and growth. XRD patterns for R0 and R1 I/S arise by interparticle diffraction from a random stacking of the crystals, with swelling interlayers formed at interfaces between crystals from water or glycol that is sorbed on crystal surfaces. It is the thickness distributions of smectite and illite crystals (also termed fundamental particles, or Nadeau particles), rather than XRD patterns for mixed-layer I/S, that are the more reliable indicators of geologic history, because such distributions are composed of well-defined crystals that are not affected by differences in surface sorption and particle arrangements, and because their thickness distribution shapes conform to the predictions of crystal growth theory, which describes their genesis.

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

NASA Technical Reports Server (NTRS)

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

2011-01-01

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

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.

Mechanisms associated with the high adsorption of dibenzo-p-dioxin from water by smectite clays.

PubMed

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

2009-04-15

Clay minerals may be an important unrecognized sorptive phase for dioxins in soils and clay deposits. Smectites, especially Cs-saponite, effectively adsorbed dibenzo-p-dioxin (DD) from water, reaching 0.8% (wt/wt). Adsorption was promoted by exchangeable cations with low hydration energies, and negative charge in the smectite arising from the tetrahedral siloxane sheets. X-ray diffraction measurements revealed that as DD loading increased to > or =8000 mg/kg the clay basal spacing increased abruptly from 12.3 to 15.2 A demonstrating DD intercalation. The 12.3 A spacing provides an interlayer distance that closely matches the molecular thickness of DD. In this configuration DD is essentially dehydrated as it interacts with the opposing hydrophobic siloxane sheets and with coplanar Cs+ via one of the dioxin ring oxygens. Ab initio calculations suggest that geometrical structures form at higher loadings in which intercalated DD molecules adopt a butterfly geometry sandwiched between dehydrated interlayer Cs+ and the siloxane surface, consistent with the 15.2 A spacing, wherein Cs+ interacts with dioxin ring oxygens and benzene ring pi-electrons. Fourier transformation infrared measurements confirm that adsorbed DD is present in orientations that are not parallel with the interlayer planar siloxane surfaces of smectite.

Evidence for Smectite Clays from MSL SAM Analyses of Mudstone at Yellowknife Bay, Gale Crater, Mars

NASA Astrophysics Data System (ADS)

McAdam, A.; Franz, H.; Mahaffy, P. R.; Eigenbrode, J. L.; Stern, J. C.; Brunner, A.; Sutter, B.; Archer, P. D.; Ming, D. W.; Morris, R. V.; Atreya, S. K.; Team, M.

2013-12-01

Drilled samples of mudstone from the Sheepbed unit at Yellowknife Bay were analyzed by MSL instruments including the Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments in MSL's Analytical Laboratory. CheMin analyses revealed the first in situ X-ray diffraction based evidence of clay minerals on Mars, which are likely trioctahedral smectites (e.g., saponite) and comprise ~20% of the mudstone sample (e.g., Bristow et al., this meeting). SAM analyses, which heated the mudstone samples to 1000oC and monitored volatiles evolved to perform in situ evolved gas analysis mass spectrometry (EGA-MS), resulted in a H2O trace exhibiting a wide evolution at temperatures <500oC, and an evolution peak at higher temperatures near ~750oC. The low temperature H2O evolution has many potential contributors, including adsorbed H2O, smectite interlayer H2O, and structural H2O/OH from bassanite and akaganeite (identified by CheMin) and H2O/OH from amorphous phases in the sample. The high temperature H2O is consistent with the evolution of H2O from the dehydroxylation of the smectite clay mineral. Comparison to EGA-MS data collected under SAM-like conditions on a variety of clay mineral reference materials indicate that a trioctahedral smectite, such as saponite, is most consistent with the high temperature H2O evolution observed. There may also be SAM EGA-MS evidence for a small high temperature H2O evolution from scoop samples from the Yellowknife Bay Rocknest sand shadow bedform. As in the mudstone samples, this evolution may indicate the detection of smectite clays, and the idea that minor clays may be present in Rocknest materials that could be expected to be at least partially derived from local sources is reasonable. But, because smectite clays were not definitively observed in CheMin analyses of Rocknest materials, they must be present at much lower abundances than the ~20% observed in the mudstone samples. This potential detection underscores the complementary nature of the MSL CheMin and SAM instruments for investigations of martian sample mineralogy. Information on the nature of Yellowknife Bay clay minerals may also be available from the detection of H2 evolved during SAM EGA-MS at high temperature. A likely source of at least some of this H2 is H2O evolved from the smectite clays at high temperature, and it is possible these evolutions can be used in a similar fashion to high temperature H2O releases to provide constraints on the clay minerals in a sample. In addition, the D/H of this high temperature H2, as well as the H2O, can be derived from SAM MS and Tunable Laser Spectrometer (TLS) data, respectively. These D/H values may help to inform the provenance of high and low temperature water evolved from martian samples (Mahaffy et al., this meeting).

Microbial Effects in Promoting the Smectite to Illite Reaction: Role of Organic Matter Intercalated in the Interlayer

DTIC Science & Technology

2007-01-01

organic matter in the smectite to illite reaction. For example, Small etal. (1994) demonstrated that potassium oxalate and potassium acetate in...potassium oxalate and potassium acetate on this reaction (Small 1994). This study supplements our previous study in that microbes play an...Keeling, J.L., Raven, M.D., and Gates, W.P, (2000) Geology and characterization of two hydrothermal nontronites from weathered metamorphic rocks at

Long-Range Interactions Restrict Water Transport in Pyrophyllite Interlayers

DOE PAGES

Zarzycki, Piotr; Gilbert, Benjamin

2016-04-27

Water diffusion within smectite clay interlayers is reduced by confinement and hence is highly determined by the interlayer spacings that are adopted during swelling. However, a molecular understanding of the short-and long-range forces governing interlayer water structure and dynamics is lacking. Using molecular dynamics simulations of water intercalated between pyrophyllite (smectite prototype) layers we provide a detailed picture of the variation of interlayered water mobility accompanying smectite expansion. Subtle changes in hydrogen bond network structure cause significant changes in water mobility that is greater for stable hydration states and reduced for intermediate separations. By studying pyrophyllite with and without externalmore » water we reveal that long-range electrostatic forces apply a restraining effect upon interlayer water mobility. Our findings are relevant for broad range of confining nanostructures with walls thin enough to permit long-range interactions that could affect the mobility of confined solvent molecules and solute species.« less

Clay mineral formation and transformation in rocks and soils

USGS Publications Warehouse

Eberl, D.D.

1983-01-01

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

Long-Range Interactions Restrict Water Transport in Pyrophyllite Interlayers

PubMed Central

Zarzycki, Piotr; Gilbert, Benjamin

2016-01-01

Water diffusion within smectite clay interlayers is reduced by confinement and hence is highly determined by the interlayer spacings that are adopted during swelling. However, a molecular understanding of the short- and long-range forces governing interlayer water structure and dynamics is lacking. Using molecular dynamics simulations of water intercalated between pyrophyllite (smectite prototype) layers we provide a detailed picture of the variation of interlayered water mobility accompanying smectite expansion. Subtle changes in hydrogen bond network structure cause significant changes in water mobility that is greater for stable hydration states and reduced for intermediate separations. By studying pyrophyllite with and without external water we reveal that long-range electrostatic forces apply a restraining effect upon interlayer water mobility. Our findings are relevant for broad range of confining nanostructures with walls thin enough to permit long-range interactions that could affect the mobility of confined solvent molecules and solute species. PMID:27118164

Mass spectrometric identification of an azobenzene derivative produced by smectite-catalyzed conversion of 3-amino-4-hydroxyphenylarsonic acid

USGS Publications Warehouse

Wershaw, R. L.; Rutherford, D.W.; Rostad, C.E.; Garbarino, J.R.; Ferrer, I.; Kennedy, K.R.; Momplaisir, G.-M.; Grange, A.

2003-01-01

The compound 3-amino-4-hydroxyphenylarsonic acid (3-amino-HPAA) reacts with smectite to form a soluble azobenzene arsonic acid compound. This reaction is of particular interest because it provides a possible mechanism for the formation of a new type of arsenic compound in natural water systems. 3-Amino-HPAA is a degradation product excreted by chickens that are fed rations amended with roxarsone. Roxarsone is used to control coccidial intestinal parasites in most of the broiler chickens grown in the United States. The structure of the azobenzene arsonic acid compound was first inferred from negative-ion and positive-ion low-resolution mass-spectrometric analyses of the supernatant of the smectite suspension. Elemental composition of the parent ion determined by high-resolution positive-ion mass spectrometric measurements was consistent with the proposed structure of the azobenzene arsonic acid compound. Published by Elsevier Science B.V.

Evaluation of BTEX and phenol removal from aqueous solution by multi-solute adsorption onto smectite organoclay.

PubMed

Carvalho, M N; da Motta, M; Benachour, M; Sales, D C S; Abreu, C A M

2012-11-15

The removal process of BTEX and phenol was evaluated. The smectite organoclay for single-solute system reached removal was evaluated by adsorption on smectite organoclay adsorbent by kinetic and equilibrium efficiencies between 55 and 90% while was reached between 30 and 90% for multi-solute system at 297 K and pH 9. The Langmuir-Freundlich model was used to fit the experimental data with correlation coefficient between 0.98 and 0.99 providing kinetic and equilibrium parameter values. Phenol and ethylbenzene presented high maximum adsorbed amount, 8.28 and 6.67 mg/g, respectively, compared to the other compounds for single-solute. Toluene and p-xylene presented high values of adsorption constant which indicates a high adsorption affinity of compounds to organoclay surface and high binding energy of adsorption. Phenol presented low kinetic adsorption constant value indicating slow rate of adsorption. Copyright © 2012 Elsevier B.V. All rights reserved.

Improvement of the Heat Resistance of Prussian Blue Nanoparticles in a Clay Film Composed of Smectite Clay and ε-Caprolactam.

PubMed

Ono, Kenta; Nakamura, Takashi; Ebina, Takeo; Ishizaki, Manabu; Kurihara, Masato

2018-06-04

Prussian blue (PB) is limited in its application by its breakdown at elevated temperatures. To improve the heat resistance of PB, we prepared a composite film comprising PB nanoparticles (NPs), smectite clay, and an organic compound. The composite film had a microstructure in which PB NPs were intercalated between smectite/organic compound layers. The predominant oxidation temperature of the PB NPs in the composite film was around 500 °C in air, higher than the oxidation temperature of bulk PB in air (250 °C). This improvement in the oxidation temperature may be due to the composite film acting as a barrier to oxygen gas. These results indicate the effectiveness of clay materials for the improvement of heat resistance for low-temperature decomposition compounds, not only PB but also other porous coordination polymers.

On the origin of mixed-layered clay minerals from the San Andreas Fault at 2.5-3 km vertical depth (SAFOD drillhole at Parkfield, California)

NASA Astrophysics Data System (ADS)

Schleicher, A. M.; Warr, L. N.; van der Pluijm, B. A.

2009-02-01

A detailed mineralogical study is presented of the matrix of mudrocks sampled from spot coring at three key locations along the San Andreas Fault Observatory at depth (SAFOD) drill hole. The characteristics of authigenic illite-smectite (I-S) and chlorite-smectite (C-S) mixed-layer mineral clays indicate a deep diagenetic origin. A randomly ordered I-S mineral with ca. 20-25% smectite layers is one of the dominant authigenic clay species across the San Andreas Fault zone (sampled at 3,066 and 3,436 m measured depths/MD), whereas an authigenic illite with ca. 2-5% smectite layers is the dominant phase beneath the fault (sampled at 3,992 m MD). The most smectite-rich mixed-layered assemblage with the highest water content occurs in the actively deforming creep zone at ca. 3,300-3,353 m (true vertical depth of ca. 2.7 km), with I-S (70:30) and C-S (50:50). The matrix of all mudrock samples show extensive quartz and feldspar (both plagioclase and K-feldspar) dissolution associated with the crystallization of pore-filling clay minerals. However, the effect of rock deformation in the matrix appears only minor, with weak flattening fabrics defined largely by kinked and fractured mica grains. Adopting available kinetic models for the crystallization of I-S in burial sedimentary environments and the current borehole depths and thermal structure, the conditions and timing of I-S growth can be evaluated. Assuming a typical K+ concentration of 100-200 ppm for sedimentary brines, a present-day geothermal gradient of 35°C/km and a borehole temperature of ca. 112°C for the sampled depths, most of the I-S minerals can be predicted to have formed over the last 4-11 Ma and are probably still in equilibrium with circulating fluids. The exception to this simple burial pattern is the occurrence of the mixed layered phases with higher smectite content than predicted by the burial model. These minerals, which characterize the actively creeping section of the fault and local thin film clay coating on polished brittle slip surfaces, can be explained by the influence of either cooler fluids circulating along this segment of the fault or the flow of K+-depleted brines.

Hydration thermodynamics of the SWy-1 montmorillonite saturated with alkali and alkaline-earth cations: A predictive model

NASA Astrophysics Data System (ADS)

Vieillard, Philippe; Blanc, Philippe; Fialips, Claire I.; Gailhanou, Hélène; Gaboreau, Stéphane

2011-10-01

The aim of the present work was to study the thermodynamic equilibria between water and a homo-ionic montmorillonite SWy-1 saturated by different cations. The choice of this smectite is justified by the large set of experimental data available from the literature for eight different interlayer cations: Na +, K +, Rb +, Cs +, Mg 2+, Ca 2+, Sr 2+, and Ba 2+. In particular, studies by Cases et al. (1992, 1997) and Bérend et al. (1995) are providing heat of adsorption data, pairs of desorption-adsorption isotherms, and information about the partition of adsorption-desorption water molecules between external surfaces and internal spaces. By calculating the effective amount of hydration water as the difference between the so-called gravimetric water and the surface covering water, a thermodynamic model was then developed, based on the concept of Ransom and Helgeson (1994) considering an asymmetric subregular binary solid solution between a fully hydrated and a anhydrous smectite. A set of six thermodynamic parameters ( ΔH∘hyd,S∘hyd and four Margules parameters) was extracted by a least square method from measurements of enthalpies of adsorption and paired adsorption-desorption isotherms for each interlayer cation. These six initial parameters were then used to determine a complete set of standard thermodynamic hydration parameters ( ΔH∘hyd,ΔG∘hyd,ΔS∘hyd, heat capacity, molar volume, and number of interlayer H 2O) and quantify, for each cation, the number of moles of hydration water molecules as a function of relative humidity and temperature. The validation of the standard state thermodynamic properties of hydration for each end member was carried out using three approaches: (1) a comparison with experimental isotherms obtained on hetero-ionic and homo-ionic SWy-1 smectite at different temperatures; (2) a comparison with the experimental integral enthalpy and entropy of hydration of the SWy-1 smectite; and (3) a comparison with experimental isotherms acquired on various smectites (Upton, MX80, Arizona) with different layer charges. Eventually, the present work demonstrates that, from a limited number of measurements, it is possible to provide the hydration thermodynamic parameters for hydrated smectites with different compositions and under different conditions of temperature and relative humidity, using the newly developed predictive model.

Growth of Iron(III)-Reducing Bacteria on Clay Minerals as the Sole Electron Acceptor and Comparison of Growth Yields on a Variety of Oxidized Iron Forms†

PubMed Central

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

2002-01-01

Smectite clay minerals are abundant in soils and sediments worldwide and are typically rich in Fe. While recent investigations have shown that the structural Fe(III) bound in clay minerals is reduced by microorganisms, previous studies have not tested growth with clay minerals as the sole electron acceptor. Here we have demonstrated that a pure culture of Shewanella oneidensis strain MR-1 as well as enrichment cultures of Fe(III)-reducing bacteria from rice paddy soil and subsurface sediments are capable of conserving energy for growth with the structural Fe(III) bound in smectite clay as the sole electron acceptor. Pure cultures of S. oneidensis were used for more detailed growth rate and yield experiments on various solid- and soluble-phase electron acceptors [smectite, Fe(III) oxyhydroxide FeOOH, Fe(III) citrate, and oxygen] in the same minimal medium. Growth was assessed as direct cell counts or as an increase in cell carbon (measured as particulate organic carbon). Cell counts showed that similar growth of S. oneidensis (108 cells ml−1) occurred with smectitic Fe(III) and on other Fe forms [amorphous Fe(III) oxyhydroxide, and Fe citrate] or oxygen as the electron acceptor. In contrast, cell yields of S. oneidensis measured as the increase in cell carbon were similar on all Fe forms tested while yields on oxygen were five times higher, in agreement with thermodynamic predictions. Over a range of particle loadings (0.5 to 4 g liter−1), the increase in cell number was highly correlated to the amount of structural Fe in smectite reduced. From phylogenetic analysis of the complete 16S rRNA gene sequences, a predominance of clones retrieved from the clay mineral-reducing enrichment cultures were most closely related to the low-G+C gram-positive members of the Bacteria (Clostridium and Desulfitobacterium) and the δ-Proteobacteria (members of the Geobacteraceae). Results indicate that growth with smectitic Fe(III) is similar in magnitude to that with Fe(III) oxide minerals and is dependent upon the mineral surface area available. Iron(III) bound in clay minerals should be considered an important electron acceptor supporting the growth of bacteria in soils or sedimentary environments. PMID:12450850

Smectites versus palagonites in Mars soil: Evidence from simulations of Viking biology labeled release experiments

NASA Technical Reports Server (NTRS)

Banin, A.; Margulies, L.

1983-01-01

The results of an experimental comparison between palagonites and a smectite (montmorillonite) in the simulation of the Viking Biology Labeled Release (LR) experiment and conclusions regarding their suitability as MarSAMs are reproved. It was found that palagonites do not cause formate decomposition and C-14 release in their natural form or after acidification and thus cannot be a completely satisfactory analog to the Mars soil studied by Viking.

Nontronite and Montmorillonite as Nutrient Sources for Life on Mars

NASA Technical Reports Server (NTRS)

Craig, P. I.; Mickol, R. L.; Archer, P. D.; Kral, T. A.

2017-01-01

Clay minerals have been identified on Mars' oldest (Noachian) terrain and their presence suggests long-term water-rock interactions. The most commonly identified clay minerals on Mars to date are nontronite (Fe-smectite) and montmorillonite (Al-smectite) [1], both of which contain variable amounts of water both adsorbed on their surface and within their structural layers. Over Mars' history, these clay miner-al-water assemblages may have served as nutrient sources for microbial life.

Mechanisms of siderophore sorption to smectite and siderophore-enhanced release of structural Fe 3+

NASA Astrophysics Data System (ADS)

Haack, Elizabeth A.; Johnston, Cliff T.; Maurice, Patricia A.

2008-07-01

Sorption of the trihydroxamate siderophores desferrioxamine-B and -D (DFOB and DFOD, respectively) and of the monohydroxamate ligand acetohydroxamic acid (aHA) to smectite were examined in batch sorption studies (pH 5.5, 0.1 M ionic strength) coupled with X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. Both DFOB and DFOD, which have similar molecular structures but different charge properties (cationic versus neutral, respectively) showed a high affinity for smectite. In contrast, the smaller aHA molecule did not sorb appreciably. XRD analysis indicated that DFOB and DFOD each absorbed in the interlamellar region of the clay to give d-spacings of 13.4-13.7 Å at equilibrium solution concentrations <250 μM. FTIR spectra of sorbed DFOB and DFOD indicated that the conformation of each species was distinct from its conformation in the crystalline or dissolved states. At elevated initial solution concentrations of 500-1500 μM, DFOB formed a bilayer in the clay interlayer. Changes in the FTIR spectra of the DFOB-loaded clay samples at these higher surface loadings were consistent with the presence of a metal-siderophore complex in the interlayer. DFOB and DFOD both enhanced Fe and Al release from smectite, but aHA did not. Possible dissolution mechanisms are discussed in light of the FTIR and batch dissolution results.

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.

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

USGS Publications Warehouse

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

2005-01-01

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

Effect of low-molecular-weight organic acids on photo-degradation of phenanthrene catalyzed by Fe(III)-smectite under visible light.

PubMed

Jia, Hanzhong; Chen, Hongxia; Nulaji, Gulimire; Li, Xiyou; Wang, Chuanyi

2015-11-01

The photolysis of polycyclic aromatic hydrocarbons (PAHs) is potentially an important process for its transformation and fate on contaminated soil surfaces. In this study, phenanthrene is employed as a model to explore PAH photodegradation with the assistance of Fe(III)-smectite under visible-light while focusing on roles played by five low-molecular-weight organic acids (LMWOAs), i.e., malic acid, oxalic acid, citric acid, ethylenediaminetetraacetic acid (EDTA), and nitrilotriacetic acid. Our results show that oxalic acid is most effective in promoting the photodegradation of phenanthrene, while only a slight increase in the rate of phenanthrene photodegradation is observed in the presence of malic acid. Electron paramagnetic resonance experiments confirm the formation of CO2(-) radicals in the presence of malic and oxalic acid, which provides strong evidence for generating OH and subsequent photoreaction pathways. The presence of EDTA or nitrilotriacetic acid significantly inhibits both Fe(II) formation and phenanthrene photodegradation because these organic anions tend to chelate with Fe(III), leading to decreases in the electron-accepting potential of Fe(III)-smectite and a weakened interaction between phenanthrene and Fe(III)-smectite. These observations provide valuable insights into the transformation and fate of PAHs in the natural soil environment and demonstrate the potential for using some LMWOAs as additives for the remediation of contaminated soil. Copyright © 2015 Elsevier Ltd. All rights reserved.

Adsorptive effects of di-tri-octahedral smectite on Clostridium perfringens alpha, beta, and beta-2 exotoxins and equine colostral antibodies.

PubMed

Lawler, Jacquelin Boggs; Hassel, Diana M; Magnuson, Roberta J; Hill, Ashley E; McCue, Patrick M; Traub-Dargatz, Josie L

2008-02-01

To determine the adsorptive capability of di-tri-octahedral smectite (DTOS) on Clostridium perfringens alpha, beta, and beta-2 exotoxins and equine colostral antibodies. 3 C perfringens exotoxins and 9 colostral samples. Alpha, beta, and beta-2 exotoxins were individually co-incubated with serial dilutions of DTOS or bismuth subsalicylate, and the amount of toxin remaining after incubation was determined via toxin-specific ELISAs. Colostral samples from healthy mares were individually co-incubated with serial dilutions of DTOS, and colostral IgG concentrations were determined via single radial immunodiffusion assay. Di-tri-octahedral smectite decreased the amount of each C perfringens exotoxin in co-incubated samples in a dose-dependent manner and was more effective than bismuth subsalicylate at reducing exotoxins in vitro. Decreases in the concentration of IgG were detected in samples of colostrum that were combined with DTOS at 1:4 through 1:16 dilutions, whereas no significant decrease was evident with DTOS at the 1:32 dilution. Di-tri-octahedral smectite effectively adsorbed C perfringens exotoxins in vitro and had a dose-dependent effect on the availability of equine colostral antibodies. Results suggested that DTOS may be an appropriate adjunctive treatment in the management of neonatal clostridiosis in horses. In vivo studies are necessary to fully assess the clinical efficacy of DTOS treatment.

A possible source of water in seismogenic subduction zones

NASA Astrophysics Data System (ADS)

Kameda, J.; Yamaguchi, A.; Kimura, G.; Iodp Exp. 322 Scientists

2010-12-01

Recent works on the subduction megathrusts have emphasized the mechanical function of fluids contributing dynamic slip-weakening. Basalt-hosting fault zones in on-land accretionary complexes present several textures of seismic slip under fluid-assisted condition such as implosion breccia with carbonate matrix and decrepitation of fluid inclusion. In order to clarify initiation and evolution processes of such fault zones as well as possible source of fluid in the seismogenic subduction zone, we examined a mineralogical/geochemical feature of basaltic basement recovered by IODP Exp. 322 at C0012, that is a reference site for subduction input in the Nankai Trough. A total of 10 samples (about 4 m depth interval from the basement top) were analyzed in this study. XRD analyses indicate that all of the samples contain considerable amount of smectite. The smectite does not appear as a form of interstratified phase with illite or chlorite. Preliminary chemical analyses by EDS in TEM suggest that the smectite is trioctahedral saponite with Ca as a dominant interlayer cation. To determine the saponite content quantitatively, cation exchange capacity (CEC) of bulk samples was measured. The samples show almost similar CEC of around 30 meq/100g, implying that bulk rock contains about 30 wt% of saponite, considering a general CEC of 100 meq/100g for monomineralic saponite. Such abundance of saponite might be a result from intense alteration of oceanic crust due to sea water circulation at low temperature. Previous experimental work suggests that saponite might be highly hydrated (two to three water layer hydration form) at the seismogenic P-T condition. Hence, altered upper oceanic crust is a possible water sink in the seismogenic zone. The water stored in the smectite interlayer region will be expelled via smectite to chlorite transition reaction, that might contribute to the dynamic weakening of the seimogenic plate boundary between the basement basalt and overlying accretionary prism.

Evidence for low-grade metamorphism, hydrothermal alteration, and diagenesis on Mars from phyllosilicate mineral assemblages

USGS Publications Warehouse

Ehlmann, Bethany L.; Mustard, John F; Clark, Roger N.; Swayze, Gregg A.; Murchie, Scott L.

2011-01-01

The enhanced spatial and spectral resolution provided by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) on the Mars Reconnaissance Orbiter (MRO) has led to the discovery of numerous hydrated silicate minerals on Mars, particularly in the ancient, cratered crust comprising the southern highlands. Phases recently identified using visible/near-infrared spectra include: smectite, chlorite, prehnite, high-charge phyllosilicates (illite or muscovite), the zeolite analcime, opaline silica, and serpentine. Some mineral assemblages represent the products of aqueous alteration at elevated temperatures. Geologic occurrences of these mineral assemblages are described using examples from west of the Isidis basin near the Nili Fossae and with reference to differences in implied temperature, fluid composition, and starting materials during alteration. The alteration minerals are not distributed homogeneously. Rather, certain craters host distinctive alteration assemblages: (1) prehnite-chlorite-silica, (2) analcime-silica-Fe,Mg-smectite-chlorite, (3) chlorite-illite (muscovite), and (4) serpentine, which furthermore has been found in bedrock units. These assemblages contrast with the prevalence of solely Fe,Mg-smectites in most phyllosilicate-bearing terrains on Mars, and they represent materials altered at depth then exposed by cratering. Of the minerals found to date, prehnite provides the clearest evidence for subsurface, hydrothermal/metamorphic alteration, as it forms only under highly restricted conditions (T = 200–400ºC). Multiple mechanisms exist for forming the other individual minerals; however, the most likely formation mechanisms for the characteristic mineralogic assemblages observed are, for (1) and (2), low-grade metamorphism or hydrothermal (<400ºC) circulation of fluids in basalt; for (3), transformation of trioctahedral smectites to chlorite and dioctahedral smectites to illite during diagenesis; and for (4), low-grade metamorphism or hydrothermal (<400ºC) circulation of fluids in ultramafic rocks. Evidence for high-grade metamorphism at elevated pressures or temperatures >400ºC has not been found.

Temperature-dependent residual shear strength characteristics of smectite-rich landslide soils

NASA Astrophysics Data System (ADS)

Shibasaki, Tatsuya; Matsuura, Sumio; Okamoto, Takashi

2015-04-01

On gentle clayey slopes in weathered argillaceous rock areas, there exist many landslides which repeatedly reactivate with slow movement. The slip surface soils of these landslides are sometimes composed dominantly of swelling clay mineral (smectite) which is well known to show extremely low residual friction angle. From field data monitored at landslide sites in Japan, it has become clear that some landslides with relatively shallow slip surface begin to move and become active in late autumn or early winter every year. In such cases, the triggering mechanisms of landslides have not been understood well enough, because landslide initiation and movement are not always clearly linked with rises in pore water pressures (ground water levels). In this study, we focus on the influence of seasonal variation in ground temperature on slope stability and have investigated the effect of temperature on the shear strength of slip surface soils. Undisturbed soil samples were collected by boring from the Busuno landslide in Japan. We performed box shear experiments on undisturbed slip surface soils at low temperature ranges (approximately 5-25 °C). XRD analysis revealed that these soils contain high fraction of smectite. Slickensided slip surface within test specimen was coincided with the shearing plane of the shear box and shear displacement was applied precisely along the localized slip surface. Experiments were performed under slow shearing rate condition (0.005mm/min) and the results showed that shear strength decreased with decreasing temperature. Temperature effect was rather significant on frictional angle than on cohesion. Ring shear experiments were also performed on normally-consolidated remoulded samples. Under residual strength condition, temperature-change experiments (cooling-event tests) ranging approximately from 5 to 25 °C were performed on smectite-rich landslide soils and commercial bentonites. As well as the results by box shear test, shear weakening behaviors were also recognized during cooling-event tests. Shear stress fluctuations, which were obtained by 1 Hz data sampling, showed that shear behavior characteristically changed in response to temperature conditions. Stick-slip behavior prevailed under room temperature conditions, whereas shear behavior gradually changed into stable sliding behavior as temperature decreased. SEM (Scanning Electric Microscope) observation on shear surfaces indicated that silt- and sand-size asperities in the vicinity of the shear surface influence the occurrence of stick-slip behavior. It is also characteristically noted that rod-shaped smectitic clays, here called "roll", developed on shear surfaces and are arrayed densely perpendicular to the shearing direction in a micrometer scale. We assume that these rolls are probably rotating slowly within shear zone and acting as a lubricant which affects the temperature-dependent frictional properties of the shearing plane. These experimental results show that residual strength characteristics of smectite-rich soils are sensitive to temperature conditions. Our findings imply that if slip surface soils contain a high fraction of smectite, a decrease in ground temperature can lead to lowered shear resistance of the slip surface and triggering of slow landslide movement.

Smectite for acute infectious diarrhoea in children.

PubMed

Pérez-Gaxiola, Giordano; Cuello-García, Carlos A; Florez, Ivan D; Pérez-Pico, Víctor M

2018-04-25

As mortality secondary to acute infectious diarrhoea has decreased worldwide, the focus shifts to adjuvant therapies to lessen the burden of disease. Smectite, a medicinal clay, could offer a complementary intervention to reduce the duration of diarrhoea. To assess the effects of smectite for treating acute infectious diarrhoea in children. We searched the Cochrane Infectious Diseases Group Specialized Register, the Cochrane Central Register of Controlled Trials (CENTRAL), MEDLINE (Pubmed), Embase (Ovid), LILACS, reference lists from studies and previous reviews, and conference abstracts, up to 27 June 2017. Randomized and quasi-randomized trials comparing smectite to a control group in children aged one month to 18 years old with acute infectious diarrhoea. Two review authors independently screened abstracts and the full texts for inclusion, extracted data, and assessed risk of bias. Our primary outcomes were duration of diarrhoea and clinical resolution at day 3. We summarized continuous outcomes using mean differences (MD) and dichotomous outcomes using risk ratios (RR), with 95% confidence intervals (CI). Where appropriate, we pooled data in meta-analyses and assessed heterogeneity. We explored publication bias using a funnel plot. Eighteen trials with 2616 children met our inclusion criteria. Studies were conducted in both ambulatory and in-hospital settings, and in both high-income and low- or middle-income countries. Most studies included children with rotavirus infections, and half included breastfed children.Smectite may reduce the duration of diarrhoea by approximately a day (MD -24.38 hours, 95% CI -30.91 to -17.85; 14 studies; 2209 children; low-certainty evidence); may increase clinical resolution at day 3 (risk ratio (RR) 2.10, 95% CI 1.30 to 3.39; 5 trials; 312 children; low-certainty evidence); and may reduce stool output (MD -11.37, 95% CI -21.94 to -0.79; 3 studies; 634 children; low-certainty evidence).We are uncertain whether smectite reduces stool frequency, measured as depositions per day (MD -1.33, 95% CI -2.28 to -0.38; 3 studies; 954 children; very low-certainty evidence). There was no evidence of an effect on need for hospitalization (RR 0.93, 95% CI 0.75 to 1.15; 2 studies; 885 children; low-certainty evidence) and need for intravenous rehydration (RR 0.77, 95% CI 0.54 to 1.11; 1 study; 81 children; moderate-certainty evidence). The most frequently reported side effect was constipation, which did not differ between groups (RR 4.71, 95% CI 0.56 to 39.19; 2 studies; 128 children; low-certainty evidence). No deaths or serious adverse effects were reported. Based on low-certainty evidence, smectite used as an adjuvant to rehydration therapy may reduce the duration of diarrhoea in children with acute infectious diarrhoea by a day; may increase cure rate by day 3; and may reduce stool output, but has no effect on hospitalization rates or need for intravenous therapy.

The origin of magnemite on Mars

NASA Technical Reports Server (NTRS)

Hargraves, R. B.

1984-01-01

An explanation for the magnetic properties of Martian surface material is discussed, specifically that the surface particles were composed primarily of smectite clay (nontronite) pigmented throughout by a red magnetic phase. The thermal treatment of nontronite in air, for long periods at 700 deg C or short periods at 900 deg C, results in destruction of the nontronite structure, a distinct reddening in color, and a spectacular increase in magnetic susceptibility and saturation magnetization (up to 4.4 Am squared/kg). Magnetic property measurements suggest that the magnetism is due to the presence of ultrafine particles of alpha or gamma Fe2O3; the precise identify was not resolved. Thermally treated nontronite has chemical, color and magnetic properties akin to those found by Viking on Mars. These results favor an origin for the fine grained Martian surface material by repeated impacts into an Fe-rich smectite-charged regolith, the smectite having resulted from hydrothermal alteration of volcanic or impact generated glass, the magnetic phase having resulted from the pressure or thermal shocked nontronite.

Phyllosilicate diversity and past aqueous activity revealed at Mawrth Vallis, Mars

USGS Publications Warehouse

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

2008-01-01

Observations by the Mars Reconnaissance Orbiter/Compact Reconnaissance Imaging Spectrometer for Mars in the Mawrth Vallis region show several phyllosilicate species, indicating a wide range of past aqueous activity. Iron/magnesium (Fe/Mg)-smectite is observed in light-toned outcrops that probably formed via aqueous alteration of basalt of the ancient cratered terrain. This unit is overlain by rocks rich in hydrated silica, montmorillonite, and kaolinite that may have formed via subsequent leaching of Fe and Mg through extended aqueous events or a change in aqueous chemistry. A spectral feature attributed to an Fe2+ phase is present in many locations in the Mawrth Vallis region at the transition from Fe/Mg-smectite to aluminum/silicon (Al/Si)-rich units. Fe2+-bearing materials in terrestrial sediments are typically associated with microorganisms or changes in pH or cations and could be explained here by hydrothermal activity. The stratigraphy of Fe/Mg-smectite overlain by a ferrous phase, hydrated silica, and then Al-phyllosilicates implies a complex aqueous history.

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.

Constraining the alteration history of a Late Cretaceous Patagonian volcaniclastic bentonite-ash-mudstone sequence using K-Ar and 40Ar/39Ar isotopes

NASA Astrophysics Data System (ADS)

Warr, L. N.; Hofmann, H.; van der Pluijm, B. A.

2017-01-01

Smectite is typically considered unsuitable for radiometric dating, as argon (40Ar) produced from decay of exchangeable potassium (40K) located in the interlayer sites can be lost during fluid-rock interaction and/or during wet sample preparation in the laboratory. However, age analysis of Late Cretaceous Argentinian bentonites and associated volcaniclastic rocks from Lago Pellegrini, Northern Patagonia, indicates that, in the case of these very low-permeability rocks, the radioactive 40Ar was retained and thus can provide information on smectite age and the timing of rock alteration. This study presents isotopic results that indicate the ash-to-bentonite conversion and alteration of the overlying tuffaceous mudstones in Northern Patagonia was complete 13-17 my after middle Campanian sedimentation when the system isotopically closed. The general absence of illite in these smectite-rich lithologies reflects the low activity of K and the low temperature (<60 °C) of the formation waters that altered the parent ash.

An AEM-TEM study of weathering and diagenesis, Abert Lake, Oregon. (1) Weathering reactions in the volcanics

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

Banfield, J.F.; Veblen, D.R.; Jones, B.F.

1991-10-01

Abert Lake in south-central Oregon provides a site suitable for the study of sequential weathering and diagenetic events. In this first of two papers, transmission electron microscopy was used to characterize the igneous mineralogy, subsolidus alteration assemblage, and the structural and chemical aspects of silicate weathering reactions that occur in the volcanic rocks that outcrop around the lake. Olivine and pyroxene replacement occurred topotactically, whereas feldspar and glass alteration produced randomly oriented smectite in channels and cavities. The tetrahedral, octahedral, and interlayer compositions of the weathering products, largely dioctahedral smectites, varied with primary mineral composition, rock type, and as themore » result of addition of elements released from adjacent reaction sites. The variability within and between the smectite assemblages highlights the microenvironmental diversity, fluctuating redox conditions, and variable solution chemistry associated with mineral weathering reactions in the surficial environment. Late-stage exhalative and aqueous alteration of the volcanics redistributed many components and formed a variety of alkali and alkali-earth carbonate, chloride, sulfate, and fluoride minerals in vugs and cracks. Overall, substantial Mg, Si, Na, Ca, and K are released by weathering reactions that include the almost complete destruction of the Mg-smectite that initially replaced olivine. The leaching of these elements from the volcanics provides an important source of these constituents in the lake water. The nature of subsequent diagenetic reactions resulting from the interaction between the materials transported to the lake and the solution will be described in part.« less

Evidence for Interlayer Collapse of Nontronite on Mars from Laboratory Visible and Near-IR Reflective Spectra

NASA Technical Reports Server (NTRS)

Morris, Richard V.; Ming, D. W.; Golden, D. C.; Graff, T. G.; Achilles, C. N.

2010-01-01

Dioctahedral smectites (e.g., nontronite and montmorillionite) are interpreted to occupy the optical surface of Mars at a number of locations on the basis of spectral features derived from interlayer H2O and MOH (M=Fe(3+)2, Fe(3+)Al, Al2, etc.) as observed by orbiting MRO-CRISM and MEx-OMEGA hyperspectral imaging spectrometers. At wavelengths shorter than approximately 2.7 micrometers, the strongest bands from interlayer H2O occur at approximately 1.4 and 1.9 micrometers from 2v1 and v1+v2, respectively, where v1 and v2 are the fundamental stretching and bending vibrations of the H2O molecule. Smectite MOH vibrations occur near 1.4 micrometers (stretching overtone) and in the region between 2.1 and 2.7 micrometers (stretching + bending combination). Because interlayer H2O can exchange with the martian environment, a number of studies have examined the strength of the interlayer H2O spectral features under Mars-like environmental conditions. The relationship between spectral properties and the underlying crystal structure of the smectites was not determined, and the extent of interlayer H2O removal was not established. We report combined visible and near-IR (VNIR), Mossbauer (MB), and powder X-ray diffraction (XRD) data for samples of the Fe-bearing smectite nontronite where the interlayer was collapsed by complete removal of interlayer H2O.

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

NASA Technical Reports Server (NTRS)

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

2009-01-01

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

Spectroscopic examinations of hydro- and glaciovolcanic basaltic tuffs: Modes of alteration and relevance for Mars

NASA Astrophysics Data System (ADS)

Farrand, W. H.; Wright, S. P.; Glotch, T. D.; Schröder, C.; Sklute, E. C.; Dyar, M. D.

2018-07-01

Hydro- and glaciovolcanism are processes that have taken place on both Earth and Mars. The amount of materials produced by these processes that are present in the martian surface layer is unknown, but may be substantial. We have used Mars rover analogue analysis techniques to examine altered tuff samples collected from multiple hydrovolcanic features, tuff rings and tuff cones, in the American west and from glaciovolcanic hyaloclastite ridges in Washington state and in Iceland. Analysis methods include VNIR-SWIR reflectance, MWIR thermal emissivity, thin section petrography, XRD, XRF, and Mössbauer spectroscopy. We distinguish three main types of tuff that differ prominently in petrography and VNIR-SWIR reflectance: minimally altered sideromelane tuff, gray to brown colored smectite-bearing tuff, and highly palagonitized tuff. Differences are also observed between the tuffs associated with hydrovolcanic tuff rings and tuff cones and those forming glaciovolcanic hyaloclastite ridges. For the locations sampled, hydrovolcanic palagonite tuffs are more smectite and zeolite rich while the palagonitized hyaloclastites from the sampled glaciovolcanic sites are largely devoid of zeolites and relatively lacking in smectites as well. The gray to brown colored tuffs are only observed in the hydrovolcanic deposits and appear to represent a distinct alteration pathway, with formation of smectites without associated palagonite formation. This is attributed to lower temperatures and possibly longer time scale alteration. Altered hydro- or glaciovolcanic materials might be recognized on the surface of Mars with rover-based instrumentation based on the results of this study.

Influence of climate and eolian dust on the major-element chemistry and clay mineralogy of soils in the northern Bighorn basin, U.S.A.

USGS Publications Warehouse

Reheis, M.C.

1990-01-01

Soil chronosequences in the northern Bighorn basin permit the study of chronologic changes in the major-element chemistry and clay mineralogy of soils formed in different climates. Two chronosequences along Rock Creek in south-central Montana formed on granitic alluvium in humid and semiarid climates over the past two million years. A chronosequence at the Kane fans in north-central Wyoming formed on calcareous alluvium in an arid climate over the past 600,000 years. Detailed analyses of elemental chemistry indicate that the soils in all three areas gradually incorporated eolian dust that contained less zirconium, considered to be chemically immobile during weathering, than did the alluvium. B and C horizons of soils in the wettest of the chronosequences developed mainly at logarithmic rates, suggesting that leaching, initially rapid but decelerating, dominated the dust additions. In contrast, soils in the most arid of the chronosequences developed at linear rates that reflect progressive dust additions that were little affected by leaching. Both weathering and erosion may cause changes with time to appear logarithmic in A horizons of soils under the moist and semiarid climatic regimes. Clay minerals form with time in the basal B and C horizons and reflect climatic differences in the three areas. Vermiculite, mixed-layer illite-smectite, and smectite form in the soils of the moist-climate chronosequence; smectite forms in the semiarid-climate chronosequence; and smectite and palygorskite form in the arid-climate chronosequence. ?? 1990.

Role of Microbes in the Smectite-to-Illite Reaction

USGS Publications Warehouse

Kim, J.; Dong, H.; Seabaugh, J.; Newell, Steven W.; Eberl, D.D.

2004-01-01

Temperature, pressure, and time have been thought to control the smectiteto-illite (S-I) reaction, an important diagenetic process used for petroleum exploration. We demonstrated that microorganisms can promote the S-I reaction by dissolving smectite through reduction of structural FE(III) at room temperature and 1 atmosphere within 14 days. This reaction typically requires conditions of 300?? to 350??C, 100 megapascals, and 4 to 5 months in the absence of microbial activity. These results challenge the conventional concept of the S-I reaction and of reaction kinetic models.

Localized and Areally Extensive Alterations in Marathon Valley, Endeavour Crater Rim, Mars

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.; Gellert, Ralf; Van Bommel, Scott; Arvidson, Raymond E.; Clark, Benton C.; Cohen, Barbara A.; Farrand, William H.; Ming, Douglas W.; Schroeder, Christian; Yen, Albert S.;

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.

The role of advanced reactive surface area characterization in improving predictions of mineral reaction rates

NASA Astrophysics Data System (ADS)

Beckingham, L. E.; Zhang, S.; Mitnick, E.; Cole, D. R.; Yang, L.; Anovitz, L. M.; Sheets, J.; Swift, A.; Kneafsey, T. J.; Landrot, G.; Mito, S.; Xue, Z.; Steefel, C. I.; DePaolo, D. J.; Ajo Franklin, J. B.

2014-12-01

Geologic sequestration of CO2 in deep sedimentary formations is a promising means of mitigating carbon emissions from coal-fired power plants but the long-term fate of injected CO2 is challenging to predict. Reactive transport models are used to gain insight over long times but rely on laboratory determined mineral reaction rates that have been difficult to extrapolate to field systems. This, in part, is due to a lack of understanding of mineral reactive surface area. Many models use an arbitrary approximation of reactive surface area, applying orders of magnitude scaling factors to measured BET or geometric surface areas. Recently, a few more sophisticated approaches have used 2D and 3D image analyses to determine mineral-specific reactive surface areas that account for the accessibility of minerals. However, the ability of these advanced surface area estimates to improve predictions of mineral reaction rates has yet to be determined. In this study, we fuse X-ray microCT, SEM QEMSCAN, XRD, SANS, and SEM-FIB analysis to determine mineral-specific accessible reactive surface areas for a core sample from the Nagaoka pilot CO2 injection site (Japan). This sample is primarily quartz, plagioclase, smectite, K-feldspar, and pyroxene. SEM imaging shows abundant smectite cement and grain coatings that decrease the fluid accessibility of other minerals. However, analysis of FIB-SEM images reveals that smectite nano-pores are well connected such that access to underlying minerals is not occluded by smectite coatings. Mineral-specific accessible surfaces are determined, accounting for the connectivity of the pore space with and without connected smectite nano-pores. The large-scale impact of variations in accessibility and dissolution rates are then determined through continuum scale modeling using grid-cell specific information on accessible surface areas. This approach will be compared with a traditional continuum scale model using mineral abundances and common surface area estimates. Ultimately, the effectiveness of advanced surface area characterization to improve mineral dissolution rates will be evaluated by comparison of model results with dissolution rates measured from a flow-through column experiment.

XRD measurement of mean crystallite thickness of illite and illite/smectite: Reappraisal of the Kubler index and the Scherrer equation

USGS Publications Warehouse

Drits, Victor A.; Środoń, Jan; Eberl, D.D.

1997-01-01

The standard form of the Scherrer equation, which has been used to calculate the mean thickness of the coherent scattering domain (CSD) of illite crystals from X-ray diffraction (XRD) full width data at half maximum (FWHM) intensity, employs a constant, Ksh, of 0.89. Use of this constant is unjustified, even if swelling has no effect on peak broadening, because this constant is valid only if all CSDs have a single thickness. For different thickness distributions, the Scherrer “constant” has very different values.Analysis of fundamental particle thickness data (transmission electron microscopy, TEM) for samples of authigenic illite and illite/smectite from diagenetically altered pyroclastics and filamentous illites from sandstones reveals a unique family of lognormal thickness distributions for these clays. Experimental relations between the distributions' lognormal parameters and mean thicknesses are established. These relations then are used to calculate the mean thickness of CSDs for illitic samples from XRD FWHM, or from integral XRD peak widths (integrated intensity/maximum intensity).For mixed-layer illite/smectite, the measured thickness of the CSD corresponds to the mean thickness of the mixed-layer crystal. Using this measurement, the mean thickness of the fundamental particles that compose the mixed-layer crystals can be calculated after XRD determination of percent smectitic interlayers. The effect of mixed layering (swelling) on XRD peak width for these samples is eliminated by using the 003 reflection for glycolated samples, and the 001, 002 or 003 reflection for dehydrated, K-saturated samples. If this technique is applied to the 001 reflection of air-dried samples (Kubler index measurement), mean CSD thicknesses are underestimated due to the mixed-layering effect.The technique was calibrated using NEW MOD©-simulated XRD profiles of illite, and then tested on well-characterized illite and illite/smectite samples. The XRD measurements are in good agreement with estimates of the mean thickness of fundamental particles obtained both from TEM measurements and from fixed cations content, up to a mean value of 20 layers. Correction for instrumental broadening under the conditions employed here is unnecessary for this range of thicknesses.

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

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.

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.

Seismic slip on clay nano-foliation

NASA Astrophysics Data System (ADS)

Aretusini, Stefano; Plümper, Oliver; Spagnuolo, Elena; Di Toro, Giulio

2017-04-01

Deformation processes active at seismic slip rates (ca. 1 m/s) on smectite-rich slipping zones are not well understood, although they likely control the mechanical behaviour of: i) subduction zone faults affected by tsunamigenic earthquakes and seismic surface rupturing, and ii) landslide decollements. Here we present a set of rotary experiments performed on water-dampened 2 mm thick clay-rich (70% wt. smectite and 30% wt. opal) gouge layers sheared at slip rates V ranging from 0.01 to 1.5 m/s, for 3 m of displacement under 5 MPa normal stress. Microstructural analyses were conducted on pre- and post-sheared gouges using focused ion beam scanning electron and transmission electron microscopy. All sheared gouges were slip weakening in the first 0.1 m of displacement, with friction coefficient decreasing from 0.4-0.3 to 0.1-0.05. Then, with progressive slip, gouges evolved to slip-strengthening (final friction coefficient of 0.47-0.35) at V ≤0.1 m/s and slip-neutral (final friction of 0.05) at V=1.5 m/s. Despite the large difference in the imposed slip rate and frictional behaviour, the slipping zone always consisted of a nano-foliation defined by sub-micrometric smectite crystals wrapping opal grains. The microstructural differences were (1) the thickness of the slipping zone which decreased from 1.5 mm at V≤0.1 m/s to 0.15 mm at V=1.5 m/s, and (2) the structure of the foliated fabric, which was S/C'-type at V≤0.1 m/s and anastomosing-type at V=1.5 m/s. The presence of a similar nano-foliation in all the smectite-rich wet gouges suggests the activation of similar frictional processes, most likely grain boundary and interlayer frictional sliding aided by water films, operating from sub-seismic to seismic strain rates ( 10-10000 1/s). Water films on crystal boundaries and interlayers possibly control the micro- and nano-mechanics of smectite deformation, therefore influencing the bulk frictional behaviour during seismic slip.

Reassessment of the volkonskoite-chromian smectite nomenclature problem.

USGS Publications Warehouse

Foord, Eugene E.; Starkey, Harry C.; Taggart, Joseph E.; Shawe, Daniel R.

1987-01-01

The name volkonskoite was first used in 1830 to describe a bright blue-green, chromium-bearing clay material from the Okhansk region, west of the Ural Mountains, U.S.S.R. Since that time, the name has been applied to numerous members of the smectite group of clay minerals, although the reported chromium content has ranged from 1% to about 30% Cr2O3. The name has also been applied to some chromian chlorites. Because volkonskoite has been used for materials that differ not only in their chromium content but also in their basic structure, the species status of the mineral has been unclear.To resolve this uncertainty, two specimens of volkonskoite from (1) Mount Efimiatsk, the type locality in the Soviet Union (USNM 16308) and (2) the Okhansk region in the Perm Basin, U.S.S.R. (USNM R4820), were examined by several mineralogical techniques. Neotype sample 16308 has the following structural formula:(Ca0.11Mg0.11Fe2+0.03K0.02)(Cr1.18Mg0.78Fe3+0.29Ca0.02)(Si3.50Al0.51)O10(OH)2 ⋅3.64H2O.Sample R4820 has the following structural formula:(Ca0.25Mg0.05Fe2+0.01K0.03Mn0.01)(Cr1.07Mg0.75Fe3+0.35(Si3.59Al0.43)O10(OH)2 ⋅4.22H2O.Mössbauer spectroscopy indicates that 91% and 98% of the iron is present as Fe3+ in samples 16308 and R4820, respectively. X-ray powder diffraction patterns of both samples have broad lines corresponding to minerals of the smectite group.On the basis of these data, volkonskoite appears to be a dioctahedral member of the smectite group that contains chromium as the dominant cation in the octahedral layer. Smectites containing less than this amount of octahedral chromium should not be called volkonskoite, but should be named by chemical element adjectives, e.g., chromian montmorillonite, chromian nontronite.

[An experimental study on the prevention of enteral bacterial translocation in scalded rats by smectite powder].

PubMed

Su, Hai-tao; Li, Yi-shu; Lu, Shu-liang; Sun, Man; Qing, Chun; Li, Zong-yu; Shao, Tie-bing; Huang, Li-bing; Qu, Bing; Yang, Xin-bo

2005-04-01

To explore the preventive and treatment effects of smectite powder on enteral bacterial translocation in scalded rats. Fifty-four Sprague-Dawley (SD) rats were randomly divided into three groups, i.e. normal control (A, n = 6), burn control (B, n = 24), and burn treatment (T, n = 24) groups. The rats in B and T groups were fed with tracing bacteria JM109, which was transfected with PUC19 plasmid in advance. The rats were subjected to 30% TBSA scald injury after the plasmid was shown to have colonized in the intestine. Smectite powder (0.6 g/day/kg) was fed to rats of T group immediately after the scalding, while those in B group received no smectite powder. Bacterial translocation in blood and mesenteric lymph nodes in all groups was observed and identified by enzyme digestion at 12 post scald hour (PSH) and on 1, 3 and 5 post-scald days (PSD). The contents of malondialdehyde (MDA) and superoxide dismutase (SOD) were determined in rat intestinal tissue. And the degree of injury to the entire small intestine was observed pathologically. The villus height of intestinal mucosa was measured, and the rate of epithelial nuclear splitting of mucosal crypts was calculated. The number of rats with positive blood bacterial culture in B group was obviously higher than that in A and T groups (P < 0.05) on 1 and 5 PSD. The bacterial quantity in mesenteric lymph nodes (MLN) in T group on 1 PSD (38 +/- 16 CFU/g) and 5 PSD (68 +/- 20 CFU/g) were obviously lower than those in B group (228 +/- 67 vs 183 +/- 29 CFU/g, P < 0.05). There was significant difference in the intestinal contents of MDA and SOD between B and T groups at each time point (P < 0.05). The rat jejunum villus height and the epithelial nuclear splitting in the small intestine mucosa in T group were evidently higher than those in B group (P < 0.05 or 0.01). Smectite powder is beneficial to the protection of the intestinal mucosa in scalded rats, and can effectively prevent postburn intestinal bacterial translocation in rats.

Links Between Clay Dehydration and Plate Boundary Earthquakes Along the Costa Rica Subduction Megathrust

NASA Astrophysics Data System (ADS)

Lauer, R. M.; Saffer, D. M.; Harris, R. N.

2016-12-01

The transformation of smectite to illite is one leading hypothesis to explain the upper transition from stable aseismic slip to seismogenesis along subduction megathrusts, through its influence on both fluid pressure and fault zone frictional properties. Here, we document a well-defined spatial correlation between plate boundary seismicity and smectite transformation at the Costa Rican subduction zone, consistent with the idea that clay transformation and associated silica deposition condition the fault for locking and stick-slip behavior. Previous efforts to explore this relationship have been impeded by a lack of studies that precisely locate seismicity at margins where the thermal structure is well-constrained. We take advantage of new results from Costa Rica that together provide a clear view of both seismicity and thermal conditions on the Middle-America megathrust. These results allow a thorough evaluation of the links between smectite dehydration and fault-slip behavior. We simulate smectite transformation using a kinetic model to assess reaction progress and quantify fluid production at the plate boundary, along 16-transects that span a 500-km length along strike. We find that large (Mw≥7.0) earthquakes are located down-dip of peak fluid production and in regions where the reaction is >50% complete. The earthquake ruptures, however, extend up-dip into the zone of peak reaction. We suggest that silica cementation that accompanies the reaction promotes lithification, embrittlement, and slip-weakening behavior that together enable the initiation of unstable slip, which can then propagate updip into fluid-rich and weak regions of the megathrust that coincide with the peak dehydration window.

Evaluation of Household Bleach as an Ovicide for the Control of Aedes Aegypti

PubMed Central

Mackay, Andrew J.; Amador, Manuel; Felix, Gilberto; Acevedo, Veronica; Barrera, Roberto

2015-01-01

Accumulations of dormant eggs in container habitats allow Aedes aegypti populations to survive harsh environmental conditions and may frustrate control interventions directed at larval and adult life stages. While sodium hypochlorite solutions (NaOCl) have long been recognized as ovicides for use against dengue vectors, the susceptibility of eggs to spray applications has not been robustly evaluated on substrate materials representative of the most frequently utilized artificial container habitats. Experiments were performed under controlled and natural conditions by applying dilutions of household bleach (52.5 ppt NaOCl) as a spray to eggs on plastic, rubber, and concrete surfaces, with and without a smectite clay thickener. Laboratory assays identified the minimum NaOCl concentrations required to eliminate eggs on plastic (10 ppt), rubber (20 ppt) and concrete (20 ppt) surfaces. Addition of smectite clay reduced the minimum effective concentration to 10 ppt NaOCl for all 3 substrates. A minimum exposure period of 24 h was required to completely eliminate egg viability on concrete surfaces, even at the highest NaOCl concentration (52.5 ppt). Field experiments verified that spray application of a 1:3 dilution of household bleach mixed with smectite clay can reduce egg hatching by ≥ 99% in shaded and sun-exposed plastic containers. Similarly, 4:1 dilution of household bleach (with or without smectite clay) eliminated ≥ 98% of eggs from concrete surfaces in outdoor, water-filled drums. In this study, we propose a practical, effective and safe strategy for using household bleach to eliminate Ae. aegypti eggs in a range of artificial container habitats. PMID:25843179

Geochemistry of volcanogenic clayey marine sediments from the Hazar-Maden Basin (Eastern Turkey)

NASA Astrophysics Data System (ADS)

Akkoca, Dicle Bal; Kürüm, Sevcan; Huff, Warren D.

2013-12-01

The Hazar-Madeıı Basin sediments were deposited along the southern branch of the Neotethys Ocean margin during Late Maastrichtian-Middle Eocene times. X-ray powder diffraction (XRD), ICP-AES, ICP-MS and scanning electron microscopy (SEM) were performed on samples of the Upper Maastrichtian-Middle Eocene Hazar Group and the Middle Eocene Maden Complex from the Hazar-Maden Basin to investigate the main effects of depositional envi- ronmental parameters in three sections belonging to deeper marine (slope), proximal arc volcanic (Mastarhill and Yukaribag sections) and shallow platform marine (Sebken section) settings. Marine sediments contain clay minerals (smectite, smectite/chlorite, chlorite, illite, interstratified illite/smectite, illite/chlorite, palygorskite), clinoptilolite, quartz, feldspar, calcite, dolomite, opal-CT and hematite. The clays are dominated by iron-rich smectites. La, Zr and Th concentrations are high in the shallow marginal Sebken section where the terrestrial detrital contribution is significant, while Sc and Co are more dominant in the deeper marine (slope) Yukaribag section, which is represented by basic-type volcanism and a higher contribution of hydrothermal phases. In a chondrite-normalized REE diagram, the negative Eu anomaly in samples from Sebken, the section which was deposited in a shallow marine environment, is less significant than that of the other two sections indicating the presence of a high terrestrial contribution in that part of the basin. A decrease in LREE v/HREEiV and Lajv/Ybv, LaiV/Sin v ratios from Sebken to Mastarhill and the Yukaribag sections indi- cates deepening of the basin and an increasing contribution of volcanism in that direction.

Illite equilibria in solutions: III. A re-interpretation of the data of Sass et al. (1987)

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

Aja, S.U.

1991-11-01

In a recent solubility study of Goose Lake and Beavers Bend illite, SASS et al. (1987) inferred the existence of three components of natural illites (K{sub 0.24}/O{sub 10}(OH){sub 2}), (K{sub 0.67}/O{sub 10}(OH){sub 2}), and (K{sub 0.90}/O{sub 10}(OH){sub 2}) which were interpreted to be smectite, illite, and K-mica, respectively. They also speculated that illite-smectite equilibrium is metastable under diagenetic conditions except between 90 and 110C where it is stabilized by an ordering transition. A re-interpretation of the data of SASS et al. (1987) indicates that the solubility-controlling phases have the following K atoms per half cell: 0.29, 0.52, 0.69, 0.084, andmore » 1.0. Furthermore, solution equilibration investigations of kaolinite-microcline mixtures have shown that these two minerals do not coexist stably. Thus, the question of an ordering transition whose main effect is to stabilize illite-smectite equilibria relative to kaolinite-microcline assemblage does not arise.« less

Chemical remagnetization and clay diagenesis: testing the hypothesis in the Cretaceous sedimentary rocks of northwestern Montana

NASA Astrophysics Data System (ADS)

Gill, J. D.; Elmore, R. D.; Engel, M. H.

Although the migration of fluids is a likely agent of remagnetization for some chemical remanent magnetizations (CRMs), widespread CRMs, which occur in rocks that have not been altered by externally derived fluids, need to explained by another mechanism. We are testing clay diagenesis as a remagnetization mechanism for such CRMs by comparing results from Mesozoic strata in the disturbed belt of Montana where the rocks contain ordered illite/smectite that formed by moderate heating as a result of thrust loading, with equivalent strata on the adjacent Sweetgrass Arch which contain unaltered smectite-rich clay mineral assemblages. The results indicate that the magnetization in the rocks in the Sweetgrass Arch is weak and dominated by a modern viscous component. In contrast, the disturbed belt rocks have higher magnetic intensities and contain a prefolding or early synfolding, reversed tertiary magnetization that is interpreted to be a CRM residing in magnetite and perhaps pyrrhotite. A presence-absence test and the timing of acquisition for the CRM suggest that magnetite authigenesis could be related to the smectite-to-illite conversion.

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.

Possible Bacteria in Nakhla

NASA Technical Reports Server (NTRS)

McKay, David S., Jr.; Westall, F.; Wentworth, S. W.; Thomas-Keptra, K.

1999-01-01

Mars Agueous Alteration Nakhla contains alteration products in an extensive network of which fill cracks, veins, and void spaces, composed of smectite, although in some cases they are amorphous and gel-like. Strong evidence presented show that these alteration products developed on Mars: some veins are offset by impact faulting of olivine followed by annealing of the olivine, and veins near the fusion crust show partial vesicle development suggesting heating and volatile liberation. The smectite-containing cracks and veins are interpreted as low temperature aqueous alteration on Mars. We have been studying these veins with optical microscopy and high resolution SEM.

Diagenesis of clay mineral assemblages in the Shikoku Basin: Inputs to the Nankai Trough megathrust and seismogenic zone

NASA Astrophysics Data System (ADS)

Underwood, M.; Guo, J.; Song, C.

2012-12-01

One of the essential components of the Nankai Trough Seismogenic Zone Experiment (NanTroSEIZE) is to document the composition and diagenetic alteration of sedimentary inputs to the subduction zone of SW Japan. Two sites were drilled seaward of the trench during IODP Expeditions 322 and 333 to demonstrate how those subduction inputs have been influenced by the basement topography of Shikoku Basin. Site C0011 was drilled on the NW flank of Kashinosaki Knoll, and Site C0012 is located near the seamount's summit. The lithostratigraphy expands and condenses from site to site, but the clay mineral assemblages are nearly identical when comparisons are made among coeval units. The early history of sedimentation (middle to late Miocene) was dominated by expandable clay minerals of the smectite group. Contents of smectite in strata older than 5.3 Ma typically exceed 65% of the clay-size fraction, and there are dozens of bentonite layers (altered volcanic ash) interbedded with the hemipelagic mudstones and turbidites. Those percentages amount to >45 wt-% smectite in the bulk mudstone. Volcanic sources for the Miocene clay probably included the ancestral Izu-Bonin island arc, the Izu-Honshu collision zone, and anomalous near-trench magma bodies in the Outer Zone of Honshu and Shikoku Island. As sedimentation progressed into the Pliocene and Pleistocene, mud supplies to the Shikoku Basin shifted increasingly to detrital illite and chlorite eroded from the uplifted accretionary complex (Outer Zone). At Site C0011, the younger hemipelagic-pyroclastic facies (upper Shikoku Basin) contains an average of 43% smectite, 36% illite, and 18% kaolinite + chlorite in the clay-size fraction. At Site C0012, comparable values are S = 51%, I = 32%, and K+C = 14%. XRD results show no evidence of smectite-to-illite diagenesis seaward of the trench, although it is important to note that Site C0011 was abandoned before reaching basaltic basement. We can predict the extent of smectite-to-illite diagenesis using simple kinetic models that account for differences in heat flow from the flank to the summit of Kashinosaki Knoll and rapid burial of Shikoku Basin facies beneath the Quaternary trench wedge. Our modeling results support the notion that illitization does not progress to detectable levels (>20% I in mixed-layer clay) until after the Shikoku Basin deposits are subducted beneath the frontal megathrust. That absence of pre-subduction diagenesis is important to consider when assessing the potential for fluid production and fluid overpressures deeper down-dip along the megathrust, as well as for identifying the potential sources for freshening of interstitial fluids.

Hydrothermal alteration in research drill hole Y-3, Lower Geyser Basin, Yellowstone National Park, Wyoming

USGS Publications Warehouse

Bargar, Keith E.; Beeson, Melvin H.

1985-01-01

Y-3, a U.S. Geological Survey research diamond-drill hole in Lower Geyser Basin, Yellowstone National Park, Wyoming, reached a depth of 156.7 m. The recovered drill core consists of 42.2 m of surficial (mostly glacial) sediments and two rhyolite flows (Nez Perce Creek flow and an older, unnamed rhyolite flow) of the Central Plateau Member of the Pleistocene Plateau Rhyolite. Hydrothermal alteration is fairly extensive in most of the drill core. The surficial deposits are largely cemented by silica and zeolite minerals; and the two rhyolite flows are, in part, bleached by thermal water that deposited numerous hydrothermal minerals in cavities and fractures. Hydrothermal minerals containing sodium as a dominant cation (analcime, clinoptilolite, mordenite, Na-smectite, and aegirine) are more abundant than calcium-bearing minerals (calcite, fluorite, Ca-smectite, and pectolite) in the sedimentary section of the drill core. In the volcanic section of drill core Y-3, calcium-rich minerals (dachiardite, laumontite, yugawaralite, calcite, fluorite, Ca-smectite, pectolite, and truscottite) are predominant over sodium-bearing minerals (aegirine, mordenite, and Na-smectite). Hydrothermal minerals that contain significant amounts of potassium (alunite and lepidolite in the sediments and illitesmectite in the rhyolite flows) are found in the two drill-core intervals. Drill core y:.3 also contains hydrothermal silica minerals (opal, [3-cristobalite, chalcedony, and quartz), other clay minerals (allophane, halloysite, kaolinite, and chlorite), gypsum, pyrite, and hematite. The dominance of calcium-bearing hydrothermal minerals in the lower rhyolitic section of the y:.3 drill core appears to be due to loss of calcium, along with potassium, during adiabatic cooling of an ascending boiling water.

The impact of splay faults on fluid flow, solute transport, and pore pressure distribution in subduction zones: A case study offshore the Nicoya Peninsula, Costa Rica

NASA Astrophysics Data System (ADS)

Lauer, Rachel M.; Saffer, Demian M.

2015-04-01

Observations of seafloor seeps on the continental slope of many subduction zones illustrate that splay faults represent a primary hydraulic connection to the plate boundary at depth, carry deeply sourced fluids to the seafloor, and are in some cases associated with mud volcanoes. However, the role of these structures in forearc hydrogeology remains poorly quantified. We use a 2-D numerical model that simulates coupled fluid flow and solute transport driven by fluid sources from tectonically driven compaction and smectite transformation to investigate the effects of permeable splay faults on solute transport and pore pressure distribution. We focus on the Nicoya margin of Costa Rica as a case study, where previous modeling and field studies constrain flow rates, thermal structure, and margin geology. In our simulations, splay faults accommodate up to 33% of the total dewatering flux, primarily along faults that outcrop within 25 km of the trench. The distribution and fate of dehydration-derived fluids is strongly dependent on thermal structure, which determines the locus of smectite transformation. In simulations of a cold end-member margin, smectite transformation initiates 30 km from the trench, and 64% of the dehydration-derived fluids are intercepted by splay faults and carried to the middle and upper slope, rather than exiting at the trench. For a warm end-member, smectite transformation initiates 7 km from the trench, and the associated fluids are primarily transmitted to the trench via the décollement (50%), and faults intercept only 21% of these fluids. For a wide range of splay fault permeabilities, simulated fluid pressures are near lithostatic where the faults intersect overlying slope sediments, providing a viable mechanism for the formation of mud volcanoes.

Quantifying mineral abundances of complex mixtures by coupling spectral deconvolution of SWIR spectra (2.1-2.4 μm) and regression tree analysis

USGS Publications Warehouse

Mulder, V.L.; Plotze, Michael; de Bruin, Sytze; Schaepman, Michael E.; Mavris, C.; Kokaly, Raymond F.; Egli, Markus

2013-01-01

This paper presents a methodology for assessing mineral abundances of mixtures having more than two constituents using absorption features in the 2.1-2.4 μm wavelength region. In the first step, the absorption behaviour of mineral mixtures is parameterised by exponential Gaussian optimisation. Next, mineral abundances are predicted by regression tree analysis using these parameters as inputs. The approach is demonstrated on a range of prepared samples with known abundances of kaolinite, dioctahedral mica, smectite, calcite and quartz and on a set of field samples from Morocco. The latter contained varying quantities of other minerals, some of which did not have diagnostic absorption features in the 2.1-2.4 μm region. Cross validation showed that the prepared samples of kaolinite, dioctahedral mica, smectite and calcite were predicted with a root mean square error (RMSE) less than 9 wt.%. For the field samples, the RMSE was less than 8 wt.% for calcite, dioctahedral mica and kaolinite abundances. Smectite could not be well predicted, which was attributed to spectral variation of the cations within the dioctahedral layered smectites. Substitution of part of the quartz by chlorite at the prediction phase hardly affected the accuracy of the predicted mineral content; this suggests that the method is robust in handling the omission of minerals during the training phase. The degree of expression of absorption components was different between the field sample and the laboratory mixtures. This demonstrates that the method should be calibrated and trained on local samples. Our method allows the simultaneous quantification of more than two minerals within a complex mixture and thereby enhances the perspectives of spectral analysis for mineral abundances.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Distributions of clay minerals in surface sediments of the middle Bay of Bengal: Source and transport pattern

NASA Astrophysics Data System (ADS)

Li, Jingrui; Liu, Shengfa; Shi, Xuefa; Feng, Xiuli; Fang, Xisheng; Cao, Peng; Sun, Xingquan; Wenxing, Ye; Khokiattiwong, Somkiat; Kornkanitnan, Narumol

2017-08-01

The clay mineral contents in 110 surface sediment samples collected from the middle of the Bay of Bengal were analyzed by X-ray diffraction (XRD) to investigate the provenance and transport patterns. The illite content was highest, followed by chlorite, kaolinite and then smectite, with average weight percent distributions of 52%, 22%, 14% and 12%, respectively. Illite and chlorite had similar distribution pattern, with higher contents in the northern and central areas and lower contents in the southern area, whereas smectite showed the opposite distribution pattern. Kaolinite show no obvious higher or lower areas and the southern ;belt; was one of the highest content areas. Based on the spatial distribution characteristics and cluster analysis results, the study area can be classified into two provinces. Province I covers the southwestern area and contains high concentrations of illite and smectite sediments. Province II covers most sites and is also characterized by high concentrations of illite, but the weight percent of smectite is only half of that of province I. According to a quantitative estimate using end-member clay minerals contents, the relative contributions from the Himalayan source and the Indian source are 63% and 37% on average, respectively. Integrative analysis indicates that the hydrodynamic environment in the study area, especially the turbidity and surface monsoonal circulation, plays an important role in the spatial distribution and dispersal of the clay fraction in the sediments. The sediments in province I are mainly from the Indian source transported by the East Indian Coastal Current (EICC) and the surface monsoon circulation with minor contributions from the Himalayan source while the sediments in province II are mainly from the Himalayan source transported by turbidity and surface monsoonal circulation with little contribution from Indian river materials.

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

NASA Technical Reports Server (NTRS)

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

Frictional Properties of the Nankai Trough Accretionary Mud Samples Collected from 1000-3000 mbsf at IODP Site C0002

NASA Astrophysics Data System (ADS)

Kanagawa, K.; Hoshino, K.; Abe, K.; Sawai, M.

2016-12-01

We conducted triaxial friction experiments on the Nankai Trough accretionary mud samples collected from 1000-3000 mbsf (meters below seafloor) at IODP Site C0002 off Kii Peninsula, at confining pressures of 44-83 MPa, pore water pressures of 32-50 MPa and temperatures of 51-98°C equivalent to their in situ conditions, and at axial displacement rates changed stepwise among 0.1, 1 and 10 µm/s, in order to investigate their frictional properties changing with depth. XRD analyses of tested mud samples revealed that the content of total clay minerals tends to increase with depth from 30 to 60 wt%, while the smectite fraction in total clay minerals decreases with depth from 0.75 to 0.3. Because the temperature at 3000 mbsf reaches 100°C, this decrease in smectite fraction with depth is likely due to the progress of smectite dehydration with increasing temperature. Friction experiments on tested mud samples revealed that the steady-state friction coefficient at an axial displacement rate of 1 µm/s tends to decrease with depth from 0.5 to 0.3, according to the increasing content of total clay minerals with depth. Velocity dependence of steady-state friction also tends to decrease with depth, likely reflecting a decrease in smectite fraction in total clay minerals. Although velocity dependence of steady-state friction is mostly positive at depths down to 3000 mbsf, it is locally neutral or negative at depths deeper than 2000 mbsf, implying that faulting at these depths is conditionally stable and possibly accompanied by slow slip events.

Phosphoric acid purification through different raw and activated clay materials (Southern Tunisia)

NASA Astrophysics Data System (ADS)

Trabelsi, Wafa; Tlili, Ali

2017-05-01

This study concerns the purification of Tunisian phosphoric acid produced by the Tunisian Chemical Group (TCG), using raw and activated clays materials from Southern Tunisia. The Gafsa basin clays samples (Jebel Hamadi (JHM); Jebel Stah (JS) and the El Hamma sample (Jebel Aïdoudi (JAD)) were activated with 3 M, HCl solution. Phosphoric acid purification was performed on raw and activated clays. Mineralogical characterisation was carried out using the X-ray powder diffraction method and infrared absorption spectroscopy. Textural changes between raw and activated clays were identified using SEM observations and specific surface analysis. Jebel Hamadi clays were almost dominated by smectite associated with kaolinite and illite traces, while Jebel Stah and Jebel Aïdoudi clays were composed of the association of smectite, illite and kaolinite. It is worth noting that the position of the smectite (001) reflection increased after the acidic activation in all studied samples, indicating the relaxation of the smectite structure along the c-axis. This was corroborated by the increasing specific surface area of the clay particles with the activation process. The specific surface area was close to 50 m2/g and 200 m2/g, for raw and activated materials, respectively. The maximum phosphoric acid purification was obtained by using activated clays with 3 N HCl for 4 h. This performance correlated with the maximum of the external specific surface area which generated strong acid sites. Furthermore, the best results of phosphoric acids purification from TCG were obtained at a specific consumption equivalent to 30 Kg of clay/ton of P2O5. These results showed that the best phosphoric acid purification was yielded by Jebel Aïdoudi clay. In all cases, the highest organic carbon reduction rates in the phosphoric acid after filtration were obtained at 90°C.

Effect of groundwater geochemistry on pentachlorophenol remediation by smectite-templated nanosized Pd0/Fe0.

PubMed

Jia, Hanzhong; Gu, Cheng; Li, Hui; Fan, Xiaoyun; Li, Shouzhu; Wang, Chuanyi

2012-09-01

Zero-valent iron holds great promise in treating groundwater, and its reactivity and efficacy depend on many surrounding factors. In the present work, the effects of solution chemistry such as pH, humic acid (HA), and inorganic ions on pentachlorophenol (PCP) dechlorination by smectite-templated Pd(0)/Fe(0) were systematically studied. Smectite-templated Pd(0)/Fe(0) was prepared by saturating the negatively charged sites of smectite clay with Fe(III) and a small amount of Pd(II), followed by borohydride reduction to convert Fe(III) and Pd(II) into zero-valent metal clusters. Batch experiments were conducted to investigate the effects of water chemistry on PCP remediation. The PCP dechlorination rate critically depends on the reaction pH over the range 6.0~10.0; the rate constant (k (obs)) increases with decreasing the reaction pH value. Also, the PCP remediation is inhibited by HA, which can be attributed to the electron competition of HA with H(+). In addition, the reduction of PCP can be accelerated by various anions, following the order: Cl(-) > HCO (3) (-) > SO (4) (2-) ~no anion. In the case of cations, Ca(2+) and Mg(2+) (10 mM) decrease the dechlorination rate to 0.7959 and 0.7798 from 1.315 h(-1), respectively. After introducing HA into the reaction systems with cations or/and anions, the dechlorination rates are similar to that containing HA alone. This study reveals that low pH and the presence of some anions such as Cl(-) facilitate the PCP dechlorination and induce the rapid consumption of nanosized zero-valent iron simultaneously. However, the dechlorination rate is no longer correlated to the inhibitory or accelerating effects by cations and anions in the presence of 10 mg/L HA.

Isolation of Phyllosilicate–Iron Redox Cycling Microorganisms from an Illite–Smectite Rich Hydromorphic Soil

PubMed Central

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

2012-01-01

The biogeochemistry of phyllosilicate–Fe redox cycling was studied in a Phalaris arundinacea (reed canary grass) dominated redoximorphic soil from Shovelers Sink, a small glacial depression near Madison, WI. The clay size fraction of Shovelers Sink soil accounts for 16% of the dry weight of the soil, yet contributes 74% of total Fe. The dominant mineral in the clay size fraction is mixed layer illite–smectite, and in contrast to many other soils and sediments, Fe(III) oxides are present in low abundance. We examined the Fe biogeochemistry of Shovelers Sink soils, estimated the abundance of Fe redox cycling microorganisms, and isolated in pure culture representative phyllosilicate–Fe oxidizing and reducing organisms. The abundance of phyllosilicate–Fe reducing and oxidizing organisms was low compared to culturable aerobic heterotrophs. Both direct isolation and dilution-to-extinction approaches using structural Fe(II) in Bancroft biotite as a Fe(II) source, and O2 as the electron acceptor, resulted in recovery of common rhizosphere organisms including Bradyrhizobium spp. and strains of Cupriavidus necator and Ralstonia solanacearum. In addition to oxidizing biotite and soluble Fe(II) with O2, each of these isolates was able to oxidize Fe(II) in reduced NAu-2 smectite with NO3- as the electron acceptor. Oxidized NAu-2 smectite or amorphous Fe(III) oxide served as electron acceptors for enrichment and isolation of Fe(III)-reducing microorganisms, resulting in recovery of a strain related to Geobacter toluenoxydans. The ability of the recovered microorganisms to cycle phyllosilicate–Fe was verified in an experiment with native Shovelers Sink clay. This study confirms that Fe in the native Shovelers Sink clay is readily available for microbial redox transformation and can be cycled by the Fe(III)-reducing and Fe(II)-oxidizing microorganisms recovered from the soil. PMID:22493596

Understanding the sorption mechanisms of aflatoxin B1 to kaolinite, illite, and smectite clays via a comparative computational study.

PubMed

Kang, Fuxing; Ge, Yangyang; Hu, Xiaojie; Goikavi, Caspar; Waigi, Michael Gatheru; Gao, Yanzheng; Ling, Wanting

2016-12-15

In current adsorption studies of biotoxins to phyllosilicate clays, multiply weak bonding types regarding these adsorptions are not well known; the major attractive forces, especially for kaolinite and illite, are difficult to be identified as compared to smectite with exchangeable cations. Here, we discriminated the bonding types of aflatoxin B1 (AFB1) contaminant to these clays by combined batch experiment with model computation, expounded their bonding mechanisms which have been not quantitatively described by researchers. The observed adsorbent-to-solution distribution coefficients (K d ) of AFB1 presented in increasing order of 18.5-37.1, 141.6-158.3, and 354.6-484.7L/kg for kaolinite, illite, and smectite, respectively. Normalization of adsorbent-specific surface areas showed that adsorption affinity of AFB1 is mainly dependent on the outside surfaces of clay aggregates. The model computation and test of ionic effect further suggested that weakly electrostatic attractions ((Si/Al-OH) 2 ⋯(OC) 2 ) are responsible for AFB1-kaolinite adsorption (K d , 18.5-37.1L/kg); a moderate electron-donor-acceptor attraction ((CO) 2 ⋯K + ⋯(O-Al) 3 ) is related to AFB1-illite adsorption (K d , 141.6-158.3L/kg); a strong calcium-bridging linkage ((CO) 2 ⋯Ca 2+ ⋯(O-Si) 4 ) is involved in AFB1-smectite adsorption (K d , 354.6-484.7L/kg). Changes in Gibbs free energy (ΔG°) suggested that the computed result is reliable, providing a good reproduction of AFB1-clay interaction. Copyright © 2016 Elsevier B.V. All rights reserved.

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

PubMed

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

2012-01-01

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

Clay mineralogy and its palaeoclimatic significance in the Luochuan loess-palaeosols over ˜1.3 Ma, Shaanxi, northwestern China

NASA Astrophysics Data System (ADS)

Won, Changdok; Hong, Hanlie; Cheng, Feng; Fang, Qian; Wang, Chaowen; Zhao, Lulu; Churchman, Gordon Jock

2018-03-01

To understand climate changes recorded in the Luochuan loess-palaeosols, Shaanxi province, northwestern China, clay mineralogy was studied using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and scanning electron microscopy (SEM) methods. XRD results show that clay mineral compositions in the Luochuan loess-palaeosols are dominantly illite, with minor chlorite, kaolinite, smectite, and illite-smectite mixed-layer clays (I/S). Illite is the most abundant species in the sediments, with a content of 61%-83%. The content of chlorite ranges from 5%-22%, and the content of kaolinite ranges from 5%-19%. Smectite (or I/S) occurs discontinuously along the loess profile, with a content of 0-8%. The Kübler index of illite (IC) ranges from 0.255°-0.491°, and the illite chemical index (ICI) ranges from 0.294-0.394. The CIA values of the loesspalaeosols are 61.9-69.02, and the R3+/(R3+ + R2+ + M+) values are 0.508-0.589. HRTEM observations show that transformation of illite to illite-smectite has occurred in both the loess and palaeosol, suggesting that the Luochuan loess-palaeosols have experienced a certain degree of chemical weathering. The Luochuan loess-palaeosols have the same clay mineral assemblage along the profile. However, the relative contents of clay mineral species, CIA, ICI, and IC values fluctuate frequently along the profile, and all these parameters display a similar trend. Moreover, climate changes suggested by the clay index are consistent with variations in the deep-sea δ18O records and the magnetic susceptibility value, and thus, climate changes in the Luochuan region have been controlled by global climate change.

Evaluation of efficacy of mineral oil, charcoal, and smectite in a rat model of equine cantharidin toxicosis.

PubMed

Qualls, H J; Holbrook, T C; Gilliam, L L; Njaa, B L; Panciera, R J; Pope, C N; Payton, M E

2013-01-01

The efficacy of orally administered therapeutics for the treatment of cantharidin intoxication has not been evaluated in controlled studies. To develop a model of acute cantharidin intoxication in laboratory rats and to evaluate in this model the relative efficacy of 3 gastrointestinal therapies used to treat equine cantharidin toxicosis. Sixty-four male Sprague-Dawley rats. A blinded, randomized, controlled study was performed on rats surgically implanted with telemetry transmitters for evaluating heart rate, locomotor activity, and body temperature. Orogastric administration of cantharidin was performed within 15 seconds before administration of mineral oil, activated charcoal, or smectite. Negative control groups received therapeutic agents alone. Urine was collected for cantharidin analysis. Rats were sacrificed 24 hours after intoxication, and tissues were collected for histopathologic evaluation. Data analysis included ANOVA procedures and contingency tables. Six of 8 cantharidin-intoxicated rats treated with mineral oil died; bradycardia and hypothermia developed in the animals of this group 0-8 hours after intoxication. Rats treated with mineral oil had higher urine cantharidin concentrations than rats receiving cantharidin alone or with smectite (P = .04). The most severe hypothermia (30.6°C ± 1.0) developed in rats administered mineral oil at 4-8 hours after intoxication, whereas those treated with charcoal (35.2°C ± 0.8) had mean body temperatures higher than all other treatment groups (P = .03). Survival times in the charcoal (P = .16) and smectite (P = .12) treatment groups were not statistically different from negative controls. Mineral oil is often used in the treatment of equine cantharidin toxicosis. Our findings suggest that mineral oil increases cantharidin absorption, worsening morbidity and fatality in rats. Copyright © 2013 by the American College of Veterinary Internal Medicine.

The spectroscopic, chemical, and photophysical properties of Martian soils and their analogs (MERC, phase 2)

NASA Technical Reports Server (NTRS)

Banin, Amos; Orenberg, James

1990-01-01

A series of variably proportioned iron/calcium smectite clays and iron loaded smectite clays containing iron up to the level found in the Martian soil were prepared from a typical montomorillonite clay using the Banin method. Evidence was obtained which supports the premise that these materials provide a unique and appropriate model soil system for the Martian surface in that they are consistent with the constraints imposed by the Viking surface elemental analysis, the reflectance data obtained by various spacecraft instruments and ground based telescopes, and the chemical reactivity measured by one of the Viking biology experiments, the Labeled Release (LR) experiment.

Opportunity, Geologic and Structural Context of Aqueous Alteration in Noachian Outcrops, Marathon Valley and Rim and Endeavour Crater

NASA Technical Reports Server (NTRS)

Crumpler, L. S.; Arvidson, R. E.; Mittlefehldt, D. W.; Jolliff, B. L.; Farrand, W. H.; Fox, V.; Golombek, M. P.

2016-01-01

In its 12th year of exploration and 1600 sols since arrival at the rim of the 22 km-diameter Noachian Endeavour impact crater, Mars Exploration Rover Opportunity traversed from the summit of the western rim segment "Cape Tribulation" to "Marathon Valley", a shallow trough dissecting the rim and the site of strong orbital detection of smectites. In situ analysis of the exposures within Marathon Valley is establishing some of the geologic and geochemical controls on the aqueous alteration responsible for smectite detection known to occur in crater rims throughout Noachian terrains of Mars.

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

NASA Technical Reports Server (NTRS)

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

Sulfate Formation From Acid-Weathered Phylosilicates: Implications for the Aqueous History of Mars

NASA Technical Reports Server (NTRS)

Craig, P. I.; Ming, D. W.; Rampe, E. B.

2014-01-01

Most phyllosilicates on Mars are thought to have formed during the planet's earliest Noachian era, then Mars underwent a global change making the planet's surface more acidic [e.g. 1]. Prevailing acidic conditions may have affected the already existing phyllosilicates, resulting in the formation of sulfates. Both sulfates and phyllosilicates have been identified on Mars in a variety of geologic settings [2] but only in a handful of sites are these minerals found in close spatial proximity to each other, including Mawrth Vallis [3,4] and Gale Crater [5]. While sulfate formation from the acidic weathering of basalts is well documented in the literature [6,7], few experimental studies investigate sulfate formation from acid-weathered phyllosilicates [8-10]. The purpose of this study is to characterize the al-teration products of acid-weathered phyllosilicates in laboratory experiments. We focus on three commonly identified phyllosilicates on Mars: nontronite (Fe-smectite), saponite (Mg-smectite), and montmorillonite (Al-smectite) [1, and references therein]. This information will help constrain the formation processes of sulfates observed in close association with phyllosilicates on Mars and provide a better understanding of the aqueous history of such regions as well as the planet as a whole.

[Efficacy of racecadotril vs. smectite, probiotics or zinc as an integral part of treatment of acute diarrhea in children under five years: A meta-analysis of multiple treatments].

PubMed

Gutiérrez-Castrellón, Pedro; Ortíz-Hernández, Anna Alejandra; Llamosas-Gallardo, Beatriz; Acosta-Bastidas, Mario A; Jiménez-Gutiérrez, Carlos; Diaz-García, Luisa; Anzo-Osorio, Anahí; Estevez-Jiménez, Juliana; Jiménez-Escobar, Irma; Vidal-Vázquez, Rosa Patricia

2015-01-01

Despite major advances in treatment, acute diarrhea continues to be a public health problem in children under five years. There is no systematic approach to treatment and most evidence is assembled comparing active treatment vs. placebo. Systematic review of evidence on efficacy of adjuvants for treatment of acute diarrhea through a network meta-analysis. A systematic search of multiple databases searching clinical trials related to the use of racecadotril, smectite, Lactobacillus GG, Lactobacillus reuteri, Saccharomyces boulardii and zinc as adjuvants in acute diarrhea was done. The primary endpoint was duration of diarrhea. Information is displayed through network meta-analysis.The superiority of each coadjutant was analyzed by Sucra approach. Network meta-analysis showed race cadotril was better when compared with placebo and other adjuvants. Sucra analysis showed racecadotril as the first option followed by smectite and Lactobacillus reuteri. Considering a strategic decision making approach, network meta-analysis allows us to establish the therapeutic superiority of racecadotril as an adjunct for the comprehensive management of acute diarrhea in children aged less than five years.

Enrofloxacin sorption on smectite clays: effects of pH, cations, and humic acid.

PubMed

Yan, Wei; Hu, Shan; Jing, Chuanyong

2012-04-15

Enrofloxacin (ENR) occurs widely in natural waters because of its extensive use as a veterinary chemotherapeutic agent. To improve our understanding of the interaction of this emerging contaminant with soils and sediments, sorption of ENR on homoionic smectites and kaolinite was studied as a function of pH, ionic strength, exchangeable cations, and humic acid concentration. Batch experiments and in situ ATR-FTIR analysis suggested multiple sorption mechanisms. Cation exchange was a major contributor to the sorption of cationic ENR species on smectite. The decreased ENR sorption with increasing ionic strength indicated the formation of outer-sphere complexes. Exchangeable cations significantly influenced the sorption capacity, and the observed order was Cs

Oxidation of Structural Fe(II) in Biotite by Lithotrophic Fe(II)-oxidizing microorganisms

NASA Astrophysics Data System (ADS)

Shelobolina, E.; Blöthe, M.; Xu, H.; Konishi, H.; Roden, E.

2008-12-01

The potential for microbial involvement in the oxidation of Fe(II)-bearing phyllosilicates is an understudied aspect of soil/sediment Fe biogeochemistry. An important property of structural Fe in Fe-bearing smectites is their ability to undergo multiple redox cycles without being mobilized. An obvious choice of mineral substrate for enumeration/isolation of Fe(II)-oxidizing microorganisms would be reduced smectite. But reduced smectite is readily oxidized by air. That is why biotite was chosen as a substrate for this study. In contrast to smectite, biotite is more stable in the presence of air, but incapable of redox cycling. Once Fe(II) is oxidized, biotite is weathered to expendable 2:1 phyllosilicates or kaolinite. First, we evaluated the ability of a neutral-pH lithoautotrophic nitrate-reducing enrichment culture (MPI culture), recovered by Straub et al (Appl. Environ. Microbiol., 1996, 62:1458-1460) from a freshwater ditch, to oxidize two different specimens of biotite. The culture was capable of multiple transfers in anaerobic nitrate-containing biotite suspensions. The growth of MPI culture resulted in decrease of 0.5 N HCl-extractable Fe(II) content and simultaneous nitrate reduction. Cell yields were comparable to those observed for other neutral-pH lithoautotrophic Fe(II)-oxidizing bacteria. High resolution TEM examination revealed structural and chemical changes at the edges of oxidized biotite and formation of reddish amorphous precipitates dominated by Si and Fe. To further evaluate efficiency of biotite for recovery of oxygen- and nitrate-dependent Fe(II) oxidizing cultures microbial enumeration study was performed using subsoil from a site near Madison, WI. The soil is rich in Fe-bearing smectite and shows evidence of redoximorphic features. The enumeration of Fe(II) oxidizing organisms from this sediment showed 10-fold higher efficiency of biotite over soluble Fe(II) for recovery of Fe(II)-oxidizers. Isolation and identification of both aerobic and nitrate-utilizing Fe(II)-oxidizing cultures is under way. This study demonstrates that biotite can be effectively used to recover and study microorganisms involved in the oxidative side of iron redox cycle in phyllosilicates. Our findings also indicate that microbial redox metabolism has the potential to vastly accelerate the oxidative weathering of otherwise relatively stable Fe(II)-bearing phyllosilicates.

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.

The clay mineral and Sr-Nd isotopic composition for fine-grained fraction of sediments from northwestern South China Sea: implications for sediment provenance

NASA Astrophysics Data System (ADS)

Cai, G.

2013-12-01

*Guanqiang Cai caiguanqiang@sina.com Guangzhou Marine Geological Survey, Guangzhou, 510760, P.R. China As the largest marginal sea in the western pacific, the South China Sea (SCS) receives large amount of terrigenous material annually through numerous rivers from surrounding continents and islands, which make it as the good place for the study of source to sink process. Yet few studies put emphasis on the northwestern continental shelf and slope in the SCS, even though most of the detrital materials derived from the Red River and Hainan Island are deposited in this area, and northwestern shelf plays a significant role in directly linking the South China, the Indochina and the South China Sea and thus controlling the source to sink process of terrestrial sediment. We presented the clay mineral and Sr-Nd isotopic composition of fine-grained fraction for sediments from northwestern SCS, in order to identify sediment source and transportation. The results show that the clay mineral of northwestern SCS sediments are mainly illite (30%~59%), smectite (20%~40%) and kaolinite (8%~35%), with minor chlorite. The illite chemical index varies between 0.19 and 0.75 with an average of 0.49, indicating an intensive hydrolysis in the source region. The 87Sr/86Sr ratios of sediments range from 0.716288 to 0.734416 (average of 0.724659), and ɛ Nd(0) values range from -10.31 to -11.62 (average of -10.93), which suggest that the source rocks of these sediments are derived from continental crust. The Hainan Island is an important source for sediments deposited in the nearshore and western shelf, especially for illite, kaolinite and smectite clay minerals. Furthermore, the relatively high contents of kaolinite and smectite in sediments from eastern shelf and southern slope of Hainan Island are also controlled by the supply of terrigenous materials from Hainan, which cannot be resulted from sedimentary differentiation of the Pearl and Red river sediments. And the correlation analysis between smectite and Sr-Nd isotopic ratios imply that the smectite in sediments mainly come from chemical weathering products of old continental crust, rather than volcanic rocks of Luzon island.

Understanding the eruption mechanisms of the explosive Bellecombe Eruptions on Piton de la Fournaise, La Réunion

NASA Astrophysics Data System (ADS)

Morgan, K.; Ort, M. H.; Di Muro, A.; Parnell, R. A.; Huff, W. D.

2017-12-01

Piton de la Fournaise (PdF) is an active basaltic volcano on La Réunion island. The Bellecombe Tephra was deposited from at least three unusually explosive eruptions between 3000-5000 ka. The Bellecombe eruptions were interpreted recently to have been due to rapid depressurization of the hydrothermal system when a deep fracture opened after lateral, seaward-directed sliding of the eastern flank, late in a large effusive eruption. This project tests this hypothesis by physically, mineralogically, and chemically characterizing the Bellecombe Tephra to look for evidence of the involvement of the PdF hydrothermal system in the eruptions and understand where the eruptions initiated. The Bellecombe tephra consists of three units separated by incipient soils. Both the Upper and Lower Bellecombe deposits are mostly medium to very fine ash. Lower Bellecombe deposits, from the first two eruptions, are mostly beds of glassy ash containing minor lithic grains and olivine crystals. Hydrothermal minerals, mostly smectite, are present in a few Lower Bellecombe beds. Since these minerals are only present in some beds, the smectite formed before deposition rather than as a product of surficial alteration. The Upper Bellecombe deposits record a third eruption and vary between clast-supported crystal- and lithic-rich lapilli beds and ash beds with abundant ash pellets. The crystals are mostly olivine, with lesser pyroxene and plagioclase and sparse hydrothermal quartz. Gabbro and oceanite clasts are abundant and trachytic pumice rare in these deposits. Hydrothermal minerals are common in most Upper Bellecombe beds. The presence of smectite in some of the Lower Bellecombe beds suggests these deposits came from a system below 200 ºC. Clays in the Upper Bellecombe beds - smectite and mixed layer R0 illite/smectite - imply a system at 40-140 ºC. The hydrothermal system was involved, but might not have been the primary impetus for these eruptions, since hydrothermal minerals are not present in all of the beds, but we find no evidence of high temperatures. The lower Bellecombe vent was near the active summit whereas the Upper Bellecombe vent was from a previously more active area, and this may be reflected in the temperatures of the hydrothermal system. The abundant olivine crystals confirm a relation to a large effusive oceanite eruption.

Applications for special-purpose minerals at a lunar base

NASA Technical Reports Server (NTRS)

Ming, Douglas W.

1992-01-01

Maintaining a colony on the Moon will require the use of lunar resources to reduce the number of launches necessary to transport goods from the Earth. It may be possible to alter lunar materials to produce minerals or other materials that can be used for applications in life support systems at a lunar base. For example, mild hydrothermal alteration of lunar basaltic glasses can produce special-purpose minerals (e.g., zeolites, smectites, and tobermorites) that in turn may be used in life support, construction, waste renovation, and chemical processes. Zeolites, smectites, and tobermorites have a number of potential applications at a lunar base. Zeolites are hydrated aluminosilicates of alkali and alkaline earth cations that possess infinite, three-dimensional crystal structures. They are further characterized by an ability to hydrate and dehydrate reversibly and to exchange some of their constituent cations, both without major change of structure. Based on their unique absorption, cation exchange, molecular sieving, and catalytic properties, zeolites may be used as a solid support medium for the growth of plants, as an adsorption medium for separation of various gases (e.g., N2 from O2), as catalysts, as molecular sieves, and as a cation exchanger in sewage-effluent treatment, in radioactive waste disposal, and in pollution control. Smectites are crystalline, hydrated 2:1 layered aluminosilicates that also have the ability to exchange some of their constituent cations. Like zeolites, smectites may be used as an adsorption medium for waste renovation, as adsorption sites for important essential plant growth cations in solid support plant growth mediums (i.e., 'soils'), as cation exchangers, and in other important application. Tobermorites are cystalline, hydrated single-chained layered silicates that have cation-exchange and selectivity properties between those of smectites and most zeolites. Tobermorites may be used as a cement in building lunar base structures, as catalysts, as media for nuclear and hazardous waste disposal, as exchange media for waste-water treatment, and in other potential applications. Special-purpose minerals synthesized at a lunar base may also have important applications at a space station and for other planetary missions. New technologies will be required at a lunar base to develop life support systems that are self-sufficient, and the use of special-purpose minerals may help achieve this self-sufficiency.

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

Microbe-Clay Mineral Reactions and Characterization Techniques

NASA Astrophysics Data System (ADS)

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

2008-12-01

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

Sorption of uranium (VI) on homoionic sodium smectite experimental study and surface complexation modeling.

PubMed

Korichi, Smain; Bensmaili, Aicha

2009-09-30

This paper is an extension of a previous paper where the natural and purified clay in the homoionic Na form were physico-chemically characterized (doi:10.1016/j.clay.2008.04.014). In this study, the adsorption behavior of U (VI) on a purified Na-smectite suspension is studied using batch adsorption experiments and surface complexation modeling (double layer model). The sorption of uranium was investigated as a function of pH, uranium concentration, solid to liquid ratio, effect of natural organic matter (NOM) and NaNO(3) background electrolyte concentration. Using the MINTEQA2 program, the speciation of uranium was calculated as a function of pH and uranium concentration. Model predicted U (VI) aqueous speciation suggests that important aqueous species in the [U (VI)]=1mg/L and pH range 3-7 including UO(2)(2+), UO(2)OH(+), and (UO(2))(3)(OH)(5)(+). The concentration of UO(2)(2+) decreased and that of (UO(2))(3)(OH)(5)(+) increased with increasing pH. The potentiometric titration values and uptake of uranium in the sodium smectite suspension were simulated by FITEQL 4.0 program using a two sites model, which is composed of silicate and aluminum reaction sites. We compare the acidity constants values obtained by potentiometric titration from the purified sodium smectite with those obtained from single oxides (quartz and alpha-alumina), taking into account the surface heterogeneity and the complex nature of natural colloids. We investigate the uranium sorption onto purified Na-smectite assuming low, intermediate and high edge site surfaces which are estimated from specific surface area percentage. The sorption data is interpreted and modeled as a function of edge site surfaces. A relationship between uranium sorption and total site concentration was confirmed and explained through variation in estimated edge site surface value. The modeling study shows that, the convergence during DLM modeling is related to the best estimation of the edge site surface from the N(2)-BET specific surface area, SSA(BET) (thus, total edge site concentrations). The specific surface area should be at least 80-100m(2)/g for smectite clays in order to reach convergence during the modeling. The range of 10-20% SSA(BET) was used to estimate the values of edge site surfaces that led to the convergence during modeling. An agreement between the experimental data and model predictions is found reasonable when 15% SSA(BET) was used as edge site surface. However, the predicted U (VI) adsorption underestimated and overestimated the experimental observations at the 10 and 20% of the measured SSA(BET), respectively. The dependence of uranium sorption modeling results on specific surface area and edge site surface is useful to describe and predict U (VI) retardation as a function of chemical conditions in the field-scale reactive transport simulations. Therefore this approach can be used in the environmental quality assessment.

Unraveling the Diversity of Early Aqueous Environments and Climate on Mars Through the Phyllosilicate Record

NASA Technical Reports Server (NTRS)

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

2017-01-01

Were Martian phyllosilicates formed on the surface or subsurface? Was early Mars warm or cold? How long was liquid water present on the surface of Mars? These are some of the many open questions about our neighboring planet. We propose that the mineralogy of the clay-bearing outcrops on Mars can help address these questions. Abundant phyllosilicates and aqueous minerals are observed nearly everywhere we can see the ancient rocks on Mars. Most bountiful among these is Fe/Mg-smectite. In this study we evaluate the nature and stratigraphy of clay outcrops observed on Mars and the presence of mixtures of other clays or other minerals with the ubiquitous Fe/Mg-smectite.

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.

Molecular Modeling of the Binding Structures in the Interlayer Adsorption of a Tetracycline Antibiotic by Smectite Clays

NASA Astrophysics Data System (ADS)

Aristilde, L.

2009-12-01

A controlling factor in the fate of antibiotics in the environment is their sequestration in soil particles including clay minerals. Of special interest is the interlayer adsorption by smectite clays, which has been shown to influence both the bioavailability and persistence of antibiotics in the soil environment. However, the interlayer structures of the bound antibiotics, essential to an accurate understanding of the adsorption mechanisms, are not well understood. Molecular simulations of oxytetracycline (OTC) with a model montmorillonite (MONT) clay were performed to gain insights into these structures for tetracycline antibiotics. Monte Carlo simulations were used for explorations of the clay layer spacing required for the adsorption of the antibiotic under different hydration states of the clay interlayer; these preliminary results were validated with previous X-ray diffraction patterns obtained following sorption experiments of OTC with MONT. Molecular dynamics relaxation simulations were performed subsequently in order to obtain geometry-optimized structures of the binding conformations of the intercalated antibiotic in the model MONT layers. This study contributes to a mechanistic understanding of the factors controlling the interlayer adsorption of the tetracycline antibiotics by the expandable smectite clay minerals. Figure 1. Optimized Monte Carlo simulation cell of OTC in the interlayer of MONT: perspective side view (top) and bottom view (bottom).

SUPPRESSION OF HUMORAL IMMUNE RESPONSES BY 2,3,7,8-TETRACHLORODIBENZO-p-DIOXIN INTERCALATED IN SMECTITE CLAY

PubMed Central

Boyd, Stephen A.; Johnston, Cliff T.; Pinnavaia, Thomas J.; Kaminski, Norbert E.; Teppen, Brian J.; Li, Hui; Khan, Bushra; Crawford, Robert B.; Kovalova, Natalia; Kim, Seong-Su; Shao, Hua; Gu, Cheng; Kaplan, Barbara L.F.

2018-01-01

2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) is a highly toxic environmental contaminant found in soils and sediments. Because of its exceptionally low water solubility, this compound exists predominantly in the sorbed state in natural environments. Clay minerals, especially expandable smectite clays, are one of the major component geosorbents in soils and sediments that can function as an effective adsorbent for environmental dioxins, including TCDD. In this study, TCDD was intercalated in the smectite clay saponite by an incipient wetness method. The primary goal of this study was to intercalate TCDD in natural K-saponite clay and evaluate its immunotoxic effects in vivo. The relative bioavailability of TCDD was evaluated by comparing the metabolic activity of TCDD administered in the adsorbed state as an intercalate in saponite and freely dissolved in corn oil. This comparison revealed nearly identical TCDD-induced suppression of humoral immunity, a well-established and sensitive sequela, in a mammalian (mouse) model. This result suggests that TCDD adsorbed by clays is likely to be available for biouptake and biodistribution in mammals, consistent with previous observations of TCDD in livestock exposed to dioxin-contaminated ball clays that were used as feed additives. Adsorption of TCDD by clay minerals does not appear to mitigate risk associated with TCDD exposure substantially. PMID:21994089

Interactions of oxytetracycline with a smectite clay: a spectroscopic study with molecular simulations.

PubMed

Aristilde, Ludmilla; Marichal, Claire; Miéhé-Brendlé, Jocelyne; Lanson, Bruno; Charlet, Laurent

2010-10-15

Binding of antibiotics to clay minerals can decrease both their physical and biological availability in soils. To elucidate the binding mechanisms of tetracycline antibiotics on smectite clays as a function of pH, we probed the interactions of oxytetracycline (OTC) with Na-montmorillonite (MONT) using X-ray diffraction (XRD), infrared (IR), and solid-state nuclear magnetic resonance (NMR) spectroscopies, and Monte Carlo molecular simulations. The XRD patterns demonstrate the presence of OTC in the MONT interlayer space at acidic pH whereas complexation of OTC by external basal and edge sites seems to prevail at pH 8. At both pH, the (1)H-(13)C NMR profile indicates restricted mobility of the adsorbed OTC species; and, -CH(3) deformation and C-N stretching IR vibration bands confirm a binding mechanism involving the protonated dimethylamino group of OTC. Changes in the (23)Na NMR environments are consistent with cation-exchange and cation complexation reactions at the different sites of adsorption. Molecular simulations indicate that MONT interlayer spacing and structural charge localization dictate favorable binding conformations of the intercalated OTC, facilitating multiple interactions in agreement with the spectroscopic data. Our results present complementary insights into the mechanisms of adsorption of TETs on smectites important for their retention in natural and engineered soil environments.

Seismic slip on clay nano-foliation

NASA Astrophysics Data System (ADS)

Aretusini, S.; Pluemper, O.; Passelègue, F. X.; Spagnuolo, E.; Di Toro, G.

2017-12-01

Deformation processes active at seismic slip rates (ca. 1 m/s) on smectite-rich slipping zones are not well understood, although they likely control the mechanical behaviour of: i) subduction zone faults affected by tsunamigenic earthquakes (e.g. Japan Trench affected by Tohoku-Oki 2011 earthquake), ii) plate-boundary faults (e.g. San Andreas Fault), and iii) landslide decollements (e.g. 1963 Vajont landslide). Here we present a set of rotary experiments performed on water-dampened 2 mm thick clay-rich (70% wt. smectite and 30% wt. opal) gouge layers sheared at slip rates V ranging from 0.01 to 1.3 m/s, for 3 m of displacement under 5 MPa normal stress. Microstructural analyses were conducted on pre- and post-sheared gouges using focused ion beam scanning electron and transmission electron microscopy. All sheared gouges were slip weakening in the first 0.1 m of displacement, with friction coefficient decreasing from 0.3-0.45 to 0.5-0.15. Then, with progressive slip, gouges evolved to slip-strengthening (final friction coefficient of 0.35-0.48) at V ≤0.1 m/s and slip-neutral (final friction of 0.05) at V=1.3 m/s. Despite the large difference in the imposed slip rate and frictional behaviour, the slipping zone always consisted of a nano-foliation defined by sub-micrometric smectite crystals wrapping opal grains. The nano-foliated layer thickness decreased from 1.5 mm at V≤0.1 m/s to 0.15 mm at V=1.3 m/s. The presence of a similar nano-foliation in all the smectite-rich wet gouges suggests the activation of similar deformation processes, dominated by frictional slip on grain boundary and basal planes. The variation of deformed thickness with slip rate shows that dynamic weakening, occurring only at seismic slip rates, is controlled by strain localization.

Potential contributions of smectite clays and organic matter to pesticide retention in soils.

PubMed

Sheng, G; Johnston, C T; Teppen, B J; Boyd, S A

2001-06-01

Soil organic matter (SOM) is often considered the dominant sorptive phase for organic contaminants and pesticides in soil-water systems. This is evidenced by the widespread use of organic-matter-normalized sorption coefficients (K(OM)) to predict soil-water distribution of pesticides, an approach that ignores the potential contribution of soil minerals to sorption. To gain additional perspective on the potential contributions of clays and SOM to pesticide retention in soils, we measured sorption of seven pesticides by a K-saturated reference smectite clay (SWy-2) and SOM (represented by a muck soil). In addition, we measured the adsorption of atrazine by five different K-saturated smectites and Ca-saturated SWy-2. On a unit mass basis, the K-SWy-2 clay was a more effective sorbent than SOM for 4,6-dinitro-o-cresol (DNOC), dichlobenil, and carbaryl of the seven pesticides evaluated, of which, DNOC was sorbed to the greatest extent. Atrazine was sorbed to a similar extent by K-SWy-2 and SOM. Parathion, diuron, and biphenyl were sorbed to a greater extent by SOM than by K-SWy-2. Atrazine was adsorbed by Ca-SWy-2 to a much lesser extent than by K-SWy-2. This appears to be related to the larger hydration sphere of Ca(2+) (compared to that of K(+)) which shrinks the effective size of the adsorption domains between exchangeable cations, and which expands the clay layers beyond the apparently optimal spacing of approximately 12.2 A for sorption of aromatic pesticide structures. Although a simple relation between atrazine adsorption by different K-smectites and charge properties of clay was not observed, the highest charge clay was the least effective sorbent; a higher charge density would result in a loss of adsorption domains. These results indicate that for certain pesticides, expandable soil clays have the potential to be an equal or dominant sorptive phase when compared to SOM for pesticide retention in soil.

Production of nanoparticles during experimental deformation of smectite and implications for seismic slip

NASA Astrophysics Data System (ADS)

Aretusini, S.; Mittempergher, S.; Plümper, O.; Spagnuolo, E.; Gualtieri, A. F.; Di Toro, G.

2017-04-01

Nanoparticles and amorphous materials are common constituents of the shallow sections of active faults. Understanding the conditions at which nanoparticles are produced and their effects on friction can further improve our understanding of fault mechanics and earthquake energy budgets. Here we present the results of 59 rotary shear experiments conducted at room humidity conditions on gouge consisting of mixtures of smectite (Ca-montmorillonite) and quartz. Experiments with 60, 50, 25, 0 wt.% Ca-montmorillonite, were performed to investigate the influence of variable clay content on nanoparticle production and their influence on frictional processes. All experiments were performed at a normal stress of 5 MPa, slip rate of 0.0003 ≤ V ≤ 1.5 ms-1, and at a displacement of 3 m. To monitor the development of fabric and the mineralogical changes during the experiments, we investigated the deformed gouges using scanning and transmission electron microscopy combined with X-ray powder diffraction quantitative phase analysis. This integrated analytical approach reveals that, at all slip rates and compositions, the nanoparticles (grain size of 10-50 nm) are partly amorphous and result from cataclasis, wear and mechanical solid-state amorphization of smectite. The maximum production of amorphous nanoparticle occurs in the intermediate slip rate range (0.0003 ≤ V ≤ 0.1 ms-1), at the highest frictional work, and is associated to diffuse deformation and slip strengthening behavior. Instead, the lowest production of amorphous nanoparticles occurs at co-seismic slip rates (V ≥ 1.3 ms-1), at the highest frictional power and is associated with strain and heat localization and slip weakening behavior. Our findings suggest that, independently of the amount of smectite nanoparticles, they produce fault weakening only when typical co-seismic slip rates (>0.1 ms-1) are achieved. This implies that estimates of the fracture surface energy dissipated during earthquakes in natural faults might be extremely difficult to constrain.

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

USGS Publications Warehouse

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

2003-01-01

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

Influence of smectite suspension structure on sheet orientation in dry sediments: XRD and AFM applications.

PubMed

Zbik, Marek S; Frost, Ray L

2010-06-15

The structure-building phenomena within clay aggregates are governed by forces acting between clay particles. Measurements of such forces are important to understand in order to manipulate the aggregate structure for applications such as dewatering of mineral processing tailings. A parallel particle orientation is required when conducting XRD investigation on the oriented samples and conduct force measurements acting between basal planes of clay mineral platelets using atomic force microscopy (AFM). To investigate how smectite clay platelets were oriented on silicon wafer substrate when dried from suspension range of methods like SEM, XRD and AFM were employed. From these investigations, we conclude that high clay concentrations and larger particle diameters (up to 5 microm) in suspension result in random orientation of platelets in the substrate. The best possible laminar orientation in the clay dry film, represented in the XRD 001/020 intensity ratio of 47 was obtained by drying thin layers from 0.02 wt.% clay suspensions of the natural pH. Conducted AFM investigations show that smectite studied in water based electrolytes show very long-range repulsive forces lower in strength than electrostatic forces from double-layer repulsion. It was suggested that these forces may have structural nature. Smectite surface layers rehydrate in water environment forms surface gel with spongy and cellular texture which cushion approaching AFM probe. This structural effect can be measured in distances larger than 1000 nm from substrate surface and when probe penetrate this gel layer, structural linkages are forming between substrate and clay covered probe. These linkages prevent subsequently smooth detachments of AFM probe on way back when retrieval. This effect of tearing new formed structure apart involves larger adhesion-like forces measured in retrieval. It is also suggested that these effect may be enhanced by the nano-clay particles interaction. 2010 Elsevier Inc. All rights reserved.

Restore the change process of Longmaxi shale pore structure during the diagenesis by the potassium and the magnesium

NASA Astrophysics Data System (ADS)

Zhou, W.

2016-12-01

The pore structure of Longmaxi shale was changing during the diagenetic process, mainly caused by the illitization and serpentinzation. The evolution of shale pore structure mainly relates to the element migration. Based on the result of electron microprobe analyser (EMPA), it is possible to find the distribution of element in shale directly and to distinguish the destroyed primary pore structure as element will remain in the migration way. The migration of potassium in Longmaxi shale mainly happened during early diagenesis phase to middle diagenesis phase (Geothermal temperature: 60°-140°). During the illitization, potassium mainly came from potassium feldspar, migrated though the connected pore structure and reacted with smectite. Illite and illite/smectite in Longmaxi shale distribute continuously in 10micron-level flocculent formation, which means that primary connective pore structure in Longmaxi shale has a same scale. The concentration of potassium has an obvious gradient that potassium content in middle of flocculation of Illite/smectite is about 6.8% and 4.8% in the boundary parts (Fig.). In addition, as SiO2 was generated during the illitization, which makes Longmaxi shale very compacted. The migration of magnesium in Longmaxi shale happened during low temperature serpentinization (Geothermal temperature: 140°-350°). Magnesium mainly came from dolomite and migrated in primary pores. According to the result of EMPA, it can be recognized that the migration path of magnesium is much simpler than potassium, which is caused as serpentinization do not have much reaction with clay minerals around (Fig.). Serpentine jams the primary pores of Longmaxi shale too. As reaction temperature of serpentinization is higher than illitization and serpentine is inserts in illite/smectite, the formation process of Longmaxi shale pore structure can be mainly divided into two phases: geothermal temperature˜140° and˜140°.

To what extent clay mineralogy affect soil aggregation? Insights from fractionation analyses conducted on soils under different land-uses.

NASA Astrophysics Data System (ADS)

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

2012-04-01

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 C content or tillage on aggregation has been documented, much less is known about the role of soil mineralogy. The aim of this study is to determine quantitatively if different clay minerals of a temperate soil contribute differently to aggregation and if their contribution is modulated by soil management. We compared the aggregate-size distribution of three cropping systems in a silt loam soil in Versailles (France): organic cropping system (ORG, tilled yearly), direct seeding mulch-based cropping system (DMC, tilled every 4 years), both from a long-term trial, and a nearby grassland. Soil samples from 0-5 cm were wet-sieved to 5 mm and air-dried before aggregate-size separation. For each aggregate class, fraction <2 µm was separated and analysed using X-ray diffraction. Organic C content was determined both in aggregates and <2-µm fractions. C content was lower in ORG than in the two other treatments. The proportion of large-macroaggregates (500-5000 µm) was greater in DMC and grassland; while microaggregates (50-250 µm) showed greater proportions in ORG. In the three treatments, microaggregates had the greatest amount of clays, with preferential accumulation of smectitic phases. In grassland, clays from all aggregated fractions showed more smectitic phases than free-clay fraction. The results indicate that smectitic phases contributed particularly to the microaggregates dynamics. Their contribution to aggregation was lower for larger aggregate sizes where the influence of organic matter was preponderant. Moreover, it was observed that cultivation (ORG and DMC treatments) reduced the relative enrichment of smectitic phases in stable aggregates which makes them more vulnerable to slaking erosion and alters their physico-chemical functions.

Mineralogical control of soil organic carbon persistence at the multidecadal time scale

NASA Astrophysics Data System (ADS)

Lutfalla, Suzanne; Barré, Pierre; Bernard, Sylvain; Le Guillou, Corentin; Chenu, Claire

2015-04-01

One of the current challenges in understanding the long term persistence of organic carbon in soils is to assess how mineral surfaces, especially at small scale, can stabilize soil organic carbon (SOC). The question we address in this work is whether different mineral species stabilize different types of SOC. Here we used the unique opportunity offered by long term bare fallows to study in situ C dynamics in several fine fractions of a silty loam soil. Indeed, with no vegetation i.e. no external input of fresh C, the plant-free soil of the Versailles 42 Plots (INRA, France) has been progressively enriched in persistent SOC during the 80 years of bare fallow. To separate mineral phases of the clay size fraction we performed a size fractionation on samples taken from 4 different plots at 5 different dates (0, 10, 22, 52, and 79 years after the beginning of the BF) and analyzed the SOC in the different fractions thus obtained. First, the clay fraction (< 2 µm) was isolated by wet sieving and centrifugation in water. Then, the clay fraction was further separated into 3 size fractions by centrifugation: fine clay (< 0.05 µm), intermediate clay (0.05 - 0.2 µm), and coarse clay (0.2 - 2 µm). X-ray diffraction was used to determine the mineralogy of the phases and we found that the coarse clay fraction on the one hand and fine and intermediate clay fractions on the other hand exhibited contrasted mineralogies. Fine and intermediate clay fractions contained almost exclusively smectite and mixed-layered illite/smectite minerals whereas coarse clays contained also discrete illite and kaolinite on top of smectite and illite/smectite. We carried out CHN elemental analysis to study the C and nitrogen dynamics with time in the different fractions. And synchrotron based spectroscopy and microscopy (NEXAFS bulk and STXM at the carbon K edge of 280 eV, CLS Saskatoon, Canada) was used to get information on the distribution and the chemical speciation of the SOC in fractions with contrasted mineralogies. Data analysis is still ongoing and full results will be presented at EGU. First results show that the dynamics and quality of the SOC differ in the different clay fractions. SOC decay was greater in coarse clays compared to intermediate clays, SOC in the coarse clay fraction displaying more diversity than in the other fractions. SOC persistence at the multidecadal timescale also seems to be mineral dependent: smectite being more efficient at protecting carbon compared to illite.

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

Bowers, Geoffrey M.; Schaef, H. Todd; Loring, John S.

This paper explores the molecular-scale interactions between CO 2 and the representative smectite mineral hectorite under supercritical conditions (90 bar, 50°C) using novel in situ X-ray diffraction (XRD), infrared (IR) spectroscopy, and magic angle spinning (MAS) nuclear magnetic resonance (NMR) techniques. Particular emphasis is placed on understanding the roles of the smectite charge balancing cation (CBC) and H O in these interactions. The data show that supercritical CO 2 (scCO 2) can be adsorbed on external surfaces and in the confined interlayer spaces of hectorite at 50°C and 90 bar, with the uptake of CO 2 into the interlayer favoredmore » at low H 2O content and when the basal spacing is similar to a monolayer hydrate of hectorite (1WL, ~12.5 Å). These results are in agreement with published spectroscopic and molecular modeling data for the related smectite Na-montmorillonite.Charge balancing cations with small radii, large hydration energies, and low polarizabilities tend to scavenge H 2O from humid scCO 2 or retain the H 2O they held before scCO 2 exposure, swelling spontaneously to a bilayer hydrate (2WL) dominated state that largely prevents CO 2-ion interactions and influences the extent of CO 2 intercalation into the interlayer. In contrast, ions with large radii, low hydration energies, and large polarizabilities more readily form close associations with CO 2 with the energetics enabling coexistence of CO 2 and H2O in the interlayer over a wide range of scCO 2 humidities. Integrating our results with those from molecular dynamics simulations of wet CO 2-bearing montmorillonites suggest that adsorbed CO 2 in 1WL-type interlayers is oriented with its long axis parallel to the clay sheets and experiences dynamics dominated by anisotropic rotation about the axis perpendicular to the CO 2 long axis at rates of at least ~105 Hz. If appreciable CO 2 is adsorbed in 2WL-type interlayers, it must experience a mean orientation and dynamic averaging affects that mimic the 1WL-type adsorption environment. External surface adsorbed CO 2 is dynamically similar to the 1WL case, but the CO 2 long axis samples a larger range of orientations with respect to the smectite surface and adopts a different mean angle between the long axis and the smectite surface. Our data also suggest that equilibrating hectorite with a largevolume of scCO 2 at 50°C and 90 bar leads to interlayer dehydration, with the extent of dehydration correlating with the hydrophilicity of the CBC.« less

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.;

Mineralogical, chemical and K-Ar isotopic changes in Kreyenhagen Shale whole rocks and <2 μm clay fractions during natural burial and hydrous-pyrolysis experimental maturation

NASA Astrophysics Data System (ADS)

Clauer, N.; Lewan, M. D.; Dolan, M. P.; Chaudhuri, S.; Curtis, J. B.

2014-04-01

Progressive maturation of the Eocene Kreyenhagen Shale from the San Joaquin Basin of California was studied by combining mineralogical and chemical analyses with K-Ar dating of whole rocks and <2 μm clay fractions from naturally buried samples and laboratory induced maturation by hydrous pyrolysis of an immature outcrop sample. The K-Ar age decreases from 89.9 ± 3.9 and 72.4 ± 4.2 Ma for the outcrop whole rock and its <2 μm fraction, respectively, to 29.7 ± 1.5 and 21.0 ± 0.7 Ma for the equivalent materials buried to 5167 m. The natural maturation does not produce K-Ar ages in the historical sense, but rather K/Ar ratios of relative K and radiogenic 40Ar amounts resulting from a combined crystallization of authigenic and alteration of initial detrital K-bearing minerals of the rocks. The Al/K ratio of the naturally matured rocks is essentially constant for the entire depth sequence, indicating that there is no detectable variation in the crystallo-chemical organization of the K-bearing alumino-silicates with depth. No supply of K from outside of the rock volumes occurred, which indicates a closed-system behavior for it. Conversely, the content of the total organic carbon (TOC) content decreases significantly with burial, based on the progressive increasing Al/TOC ratio of the whole rocks. The initial varied mineralogy and chemistry of the rocks and their <2 μm fractions resulting from differences in detrital sources and depositional settings give scattered results that homogenize progressively during burial due to increased authigenesis, and concomitant increased alteration of the detrital material. Hydrous pyrolysis was intended to alleviate the problem of mineral and chemical variations in initially deposited rocks of naturally matured sequences. However, experiments on aliquots from thermally immature Kreyenhagen Shale outcrop sample did not mimic the results from naturally buried samples. Experiments conducted for 72 h at temperatures from 270 to 365 °C did not induce significant changes at temperatures above 310 °C in the mineralogical composition and K-Ar ages of the rock and <2 μm fraction. The K-Ar ages of the <2 μm fraction range from 72.4 ± 4.2 Ma in the outcrop sample to 62.4 ± 3.4 Ma in the sample heated the most at 365 °C for 216 h. This slight decrease in age outlines some loss of radiogenic 40Ar, together with losses of organic matter as oil, gas, and aqueous organic species. Large amounts of smectite layers in the illite-smectite mixed layers of the pyrolyzed outcrop <2 μm fraction remain during thermal experiments, especially above 310 °C. With no illitization detected above 310 °C, smectite appears to have inhibited rather than promoted generation of expelled oil from decomposition of bitumen. This hindrance is interpreted to result from bitumen impregnating the smectite interlayer sites and rock matrix. Bitumen remains in the <2 μm fraction despite leaching with H2O2. Its presence in the smectite interlayers is apparent by the inability of the clay fraction to fully expand or collapse once bitumen generation from the thermal decomposition of the kerogen is completed, and by almost invariable K-Ar ages confirming for the lack of any K supply and/or radiogenic 40Ar removal. This suggests that once bitumen impregnates the porosity of a progressively maturing source rock, the pore system is no longer wetted by water and smectite to illite conversion ceases. Experimental attempts to evaluate the smectite conversion to illite should preferentially use low-TOC rocks to avoid inhibition of the reaction by bitumen impregnation.

Estimation of soil saturated hydraulic conductivity by artificial neural networks ensemble in smectitic soils

NASA Astrophysics Data System (ADS)

Sedaghat, A.; Bayat, H.; Safari Sinegani, A. A.

2016-03-01

The saturated hydraulic conductivity ( K s ) of the soil is one of the main soil physical properties. Indirect estimation of this parameter using pedo-transfer functions (PTFs) has received considerable attention. The Purpose of this study was to improve the estimation of K s using fractal parameters of particle and micro-aggregate size distributions in smectitic soils. In this study 260 disturbed and undisturbed soil samples were collected from Guilan province, the north of Iran. The fractal model of Bird and Perrier was used to compute the fractal parameters of particle and micro-aggregate size distributions. The PTFs were developed by artificial neural networks (ANNs) ensemble to estimate K s by using available soil data and fractal parameters. There were found significant correlations between K s and fractal parameters of particles and microaggregates. Estimation of K s was improved significantly by using fractal parameters of soil micro-aggregates as predictors. But using geometric mean and geometric standard deviation of particles diameter did not improve K s estimations significantly. Using fractal parameters of particles and micro-aggregates simultaneously, had the most effect in the estimation of K s . Generally, fractal parameters can be successfully used as input parameters to improve the estimation of K s in the PTFs in smectitic soils. As a result, ANNs ensemble successfully correlated the fractal parameters of particles and micro-aggregates to K s .

Alumina+Silica+/-Germanium Alteration in Smectite-Bearing Marathon Valley, Endeavour Crater Rim, Mars

NASA Technical Reports Server (NTRS)

Mittlefehldt, D. W.; Gellert, R.; Van Bommel, S.; Arvidson, R. E.; Clark, B. C.; Ming, D. W.; Schroeder, C.; Yen, A. S.; Fox, V. K.; Farrand, W. H.;

Optical (diffuse reflectance) and Mossbauer spectroscopic study of nontronite and related Fe-bearing smectites

USGS Publications Warehouse

Sherman, David M.; Vergo, N.

1988-01-01

Near-ultraviolet to near-infrared optical (diffuse reflectance) spectra of several nontronites and related Fe-bearing smectites [(Fe2+,Fe3+)-bearing saponite and (Fe2+,Fe3+)-bearing montmorillonite] are presented and interpreted. Mossbauer spectra at 298 K are also presented to help interpret the optical spectra. The optical spectra of nontronites are dominated by the ligand field transitions of Fe3+ in octahedral coordination sites. In addition to the ligand field transitions of single Fe3+ cations, a broad absorption band centered near 22000 cm-1 is observed that may be due to the simultaneous excitation of two Fe3+ cations to the 4T1g (4G) state. Alternatively, this band may represent excitations to the 2A2g and 2T1g ligand field states. For most samples, the amount of tetrahedrally coordinated Fe3+ was below that detectable by Mossbauer spectroscopy (1-3% of total Fe). However, the optical spectra of all of the nontronites show an absorption band near 23000 cm-1. This band is assigned to the 6A1 ??? 4E,4A1 transition of tetrahedrally coordinated Fe3+. The optical spectra of mixed-valence Fe-bearing smectites show a broad absorption band at 14000-15000 cm-1 owing to Fe2+ ??? Fe3+ charge transfer. -from Authors

Secondary mineral formation associated with respiration of nontronite, NAu-1 by iron reducing bacteria

PubMed Central

O'Reilly, S Erin; Watkins, Janet; Furukawa, Yoko

2005-01-01

Experimental batch and miscible-flow cultures were studied in order to determine the mechanistic pathways of microbial Fe(III) respiration in ferruginous smectite clay, NAu-1. The primary purpose was to resolve if alteration of smectite and release of Fe precedes microbial respiration. Alteration of NAu-1, represented by the morphological and mineralogical changes, occurred regardless of the extent of microbial Fe(III) reduction in all of our experimental systems, including those that contained heat-killed bacteria and those in which O2, rather than Fe(III), was the primary terminal electron acceptor. The solid alteration products observed under transmission electron microscopy included poorly crystalline smectite with diffuse electron diffraction signals, discrete grains of Fe-free amorphous aluminosilicate with increased Al/Si ratio, Fe-rich grains, and amorphous Si globules in the immediate vicinity of bacterial cells and extracellular polymeric substances. In reducing systems, Fe was also found as siderite. The small amount of Fe partitioned to the aqueous phase was primarily in the form of dissolved Fe(III) species even in the systems in which Fe(III) was the primary terminal electron acceptor for microbial respiration. From these observations, we conclude that microbial respiration of Fe(III) in our laboratory systems proceeded through the following: (1) alteration of NAu-1 and concurrent release of Fe(III) from the octahedral sheets of NAu-1; and (2) subsequent microbial respiration of Fe(III).

The Role of Microbial Iron Reduction in the Formation of Proterozoic Molar Tooth Structures

NASA Astrophysics Data System (ADS)

Hodgskiss, M. S. W.; Kunzmann, M.; Halverson, G. P.; Poirier, A.

2016-12-01

Molar tooth structures are poorly understood early diagenetic, microspar-filled voids in clay-rich carbonate sediments. They are a common structure in sedimentary successions dating from 2600-720 Ma, but do not occur in rocks older or younger. Despite being volumetrically significant in carbonate rocks of this age, their formation and disappearance are poorly understood. Here, we present iron isotope data, supported by carbon and oxygen isotopes, major and minor element concentrations, and total organic carbon and pyrite contents for samples from ten regions spanning 1870-635 Ma. The iron isotopic composition of molar tooth structures is almost always lighter (modal depletion of 2‰) than the carbonate or siliciclastic components in the host sediment, whereas carbon isotopes are indistinguishable. We interpret the isotopically light iron in molar tooth structures to have been produced by microbial iron reduction utilising Fe-oxyhydroxides and smectites. The microbial conversion of smectite to illite results in a volume reduction of clay minerals ( 30%), while locally increasing pore water alkalinity. Therefore, this biogeochemical process is a viable mechanism to produce voids and subsequently precipitate carbonate minerals. The disappearance of molar tooth structures is likely linked to a combination of a decrease in smectite abundance, a decline in the marine DIC reservoir, and increase in the concentration of O2 in shallow seawater in the mid-Neoproterozoic.

Redox properties of structural Fe in clay minerals. 2. Electrochemical and spectroscopic characterization of electron transfer irreversibility in ferruginous smectite, SWa-1.

PubMed

Gorski, Christopher A; Klüpfel, Laura; Voegelin, Andreas; Sander, Michael; Hofstetter, Thomas B

2012-09-04

Structural Fe in clay minerals is an important, albeit poorly characterized, redox-active phase found in many natural and engineered environments. This work develops an experimental approach to directly assess the redox properties of a natural Fe-bearing smectite (ferruginous smectite, SWa-1, 12.6 wt % Fe) with mediated electrochemical reduction (MER) and oxidation (MEO). By utilizing a suite of one-electron-transfer mediating compounds to facilitate electron transfer between structural Fe in SWa-1 and a working electrode, we show that the Fe2+/Fe3+ couple in SWa-1 is redox-active over a large range of potentials (from E(H) = -0.63 V to +0.61 V vs SHE). Electrochemical and spectroscopic analyses of SWa-1 samples that were subject to reduction and re-oxidation cycling revealed both reversible and irreversible structural Fe rearrangements that altered the observed apparent standard reduction potential (E(H)(ø)) of structural Fe. E(H)(ø)-values vary by as much as 0.56 V between SWa-1 samples with different redox histories. The wide range of E(H)-values over which SWa-1 is redox-active and redox history-dependent E(H)(ø)-values underscore the importance of Fe-bearing clay minerals as redox-active phases in a wide range of redox regimes.

Suppression of humoral immune responses by 2,3,7,8-tetrachlorodibenzo-p-dioxin intercalated in smectite clay.

PubMed

Boyd, Stephen A; Johnston, Cliff T; Pinnavaia, Thomas J; Kaminski, Norbert E; Teppen, Brian J; Li, Hui; Khan, Bushra; Crawford, Robert B; Kovalova, Natalia; Kim, Seong-Su; Shao, Hua; Gu, Cheng; Kaplan, Barbara L F

2011-12-01

2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) is a highly toxic environmental contaminant found in soils and sediments. Because of its exceptionally low water solubility, this compound exists predominantly in the sorbed state in natural environments. Clay minerals, especially expandable smectite clays, are one of the major component geosorbents in soils and sediments that can function as an effective adsorbent for environmental dioxins, including TCDD. In this study, TCDD was intercalated in the smectite clay saponite by an incipient wetness method. The primary goal of this study was to intercalate TCDD in natural K-saponite clay and evaluate its immunotoxic effects in vivo. The relative bioavailability of TCDD was evaluated by comparing the metabolic activity of TCDD administered in the adsorbed state as an intercalate in saponite and freely dissolved in corn oil. This comparison revealed nearly identical TCDD-induced suppression of humoral immunity, a well-established and sensitive sequela, in a mammalian (mouse) model. This result suggests that TCDD adsorbed by clays is likely to be available for biouptake and biodistribution in mammals, consistent with previous observations of TCDD in livestock exposed to dioxin-contaminated ball clays that were used as feed additives. Adsorption of TCDD by clay minerals does not appear to mitigate risk associated with TCDD exposure substantially. Copyright © 2011 SETAC.

Visible light photodegradation of phenanthrene catalyzed by Fe(III)-smectite: role of soil organic matter.

PubMed

Jia, Hanzhong; Li, Li; Fan, Xiaoyun; Liu, Mingdeng; Deng, Wenye; Wang, Chuanyi

2013-07-15

In the present study, phenanthrene is employed as a model to explore the roles played by three soil organic matter (SOM) fractions, i.e., dissolved organic matter (DOM), humic acid (HA), and fulvic acid (FA), in its photodegradation with assistance of Fe(III)-smectite under visible-light. Slight decrease in phenanthrene photodegradation rate was observed in the presence of DOM, which is explained in terms of oxidative-radical competition between DOM and target phenanthrene molecules due to the high electron-donor capacity of phenolic moieties in DOM. On the other hand, a critic content is observed with FA (0.70mg/g) and HA (0.65mg/g). Before reaching the critic content, the removal of phenanthrene is accelerated; while after that, the photodegradation rate is suppressed. The acceleration of phenanthrene degradation can be attributed to the photosensitization of FA and HA. Due to the strong interaction between phenanthrene and the phenyl rings, however, the retention of phenanthrene on SOM-Fe(III)-smectite in the presence of high content of HA or FA is enhanced, thus slowing down its photodegradation. Those observations provide valuable insights into the transformation and fate of PAHs in the natural soil environment and open a window for using clay-humic substances complexes for remediation of contaminated soil. Copyright © 2013 Elsevier B.V. All rights reserved.

Ancient Aqueous Environments at Endeavour Crater, Mars

NASA Technical Reports Server (NTRS)

Arvidson, R. E.; Squyres, S. W.; Bell, J. F.; Catalano, J. G.; Clark, B. C.; Crumpler, L. S.; de Souza, P. A.; Fairen, A. G.; Farrand, W. H.; Fox, V. K.;

Ancient aqueous environments at Endeavour crater, Mars

USGS Publications Warehouse

Arvidson, R. E.; Squyres, S. W.; Bell, J.F.; Catalano, J.G.; Clark, B. C.; Crumpler, L.S.; de Souza, P.A.; Fairén, A.G.; Farrand, W. H.; Fox, V.K.; Gellert, Ralf; Ghosh, A.; Golombeck, M.P.; Grotzinger, J.P.; Guinness, E.A.; Herkenhoff, Kenneth E.; Jolliff, B.L.; Knoll, A.H.; Li, R.; McLennan, S.M.; Ming, D. W.; Mittlefehldt, D. W.; Moore, Johnnie N.; Morris, R.V.; Murchie, S.L.; Parker, T.J.; Paulsen, G.; Rice, J.W.; Ruff, S.W.; Smith, M.D.; Wolff, M.J.

2014-01-01

Opportunity has investigated in detail rocks on the rim of the Noachian age Endeavour crater, where orbital spectral reflectance signatures indicate the presence of Fe+3-rich smectites. The signatures are associated with fine-grained, layered rocks containing spherules of diagenetic or impact origin. The layered rocks are overlain by breccias, and both units are cut by calcium sulfate veins precipitated from fluids that circulated after the Endeavour impact. Compositional data for fractures in the layered rocks suggest formation of Al-rich smectites by aqueous leaching. Evidence is thus preserved for water-rock interactions before and after the impact, with aqueous environments of slightly acidic to circum-neutral pH that would have been more favorable for prebiotic chemistry and microorganisms than those recorded by younger sulfate-rich rocks at Meridiani Planum.

Controlled synthesis of carbon-encapsulated copper nanostructures by using smectite clays as nanotemplates.

PubMed

Tsoufis, Theodoros; Colomer, Jean-François; Maccallini, Enrico; Jankovič, Lubos; Rudolf, Petra; Gournis, Dimitrios

2012-07-23

Rhomboidal and spherical metallic-copper nanostructures were encapsulated within well-formed graphitic shells by using a simple chemical method that involved the catalytic decomposition of acetylene over a copper catalyst that was supported on different smectite clays surfaces by ion-exchange. These metallic-copper nanostructures could be separated from the inorganic support and remained stable for months. The choice of the clay support influenced both the shape and the size of the synthesized Cu nanostructures. The synthesized materials and the supported catalysts from which they were produced were studied in detail by TEM and SEM, powder X-ray diffraction, thermal analysis, as well as by Raman and X-ray photoelectron spectroscopy. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modelling of clay diagenesis using a combined approach of crystalchemistry and thermochemistry: a case study in the smectite illitization.

NASA Astrophysics Data System (ADS)

Geloni, Claudio; Previde Massara, Elisabetta; Di Paola, Eleonora; Ortenzi, Andrea; Gherardi, Fabrizio; Blanc, Philippe

2017-04-01

Diagenetic transformations occurring in clayey and arenaceous sediments is investigated in a number of hydrocarbon reservoirs with an integrated approach that combines mineralogical analysis, crystalchemistry, estimation of thermochemical parameters of clay minerals, and geochemical modelling. Because of the extremely variable crystalchemistry of clays, especially in the smectite - illite compositional range, the estimation of thermochemical parameters of site-specific clay-rich rocks is crucial to investigate water-rock equilibria and to predict mineralogical evolutionary patterns at the clay-sandstone interface. The task of estimating the thermochemical properties of clay minerals and predicting diagenetic reactions in natural reservoirs is accomplished through the implementation of an informatized, procedure (IP) that consists of: (i) laboratory analysis of smectite, illite and mixed layers (I/S) for the determination of their textural characteristics and chemical composition; (ii) estimation of the thermodynamic and structural parameters (enthalpy, entropy, and free energy of formation, thermal capacity, molar volume, molar weight) with a MS Excel tool (XLS) specifically developed at the French Bureau of Geological and Mining Researches (BRGM); (iii) usage of the SUPCRT (Johnson et al., 1992) software package (thereinafter, SSP) to derive log K values to be incorporated in thermodynamic databases of the standard geochemical codes; (iv) check of the consistency of the stability domains calculated with these log K values with relevant predominance diagrams; (v) final application of geochemical and reactive transport models to investigate the reactive mechanisms under different thermal conditions (40-150°C). All the simulations consider pore waters having roughly the same chemical composition of reservoir pore waters, and are performed with The Geochemist Workbench (Bethke and Yeakel, 2015), PHREEQC (Parkhurst, 1999) and TOUGHREACT (Xu, 2006). The overall procedure benefits from: (i) (minor) improvements of the I/O structure of the SSP; (ii) the development of a suite of python scripts to automate the steps needed to augment the thermodynamic database by integrating the external information provided by potential users with the XLS tool and the SSP; (iii) the creation of specific outputs to allow for more convenient handling and inspection of computed parameters of the thermodynamic database. A case study focused on non-isothermal smectite-illite transformation is presented to show the capability of our numerical models to account for clay compaction under 1D geometry conditions. This model considers fluid flow driven by the compaction of a clay layer, and chemistry-fluid flow mutual feedback with the underlying sandstone during the advancement of the diagenesis. Due to this complex interaction, as a result of the smectite-illite transformation in the clays, significant quartz cementation affects the sandstone adjacent to the compacting clay.

Degradation of Nitrobenzene Using Bio-Reduced Fe-Clays: Progress Towards the Development of an in-situ Groundwater Remediation Technology

NASA Astrophysics Data System (ADS)

White, M. L.; Fialips, C. I.

2008-12-01

Clay minerals are widely used in agricultural, industrial and environmental engineering applications due to their specific physical and chemical properties and their high abundance in soils in sediments. Currently however, Fe-bearing clays are not widely exploited in these applied fields. Fe-rich smectites, such as nontronite, can contain up to 20wt% of Fe2O3 as structural Fe(III) and if a suitable electron donor is available, this Fe(III) can be utilized by Fe-reducing bacteria as a terminal electron acceptor. When reduced, the overall reactivity of Fe-smectites changes, particularly where interactions with water and various organic compounds are involved. For instance, the presence of reduced Fe-smectites has been found to induce the degradation of certain organic contaminants found in groundwaters and the subsurface, e.g. chlorinated aliphatics and nitroaromatic compounds. The goal of this study is to develop an in-situ groundwater remediation technology that targets redox- sensitive organics, in the form of a permeable Bio Fe-clay barrier. To achieve this, the iron-reducing bacterium Shewanella algae BrY was first used to reduce structural FeIII in <2micron fractions of the Fe- rich smectite nontronite (NAu-2, 41.74wt% Fe2O3) and a Fe-bearing montmorrillonite (Speeton Clay, Yorkshire, UK, ~8wt% Fe2O3). S. algae BrY was able to reduce structural FeIII within these clays to maximum Fe(II)/Fe(II)+Fe(III) ratios 0.34 and 0.19 for the nontronite and Speeton Clay, respectively, in the presence and absence of the electron shuttle, AQDS (9, 10-anthraquinone-2, 6-disulfonic acid). These results are novel because the capability of S. algae BrY to reduce structural Fe(III) in smectite clays has not previously been tested. Nitrobenzene was selected as the test redox-sensitive organic compound as it is a common subsurface contaminant and is of global ecotoxicological concern. To test the capability of bio- reduced Fe-clays to transform nitrobenzene to aniline (the less toxic and more stable degradation product of nitrobenzene), nontronite suspensions with reduction levels of 20% and 30% were spiked with various concentrations of nitrobenzene and monitored for 5 days. Results showed that when reduced clay, S. algae BrY and AQDS were present, 100% of the nitrobenzene had been transformed to aniline within 24 hours. Further recent results suggest that bio-reduced nontronite alone is also capable of degrading nitrobenzene but at a slower rate than when AQDS is present. Future experiments will constrain absorption and degradation rates of nitrobenzene in contact with the reduced Fe-clays and the role(s) of the Fe-reducing bacteria. Results to date will be presented.

The Ponto-Caspian basin as a final trap for southeastern Scandinavian Ice-Sheet meltwater

NASA Astrophysics Data System (ADS)

Tudryn, Alina; Leroy, Suzanne A. G.; Toucanne, Samuel; Gibert-Brunet, Elisabeth; Tucholka, Piotr; Lavrushin, Yuri A.; Dufaure, Olivier; Miska, Serge; Bayon, Germain

2016-09-01

This paper provides new data on the evolution of the Caspian Sea and Black Sea from the Last Glacial Maximum until ca. 12 cal kyr BP. We present new analyses (clay mineralogy, grain-size, Nd isotopes and pollen) applied to sediments from the river terraces in the lower Volga, from the middle Caspian Sea and from the western part of the Black Sea. The results show that during the last deglaciation, the Ponto-Caspian basin collected meltwater and fine-grained sediment from the southern margin of the Scandinavian Ice Sheet (SIS) via the Dniepr and Volga Rivers. It induced the deposition of characteristic red-brownish/chocolate-coloured illite-rich sediments (Red Layers in the Black Sea and Chocolate Clays in the Caspian Sea) that originated from the Baltic Shield area according to Nd data. This general evolution, common to both seas was nevertheless differentiated over time due to the specificities of their catchment areas and due to the movement of the southern margin of the SIS. Our results indicate that in the eastern part of the East European Plain, the meltwater from the SIS margin supplied the Caspian Sea during the deglaciation until ∼13.8 cal kyr BP, and possibly from the LGM. That led to the Early Khvalynian transgressive stage(s) and Chocolate Clays deposition in the now-emerged northern flat part of the Caspian Sea (river terraces in the modern lower Volga) and in its middle basin. In the western part of the East European Plain, our results confirm the release of meltwater from the SIS margin into the Black Sea that occurred between 17.2 and 15.7 cal kyr BP, as previously proposed. Indeed, recent findings concerning the evolution of the southern margin of the SIS and the Black Sea, show that during the last deglaciation, occurred a westward release of meltwater into the North Atlantic (between ca. 20 and 16.7 cal kyr BP), and a southward one into the Black Sea (between 17.2 and 15.7 cal kyr BP). After the Red Layers/Chocolate Clays deposition in both seas and until 12 cal kyr BP, smectite became the dominant clay mineral. The East European Plain is clearly identified as the source for smectite in the Caspian Sea sediments. In the Black Sea, smectite originated either from the East European Plain or from the Danube River catchment. Previous studies consider smectite as being only of Anatolian origin. However, our results highlight both, the European source for smectite and the impact of this source on the depositional environment of the Black Sea during considered period.

Smectite Dehydration, Membrane Filtration, and Pore-Water Freshening in Deep Ultra-Low Permeability Formations: Deep Processes in the Nankai Accretionary Wedge

NASA Astrophysics Data System (ADS)

Brown, K. M.; Sample, J. C.; Even, E.; Poeppe, D.; Henry, P.; Tobin, H. J.; Saffer, D. M.; Hirose, T.; Toczko, S.; Maeda, L.

2014-12-01

We address the fundamental questions surrounding the nature of water and chemical transport processes deep within sedimentary basin and accretionary-wedge environments. Consolidation and permeability studies conducted to 165 MPa (~10km depth) indicate that ultra-tight clay formations (10-18 m2 to10-21 m2) can substantially modify the fluids migrating through then. Pore-water extractions conducted on smectite/illite rich core samples obtained from 1-3 km depths at IODP (NanTroSEIZE, Chikyu) deep-riser drilling Site C0002, at the elevated loads required to squeeze waters from such deeply buried sediment (stresses up to 100 MPa),resulted in anomalous patterns of sequential freshening with progressive loading. More accurate laboratory investigations (both incremental loading and Constant Rate of Strain test) revealed that such freshening initiates above 20 MPa and progresses with consolidation to become greater than 20% by effective normal load of 165 MPa. Log-log plots of stress vs. hydraulic conductivity reveal that trends remain linear to elevated stresses and total porosities as low at 14%. The implications are that stress induced smectite dehydration and/or membrane filtration effects cause remarkable changes in pore water chemistry with fluid migration through deep, tight, clay-rich formations. These changes should occur in addition to any thermally induced diagenetic and clay-dehydration effects on pore water chemistry. Work is progressing to evaluate the impact of clay composition and temperature to ascertain if purely illitic compositions show similar trends and if the mass fractionation of water and other isotopes also occurs. Such studies will ascertain if the presence of smectite is a prerequisite for freshening or if membrane filtration is a major process in earth systems containing common clay minerals. The results have major implications for interpretations of mass chemical balances, pore water profiles, and the hydrologic, geochemical, and stress state controls on deep system behavior in all deep accretionary wedge and basin environments where clays are abundant. This research used samples provided by the International Ocean Discovery Program (IODP).

Leachable Li and Mg Evidence for Hydrological Changes in the Mono Basin, CA, USA

NASA Astrophysics Data System (ADS)

Sahajpal, R.; Hemming, N.; Zimmerman, S. R.; Hemming, S. R.

2007-12-01

Hydrology in closed basin lakes, such as Mono Lake of the US western Great Basin, is sensitive to regional climate changes. Lake level history of the Mono Basin has been put into a precise age framework using the paleomagnetic intensity of the Wilson Creek Formation sediments to North Atlantic records, and accordingly Greenland's GISP2 oxygen isotope record (Zimmerman et al., 2006, EPSL, v. 252, pp. 94- 106). This allows correlation of the lake level indicators and Greenland climate at high resolution. The physical evidence for lake level, based on the association of strata in near shore terraces, can be confidently correlated to proxies of lake chemistry preserved in the strata. We have tested the application of leachable Li, following the procedure developed by Bischoff et al. (1997, Quaternary Research, v. 48, pp. 313-325) for Owens Lake. At Owens Lake there is a positive correlation between salinity based on diatoms with leachable Li concentrations. In contrast, at Mono Lake the leachable Li concentration follows the bulk carbonate concentration, generally correlating low lake levels (high salinity) with low leachable Li concentrations. Our preferred explanation for both the carbonate and leachable Li concentrations is based on the fact that the Mono Basin rarely overflows, and therefore precipitation of minerals during evaporation leads to chemical divides (Garrels and Mackenzie., 1967, in "Equilibrium Concepts in Natural Water Systems", W. Stumm, Ed., pp. 222-242). As Li behaves conservatively compared to elements like Ca2+ and Mg2+, it might be expected that the leachable Li would be higher when lake level is lower. However, the host for the Li appears to be Mg-smectite. Therefore, the concentration of leachable Li in the sediment is controlled by the concentration of Mg-smectite, as well as the Li/Mg of the water from which the Mg- smectite precipitated and the Kd of the Li into the Mg-smectite. We are studying the Li and Mg systematics of these samples in order to deconvolve these factors and contribute to paleo-hydrological studies of this and other closed basin lakes.

Multispectral VNIR Observations by the Opportunity Rover Pancam of Multiple Episodes of Aqueous Alteration in Marathon Valley, Endeavour Crater, Mars

NASA Technical Reports Server (NTRS)

Farrand, William H.; Bell, James F., III; Johnson, Jeffrey R.; Arvidson, Raymond E.; Mittlefehldt, David W.; Ruff, Steven W.; Rice, Melissa S.

2016-01-01

Since early 2015, the Mars Exploration Rover Opportunity has been exploring the break in the rim of Endeavour Crater dubbed Marathon Valley by the rover team. Marathon Valley was identified by orbital hyperspectral data from the MRO CRISM as having a relatively strong spectral feature in the 2.3 micrometer region indicative of an Mg or Fe-OH combination overtone absorption band indicative of smectite clay. Earlier in its mission, Opportunity examined the Matijevic Hill region on the more northerly Cape York crater rim segment and found evidence for smectite clays in a stratigraphically lower, pre-impact formed unit dubbed the Matijevic formation. However, the smectite exposures in Marathon Valley appear to be associated with the stratigraphically higher Shoemaker formation impact breccia. Evidence for alteration in this unit in Marathon Valley is provided by Pancam multispectral observations in the 430 to 1010 nm visible/near infrared (VNIR) spectral range. Sinuous troughs ("red zones") contain fragmented cobbles and pebbles displaying higher blue-to-red slopes, moderately higher 535 nm band depths, elevated 754 to 934 nm, and negative 934 to 1009 nm slopes. The lack of an absorption at 864 to 904 nm indicates the lack of crystalline red hematite in these red zones, but likely an enrichment in nanophase ferric oxides. The negative 934 to 1009 nm slope is potentially indicative of the presence of adsorbed or structurally bound water. A scuff in a red zone near the southern wall of Marathon Valley uncovered light-toned soils and a pebble with an 803 to 864 nm absorption resembling that of light-toned Fe-sulfate bearing soils uncovered by the Spirit rover in the Columbia Hills of Gusev crater. APXS chemical measurements indicated enrichments of Mg and S in the scuff soils and the pebble, Joseph Field, with the strongest 803 nm band- consistent with Mg and Fe sulfates. The presence of Fe and Mg sulfates can be interpreted as evidence of a potentially later episode of aqueous alteration with an earlier, neutral to alkaline pH episode forming the Fe/Mg smectites and a later acid pH episode forming the Fe and Mg sulfates.

Past environmental/climatic changes in the northern part of the South China Sea, input from multi-proxy analysis of core MD12-3432

NASA Astrophysics Data System (ADS)

Chen, Quan; Kissel, Catherine; Liu, Zhifei

2017-04-01

In the South China Sea, the magnetic component of marine sediment is a powerful recorder of paleoenvironmental changes linked to the regional and global climate. Based on the knowledge of the sedimentary signature of the potential sources for terrigenous sediments, the composition of marine sediments can be used to decipher the different mechanisms, forcing, and transport vectors. We report here the analysis of the magnetic properties combined with sortable silt and clay mineralogy of a 51 m long sedimentary sequence retrieved from the northern South China Sea and covering the last 400 ka. Magnetic minerals with different coercivities (magnetite, pyrrhotite and hematite) are mixed in the sequence and their relative concentration varies with time. Glacial low sea-levels reduce the land-site distance and they are illlustrated by higher concentrations in magnetites and iron-sulfides (pyrrhotite) related to the sediments previously deposited on the continental shelf and re-worked by the river. This is accompanied by increasing kaolinite content within the clay assemblage (Pearl River signature) and by coarser grains. Superimposed to this eccentricity periodicity, hematite content and smectite/(illite+chlorite) ratio present a predominant precession periodicity synchronous with the northern hemisphere summer insolation changes and therefore with that of the East Asian summer monsoon. Events of high hematite content, in phase with finer grains, coincide with precession lows, while smectite/(illite+chlorite) ratio is maximum during precession highs. Knowing that smectite is mainly produced by contemporaneous chemical weathering intensity in Luzon, we use the smectite/(illite+chlorite) ratio as a tracer for increasing weathering rate in Luzon, in turn related to enhanced East Asian summer monsoon. Hematite is not produced in large amount on adjacent lands and its association with fine sediment grains suggests that its periodic supply is related to the eolian dust transported from the Central China deserts to the studied site. Higher hematite content at this latitude may therefore be used as a tracer for weak East Asian summer monsoon intensity.

Coeval Formation of Aqueous Minerals on Mars

NASA Astrophysics Data System (ADS)

Fairen, A.; Uceda, E.; Gil, C.; Palmero Rodriguez, A.; Gago-Duport, L.

2015-12-01

Understanding the geochemical conditions on early Mars requires an explanation for the presence of sulfates and phyllosilicates, which must be also consistent with the absence of widespread sedimentary carbonates. In addition, sulfates and phyllosilicates do not generally occur together on Mars, which has been interpreted as a marker for detached mineral formation due to differing planetary environmental conditions separated dramatically, either in time or in space. Here, thermodynamic equilibrium calculations are used to determine the stability boundaries for phyllosilicates, ferrous and ferric sulfates, carbonates and iron oxyhydroxides precipitation on early Mars, at different atmospheric CO2 pressures and both under reducing and oxidizing conditions. Results suggest that phyllosilicates formed in mildly acidic to alkaline aqueous solutions, with a pH>4 for nontronite and a pH>6 for other smectites with low content in Fe and Mg (montmorillonite, saponite). Sulfate deposition dominates in solutions moderately to highly acidic, with a pH<6 conducive to the synthesis of kieserite. In the overlapping phyllosilicates/sulfates pH range, between 4 and 6, a competition for Mg between nontronite and kieserite is expected, and the formation of nontronite would be favored in areas where SiO2 activity in surface waters was high as a result of intense weathering of the early basaltic crust. Carbonates formed at pH>6, overlapping with the synthesis of low-Fe-Mg smectites. Model calculations anticipate the co-precipitation of smectites and siderite or any alteration product that could have resulted from the later substitution of Fe in siderite, such as Mg- or Mn-carbonate, triggering a competition for Mg between magnesite and low-Fe-Mg smectites. As expected, the model does not predict coeval synthesis of carbonates and sulfates. Goethite and other oxyhydroxides precipitate at pH below 2, a range at which jarosite and goethite are the expected iron-bearing phases. These results suggest that the major water-alteration products on the Martian surface were deposited simultaneously in space and in time, creating diverse geochemical conditions over the entire surface of a cold Mars during the wet Noachian/Hesperian times.

The Cretaceous glauconitic sandstones of Abu Tartur, Egypt

NASA Astrophysics Data System (ADS)

Pestitschek, Brigitte; Gier, Susanne; Essa, Mahmoud; Kurzweil, Johannes

2010-05-01

The Abu Tartur mine is located in the Western Desert of Egypt, 50 km west of El Kharga City. Geologically, the Abu Tartur plateau is built by a sequence of Upper Cretaceous (Campanian - Maastrichtian) phosphorites, black shales and glauconitic sandstones. The phosphate deposits are of great economic importance and have been mined since their discovery in 1967. Outcrop sections were measured, sampled, sedimentologically characterized and described. One specific glaucony layer was investigated mineralogically and chemically in detail and compared to a subsurface sample from the mine. Two depositional regimes can be interpreted based on sedimentary architecture and structures: 1) a deeper-water hemipelagic environment, where phosphorites and organic carbon-rich shales were deposited and 2) a shallower, prograding higher energy shelf environment with glauconies. From a sequence stratigraphic perspective 1) was deposited during the transgressive systems tract and the early highstand while 2) was deposited during the remaining highstand and a lowstand prograding wedge (Glenn & Arthur, 1990). Petrographic and SEM investigations show that the glaucony grains are of authochtonous origin. XRF, EMPA and thin-section analyses show that the glaucony grains from the outcrop differ significantly in their chemical composition, morphology and color from the grains of the mine sample. The fresh glauconies are enriched in Fe2O3 and K2O compared to the surface samples. XRD analyses of the clay fraction of the six outcrop samples and the mine sample show that the grains consist of illite(glauconite)/smectite mixed-layers, with more illite layers (80 %) in the mine sample. The charge distribution diagram muscovite-pyrophyllite-celadonite shows a clear trend from smectitic glaucony to illitic glaucony, the mine sample plots exactly in the field for glauconites. All these features indicate that the surface samples are strongly altered by weathering and that glauconite progressively transforms into iron-rich illte/smectite mixed layers and then into smectites. For any chemical and mineralogical characterization of glauconites at surface, these weathering effects have to be taken into consideration. GLENN, C. R. & ARTHUR, M. A. (1990): Anatomy and origin of a Cretaceous phosphorites-greensand giant, Egypt. Sedimentology, 37, 123-154.

Hydrothermal alteration of graywacke and basalt by 4 molal NaCl.

USGS Publications Warehouse

Rosenbauer, R.J.; Bischoff, J.L.; Radtke, A.S.

1983-01-01

Rock-water interaction experiments were carried out at 350oC and 500 bar at a 1/10 rock/fluid ratio using 4 molal NaCl brine. Reaction of brine and greywacke lead to the conversion of illite, dolomite and quartz to albite and smectite. In the process, the rock gained Na and released Ca, K, heavy metals and CO2 to solution. Metal mobilization was found to primarily depend on acidity which was produced by Na metasomatism and by dedolomitization. Reaction of brine and basalt produced only minor alteration in which some smectite and little albite formed. No significant acidity was produced nor did metals become mobilized. Production of acidity during albitization depends entirely on the phase being altered. Albitization of greywacke produces H+ whereas the albitization of basalt apparently consumes this ion. -J.E.S.

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.

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.

Overpressure generation by load transfer following shale framework weakening due to smectite diagenesis

USGS Publications Warehouse

Lahann, R.W.; Swarbrick, R.E.

2011-01-01

Basin model studies which have addressed the importance of smectite conversion to illite as a source of overpressure in the Gulf of Mexico have principally relied on a single-shale compaction model and treated the smectite reaction as only a fluid-source term. Recent fluid pressure interpretation and shale petrology studies indicate that conversion of bound water to mobile water, dissolution of load-bearing grains, and increased preferred orientation change the compaction properties of the shale. This results in substantial changes in effective stress and fluid pressure. The resulting fluid pressure can be 1500-3000psi higher than pressures interpreted from models based on shallow compaction trends. Shale diagenesis changes the mineralogy, volume, and orientation of the load-bearing grains in the shale as well as the volume of bound water. This process creates a weaker (more compactable) grain framework. When these changes occur without fluid export from the shale, some of the stress is transferred from the grains onto the fluid. Observed relationships between shale density and calculated effective stress in Gulf of Mexico shelf wells confirm these changes in shale properties with depth. Further, the density-effective stress changes cannot be explained by fluid-expansion or fluid-source processes or by prediagenesis compaction, but are consistent with a dynamic diagenetic modification of the shale mineralogy, texture, and compaction properties during burial. These findings support the incorporation of diagenetic modification of compaction properties as part of the fluid pressure interpretation process. ?? 2011 Blackwell Publishing Ltd.

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.;

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.

Iridium contents in the Late Cretaceous-Early Tertiary clays in relation to the K/T boundary, North Jordan

NASA Astrophysics Data System (ADS)

Abboud, Iyad Ahmed

2016-06-01

The mineralogy, lithology, and geochemistry of five discrete laminations across the K/T boundary of clayey shale at the Yarmouk River area, Jordan, were examined. There were no marked changes in the mineralogy of the clayey shale within the K/T boundary. This outcrop consists of more than 100 m of Maastrichtian oil shale overlying about 20 m limestone. Marly limestone included many clay laminations from organic and volcanic origins, which are considered an evidence of the K/T boundary through detected iridium anomalies. Any of these particular lamellae range from 2 mm to 5 mm in thickness. Smectite was the predominant clay mineral in smectitic shale laminations. It was located at eight meters above the K/T boundary and includes some anomalous concentrations of iridium and traces of other elements. The analysis of geochemical platinum group at the K/T boundary clays showed anomalous enrichments of iridium, compared with other carbonate rocks as a result of weathering processes of oil shale, or through concentration from weathering of basalt flows, but not pointing to an impact process. The clays in late Maastrichtian have Ir-Sc prevailed anomalies and synchronize with increasing of terrigenous and volcanogenic traced elements. Kaolin, smectite, and volkonskoite were the dominant clay minerals at the K/T boundary with high concentrations of iridium. The concentration levels of iridium in some laminations of the Yarmouk sediments ranged between 1.6 and 7.8 ppb.

The role of microbial iron reduction in the formation of Proterozoic molar tooth structures

NASA Astrophysics Data System (ADS)

Hodgskiss, Malcolm S. W.; Kunzmann, Marcus; Poirier, André; Halverson, Galen P.

2018-01-01

Molar tooth structures are poorly understood early diagenetic, microspar-filled voids in clay-rich carbonate sediments. They are a common structure in sedimentary successions dating from 2600-720 Ma, but do not occur in rocks older or younger, with the exception of two isolated Ediacaran occurrences. Despite being locally volumetrically significant in carbonate rocks of this age, their formation and disappearance in the geological record remain enigmatic. Here we present iron isotope data, supported by carbon and oxygen isotopes, major and minor element concentrations, and total organic carbon and sulphur contents for 87 samples from units in ten different basins spanning ca. 1900-635 Ma. The iron isotope composition of molar tooth structures is almost always lighter (modal depletion of 2‰) than the carbonate or residue components in the host sediment. We interpret the isotopically light iron in molar tooth structures to have been produced by dissimilatory iron reduction utilising Fe-rich smectites and Fe-oxyhydroxides in the upper sediment column. The microbial conversion of smectite to illite results in a volume reduction of clay minerals (∼30%) while simultaneously increasing pore water alkalinity. When coupled with wave loading, this biogeochemical process is a viable mechanism to produce voids and subsequently precipitate carbonate minerals. The disappearance of molar tooth structures in the mid-Neoproterozoic is likely linked to a combination of a decrease in smectite abundance, a decline in the marine DIC reservoir, and an increase in the concentration of O2 in shallow seawater.

Clay mineral diversity and abundance in sedimentary rocks of Gale crater, Mars.

PubMed

Bristow, Thomas F; Rampe, Elizabeth B; Achilles, Cherie N; Blake, David F; Chipera, Steve J; Craig, Patricia; Crisp, Joy A; Des Marais, David J; Downs, Robert T; Gellert, Ralf; Grotzinger, John P; Gupta, Sanjeev; Hazen, Robert M; Horgan, Briony; Hogancamp, Joanna V; Mangold, Nicolas; Mahaffy, Paul R; McAdam, Amy C; Ming, Doug W; Morookian, John Michael; Morris, Richard V; Morrison, Shaunna M; Treiman, Allan H; Vaniman, David T; Vasavada, Ashwin R; Yen, Albert S

2018-06-01

Clay minerals provide indicators of the evolution of aqueous conditions and possible habitats for life on ancient Mars. Analyses by the Mars Science Laboratory rover Curiosity show that ~3.5-billion year (Ga) fluvio-lacustrine mudstones in Gale crater contain up to ~28 weight % (wt %) clay minerals. We demonstrate that the species of clay minerals deduced from x-ray diffraction and evolved gas analysis show a strong paleoenvironmental dependency. While perennial lake mudstones are characterized by Fe-saponite, we find that stratigraphic intervals associated with episodic lake drying contain Al-rich, Fe 3+ -bearing dioctahedral smectite, with minor (3 wt %) quantities of ferripyrophyllite, interpreted as wind-blown detritus, found in candidate aeolian deposits. Our results suggest that dioctahedral smectite formed via near-surface chemical weathering driven by fluctuations in lake level and atmospheric infiltration, a process leading to the redistribution of nutrients and potentially influencing the cycling of gases that help regulate climate.

Oligocene lacustrine tuff facies, Abu Treifeya, Cairo-Suez Road, Egypt

NASA Astrophysics Data System (ADS)

Abdel-Motelib, Ali; Kabesh, Mona; El Manawi, Abdel Hamid; Said, Amir

2015-02-01

Field investigations in the Abu Treifeya area, Cairo-Suez District, revealed the presence of Oligocene lacustrine volcaniclastic deposits of lacustrine sequences associated with an Oligocene rift regime. The present study represents a new record of lacustrine zeolite deposits associated with saponite clay minerals contained within reworked clastic vitric tuffs. The different lithofacies associations of these clastic sequences are identified and described: volcaniclastic sedimentary facies represent episodic volcaniclastic reworking, redistribution and redeposition in a lacustrine environment and these deposits are subdivided into proximal and medial facies. Zeolite and smectite minerals are mainly found as authigenic crystals formed in vugs or crusts due to the reaction of volcanic glasses with saline-alkaline water or as alteration products of feldspars. The presence of abundant smectite (saponite) may be attributed to a warm climate, with alternating humid and dry conditions characterised by the existence of kaolinite. Reddish iron-rich paleosols record periods of non-deposition intercalated with the volcaniclastic tuff sequence.

The fate of iron on Mars: Mechanism of oxidation of basaltic minerals to ferric-bearing assemblages

NASA Technical Reports Server (NTRS)

Burns, Roger G.

1992-01-01

Perhaps the most conspicuous indication that chemical weathering has occurred on the surface of Mars is the overall color of the red planet and the spectroscopic features that identify ferric-bearing assemblages in the martian regolith. Apparently, Fe(2+) ions in primary minerals in parent igneous rocks on the martian surface have been oxidized to ferric iron, which occurs in degradation products that now constitute the regolith. The mineralogy of the unweathered igneous rocks prior to weathering on the martian surface is reasonably well constrained, mainly as a result of petrographic studies of the SNC meteorites. However, the alteration products resulting from oxidative weathering of these rocks are less well-constrained. The topics covered include the following: primary rocks subjected to chemical weathering; dissolution processes; oxidation of dissolved Fe(2+); mechanism of polymerization of hydrous ferric oxides; terrestrial occurrences of ferromagnesian smectites; and dehydroxylated Mg-Fe smectites on Mars.

Origin and significance of clay-coated fractures in mudrock fragments of the SAFOD borehole (Parkfield, California)

USGS Publications Warehouse

Schleicher, A.M.; van der Pluijm, B.A.; Solum, J.G.; Warr, L.N.

2006-01-01

The clay mineralogy and texture of rock fragments from the SAFOD borehole at 3067 m and 3436 m measured depth (MD) was investigated by electron microscopy (SEM, TEM) and X-ray-diffraction (XRD). The washed and ultrasonically cleaned samples show slickenfiber striations and thin films of Ca-K bearing smectite that are formed on polished fault surfaces, along freshly opened fractures and within adjacent mineralized veins. The cation composition and hydration behavior of these films differ from the Namontmorillonite of the fresh bentonite drilling mud, although there is more similarity with circulated mud recovered from 3479 m MD. We propose that these thin film smectite precipitates formed by natural nucleation and crystal growth during fault creep, probably associated with the shallow circulation of low temperature aqueous fluids along this shallow portion of the San Andreas Fault. Copyright 2006 by the American Geophysical Union.

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

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

Subglacial hydrothermal alteration minerals in Jökulhlaup deposits of Southern Iceland, with implications for detecting past or present habitable environments on Mars.

PubMed

Warner, Nicholas H; Farmer, Jack D

2010-06-01

Jökulhlaups are terrestrial catastrophic outfloods, often triggered by subglacial volcanic eruptions. Similar volcano-ice interactions were likely important on Mars where magma/lava may have interacted with the planet's cryosphere to produce catastrophic floods. As a potential analogue to sediments deposited during martian floods, the Holocene sandurs of Iceland are dominated by basaltic clasts derived from the subglacial environment and deposited during jökulhlaups. Palagonite tuffs and breccias, present within the deposits, represent the primary alteration lithology. The surface abundance of palagonite on the sandurs is 1-20%. X-ray diffraction (XRD) analysis of palagonite breccias confirms a mineral assemblage of zeolites, smectites, low-quartz, and kaolinite. Oriented powder X-ray diffractograms (< 2 microm fraction) for palagonite breccia clasts and coatings reveal randomly ordered smectite, mixed layer smectite/illite, zeolites, and quartz. Visible light-near infrared (VNIR) and shortwave infrared (SWIR) lab spectroscopic data of the same palagonite samples show H2O/OH(-) absorptions associated with clays and zeolites. SWIR spectra derived from Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) images of the sandurs reveal Al-OH(-) and Si-OH(-) absorption features. The identified alteration mineral assemblage is consistent with low temperature (100-140 degrees C) hydrothermal alteration of basaltic material within the subglacial environment. These results suggest that potential martian analog sites that contain a similar suite of hydrated minerals may be indicative of past hydrothermal activity and locations where past habitable environments for microbial life may be found.

The Lower Silurian Osmundsberg K-bentonite. Part II: Mineralogy, geochemistry, chemostratigraphy and tectonomagmatic significance

USGS Publications Warehouse

Huff, W.D.; Bergstrom, Stig M.; Kolata, Dennis R.; Sun, H.

1998-01-01

The Lower Silurian Osmundsberg K-bentonite is a widespread ash bed that occurs throughout Baltoscandia and parts of northern Europe. This paper describes its characteristics at its type locality in the Province of Dalarna, Sweden. It contains mineralogical and chemical characteristics that permit its regional correlation in sections elsewhere in Sweden as well as Norway, Estonia, Denmark and Great Britain. The < 2 ??m clay fraction of the Osmundsberg bed contains abundant kaolinite in addition to randomly ordered (RO) illite/smectite (I/S). Modelling of the X-ray diffraction tracings showed the I/S consists of 18% illite and 82 % smectite. The high smectite and kaolinite content is indicative of a history with minimal burial temperatures. Analytical data from both pristine melt inclusions in primary quartz grains as well as whole rock samples can be used to constrain both the parental magma composition and the probable tectonic setting of the source volcanoes. The parental ash was dacitic to rhyolitic in composition and originated in a tectonically active collision margin setting. Whole rock chemical fingerprinting of coeval beds elsewhere in Baltoscandia produced a pronounced clustering of these samples in the Osmundsberg field of the discriminant analysis diagram. This, together with well-constrained biostratigraphic and lithostratigraphic data, provides the basis for regional correlation and supports the conclusion that the Osmundsberg K-bentonite is one of the most extensive fallout ash beds in the early Phanerozoic. The source volcano probably lay to the west of Baltica as part of the subduction complex associated with the closure of Iapetus.

Steeply dipping heaving bedrock, Colorado: Part 2 - Mineralogical and engineering properties

USGS Publications Warehouse

Noe, D.C.; Higgins, J.D.; Olsen, H.W.

2007-01-01

This paper describes the mineralogical and engineering properties of steeply dipping, differentially heaving bedrock, which has caused severe damage near the Denver area. Several field sites in heave-prone areas have been characterized using high sample densities, numerous testing methodologies, and thousands of sample tests. Hydrometer testing shows that the strata range from siltstone to claystone (33 to 66 percent clay) with occasional bentonite seams (53 to 98 percent clay mixed with calcite). From X-ray diffraction analyses, the claystone contains varying proportions of illite-smectite and discrete (pure) smectite, and the bentonite contains discrete smectite. Accessory minerals include pyrite, gypsum, calcite, and oxidized iron compounds. The dominant exchangeable cation is Ca2+, except where gypsum is prevalent, and Mg2+ and Na1+ are elevated. Scanning electron microscope analyses show that the clay fabric is deformed and porous and that pyrite is absent within the weathered zone. Unified Soil Classification for the claystone varies from CL to CH, and the bentonite is CH to MH. Average moisture content values are 17 percent for claystone and 32 percent for bentonite, and these are typically 0 to 5 percent lower than the plastic limit. Swell-consolidation and suction testing shows a full range of swelling potentials from low to very high. These findings confirm that type I (bed-parallel, symmetrical to asymmetrical) heave features are strongly associated with changes in bedrock composition and mineralogy. Composition changes are not necessarily a factor for type II (bed-parallel to bed-oblique, strongly asymmetrical) heave features, which are associated with movements along subsurface shear zones.

Radiation-stability of smectite.

PubMed

Sorieul, Stéphanie; Allard, Thierry; Wang, Lumin M; Grambin-Lapeyre, Caroline; Lian, Jie; Calas, Georges; Ewings, Rodney C

2008-11-15

The safety assessment of geological repositories for high-level nuclear waste and spent nuclear fuel requires an understanding of the response of materials to high temperatures and intense radiation fields. Clays, such as smectite, have been proposed as backfill material around waste packages, but their response to intense radiation from short-lived fission products and alpha decay of sorbed actinides remains poorly understood. Cumulative doses may amorphize clays and may alter their properties of sorption, swelling, or water retention. We describe the amorphization of smectites induced by electron and heavy ion irradiations to simulate ionizing radiation and alpha recoil nuclei, respectively. A new "bell-shaped" evolution of the amorphization dose with temperature has been determined. The maximum dose for amorphization occurs at about 300-400 degrees C, showing that temperature-induced dehydroxylation enhances amorphization. The exact shape of the bell-shaped curves depends on the interlayer cation. At ambient temperature, ionizing radiation and alpha-decay events do not show the same efficiency. The former results in amorphization at doses between 10(10)-10(11) Gy which are greater than the total radiation dose expected for radioactive waste over 10(6) years. In contrast, alpha-decay events amorphize clays at doses as low as 0.13-0.16 displacements per atom, i.e. doses consistent with nuclear waste accumulated over approximately 1000 yrs. However, the limited penetration of alpha particles and recoil nuclei, in the 100 nm - 20 microm range, will minimize damage. Clays will not be amorphized unless the waste package is breached and released actinides are heavily sorbed onto the clay overpack.

Effect of phosphate on U(VI) sorption to montmorillonite: Ternary complexation and precipitation barriers

NASA Astrophysics Data System (ADS)

Troyer, Lyndsay D.; Maillot, Fabien; Wang, Zheming; Wang, Zimeng; Mehta, Vrajesh S.; Giammar, Daniel E.; Catalano, Jeffrey G.

2016-02-01

Phosphate addition is a potential treatment method to lower the solubility of U(VI) in soil and groundwater systems by causing U(VI) phosphate precipitation as well as enhancing adsorption. Previous work has shown that iron oxide surfaces may facilitate the nucleation of U(VI) phosphate minerals and, that under weakly acidic conditions, phosphate also enhances U(VI) adsorption to such phases. Like iron oxides, clays are important reactive phases in the subsurface but little is known about the interaction of U(VI) and phosphate with these minerals. The effect of aqueous phosphate on U(VI) binding to Wyoming montmorillonite (SWy-2) in air-equilibrated systems was investigated. Equilibrium U(VI) uptake to montmorillonite was determined at pH 4, 6 and 8 at discrete initial phosphate concentrations between 0 and 100 μM. The observed behavior of U(VI) indicates a transition from adsorption to precipitation with increasing total uranium and phosphate concentrations at all pH values. At the highest phosphate concentration examined at each pH value, a barrier to U(VI) phosphate nucleation is observed. At lower concentrations, phosphate has no effect on macroscopic U(VI) adsorption. To assess the mechanisms of U(VI)-phosphate interactions on smectite surfaces, U(VI) speciation was investigated under selected conditions using laser-induced fluorescence spectroscopy (LIFS) and extended X-ray absorption fine-structure (EXAFS) spectroscopy. Samples above the precipitation threshold display EXAFS and LIFS spectral signatures consistent with the autunite family of U(VI) phosphate minerals. However, at lower U(VI) concentrations, changes in LIFS spectra upon phosphate addition suggest that U(VI)-phosphate ternary surface complexes form on the montmorillonite surface at pH 4 and 6 despite the lack of a macroscopic effect on adsorption. The speciation of solid-associated U(VI) below the precipitation threshold at pH 8 is dominated by U(VI)-carbonate surface complexes. This work reveals that ternary complexation may occur without a macroscopic signature, which is attributed to phosphate not appreciably binding to smectite in the absence of U(VI), with U(VI) surface complexes serving as the sole reactive surface sites for phosphate. This study shows that phosphate does not enhance U(VI) adsorption to smectite clay minerals, unlike oxide phases, and that a barrier to homogeneous nucleation of U(VI) phosphates was not affected by the presence of the smectite surface.

Heterogeneous distribution of pelagic sediments incoming the Japan Trench possibly controlling slip propagation on shallow plate boundary fault

NASA Astrophysics Data System (ADS)

Yamaguchi, A.; Nakamura, Y.; Fukuchi, R.; Kurano, H.; Ikehara, K.; Kanamatsu, T.; Arai, K.; Usami, K.; Ashi, J.

2017-12-01

Catastrophic tsunami of the 2011 Tohoku Earthquake was triggered by large coseismic slip reached to the Japan Trench axis (e.g. Fujiwara et al., 2011, Science; Kodaira et al., 2012, Nature Geoscience). Results of the IODP Expedition 343 (JFAST) suggest that small friction of smectite-rich pelagic clay caused slip propagation on shallow plate boundary fault (Ujiie et al., 2013, Science; Kameda et al., 2015, Geology; Moore et al., 2015, Geosphere). On the other hand, JAMSTEC high-resolution seismic profiles show that incoming sediments have large heterogeneities in thicknesses, and two areas of extremely thin sediments on the Pacific Plate (thickness less than 100 m) were found at around 39°N (Nakamura et al., AGU 2017, this session). To reconcile whether the smectite-rich pelagic clay even exists in these areas, we sampled surface sediments during the R/V Shinsei Maru KS-15-3 cruise. Seven piston cores were retrieved from seaward trench slope, horst, graben, and graben edge. Core lithologies are mainly diatomaceous ooze/clay including tephra layers, not resemble to pelagic clays discovered in JFAST. Ages of tephra layers were estimated by correlating mineral assemblages and refractive indices of volcanic glasses to Japanese widespread tephras. Averaged sedimentation rates of seaward trench slope, horst, graben, and graben edge are estimated to be 25-30, 6.5-20, 45, 0.9 cm/kyr, respectively. These sedimentation rates imply that sediments on seaward trench slope and horst have been deposited in the last 160-500 kyr, suggesting that entire pelagic sediments, including smectite-rich pelagic clay, have been removed by some reasons in the last 0.5 million years. Possible reason for such modification of sediment is near-trench igneous activity known as petit-spot volcanism (Hirano et al., 2006, Science). The lack of smectite-rich pelagic clay near 39°N of the Japan Trench is consistent with results of tsunami inversions proposing shallow large coseismic slip propagated to 39°N and stopped northward (Koketsu et al., 2011, Earth Planet. Sci. Lett.; Satake et al., 2013, Bull. Seism. Soc. Am.). In the off-Sanriku Japan Trench, slip propagation is likely to be controlled by frictional property of incoming sediments, and sediment disappearance due to petit-spot volcanism may affect rupture area segmentation.

Remobilization of toxic heavy metals adsorbed to bacterial wall-clay composites.

PubMed Central

Flemming, C A; Ferris, F G; Beveridge, T J; Bailey, G W

1990-01-01

Significant quantities of Ag(I), Cu(II), and Cr(III) were bound to isolated Bacillus subtilis 168 walls, Escherichia coli K-12 envelopes, kaolinite and smectite clays, and the corresponding organic material-clay aggregates (1:1, wt/wt). These sorbed metals were leached with HNO3, Ca(NO3)2, EDTA, fulvic acid, and lysozyme at several concentrations over 48 h at room temperature. The remobilization of the sorbed metals depended on the physical properties of the organic and clay surfaces and on the character and concentration of the leaching agents. In general, the order of remobilization of metals was Cr much less than Ag less than Cu. Cr was very stable in the wall, clay, and composite systems; pH 3.0, 500 microM EDTA, 120-ppm [mg liter-1] fulvic acid, and 160-ppm Ca remobilized less than 32% (wt/wt) of sorbed Cr. Ag (45 to 87%) and Cu (up to 100%) were readily removed by these agents. Although each leaching agent was effective at mobilizing certain metals, elevated Ca or acidic pH produced the greatest overall mobility. The organic chelators were less effective. Lysozyme digestion of Bacillus walls remobilized Cu from walls and Cu-wall-kaolinite composites, but Ag, Cr, and smectite partially inhibited enzyme activity, and the metals remained insoluble. The extent of metal remobilization was not always dependent on increasing concentrations of leaching agents; for example, Ag mobility decreased with some clays and some composites treated with high fulvic acid, EDTA, and lysozyme concentrations. Sometimes the organic material-clay composites reacted in a manner distinctly different from that of their individual counterparts; e.g., 25% less Cu was remobilized from wall- and envelope-smectite composites than from walls, envelopes, or smectite individually in 500 microM EDTA. Alternatively, treatment with 160-ppm Ca removed 1.5 to 10 times more Ag from envelope-kaolinite composites than from the individual components. The particle size of the deposited metal may account for some of the stability changes; those metals that formed large, compact aggregates (Cr and Ag) as seen by transmission electron microscopy were less likely to be remobilized. In summary, it is apparent that remobilization of toxic heavy metals in sediments, soils, and the vadose zone is a complicated issue. Predictions based on single inorganic or organic component systems are too simplistic. Images PMID:2126702

Thickness distributions and evolution of growth mechanisms of NH4-illite from the fossil hydrothermal system of Harghita Bai, Eastern Carpathians, Romania

USGS Publications Warehouse

Bobos, Iuliu; Eberl, Dennis D.

2013-01-01

The crystal growth of NH4-illite (NH4-I) from the hydrothermal system of Harghita Bãi (Eastern Carpathians) was deduced from the shapes of crystal thickness distributions (CTDs). The 4-illite-smectite (I-S) interstratified structures (R1, R2, and R3-type ordering) with a variable smectite-layer content. The NH4-I-S (40–5% S) structures were identified underground in a hydrothermal breccia structure, whereas the K-I/NH4-I mixtures were found at the deepest level sampled (−110 m). The percentage of smectite interlayers generally decreases with increasing depth in the deposit. This decrease in smectite content is related to the increase in degree of fracturing in the breccia structure and corresponds to a general increase in mean illite crystal thickness. In order to determine the thickness distributions of NH4-I crystals (fundamental illite particles) which make up the NH4-I-S interstratified structures and the NH4,-I/K-I mixtures, 27 samples were saturated with Li+ and aqueous solutions of PVP-10 to remove swelling and then were analyzed by X-ray diffraction. The profiles for the mean crystallite thickness (Tmean) and crystallite thickness distribution (CTD) of NH4-I crystallites were determined by the Bertaut-Warren-Averbach method using the MudMaster computer code. The Tmean of NH4-I from NH4-I-S samples ranges from 3.4 to 7.8 nm. The Tmean measured for the NH4-I/K-I mixture phase ranges from 7.8 nm to 11.7 nm (NH4-I) and from 12.1 to 24.7 nm (K-I).The CTD shapes of NH4-I fundamental particles are asymptotic and lognormal, whereas illites from NH4-I/K-I mixtures have bimodal shapes related to the presence of two lognormal-like CTDs corresponding to NH4-I and K-I.The crystal-growth mechanism for NH4-I samples was simulated using the Galoper code. Reaction pathways for NH4-I crystal nucleation and growth could be determined for each sample by plotting their CTD parameters on an α–β2 diagram constructed using Galoper. This analysis shows that NH4-I crystals underwent simultaneous nucleation and growth, followed by surface-controlled growth without simultaneous nucleation.

Chemistry, mineralogy and alteration intensity of hydrothermal altered Mt Unzen conduit rocks (Shimabara/Japan)

NASA Astrophysics Data System (ADS)

Hess, Kai-Uwe; Yilmaz, Tim; Gilg, H. Albert; Janots, Emilie; Mayer, Klaus; Nakada, Setsuya; Dingwell, Donald

2017-04-01

Investigations were carried out on hydrothermally altered coherent dacitic dykes samples from (USDP-4) drill core at Mt Unzen stratovolcano (Shimabara/Japan). XRF, XRD, EMPA, C-O-isotope, hot-cathode CL and SEM analysis led to insights concerning chemistry, mineralogy, and intensity and type of alteration as well as the origin of carbonate-precipitating fluids. Additionally a textural characterization of the occurring replacement features in the volcanic conduit rocks was performed. The occurrence of the main secondary phases such as chlorite, pyrite, carbonates, and R1 (Reichweite parameter) illite-smectite and kaolinite group minerals indicate a weak to moderate propylitic to phyllic hydrothermal alteration. The dacitic samples of the dykes show different hydrothermal alteration features: (i) carbonate and chlorite pseudomorphs after hornblende as well as core and zonal textures due to replacement of plagioclase by R1 illite-smectite as well as kaolinite group minerals, (ii) colloform banded fracture fillings and fillings in dissolution vugs, and (iii) chlorite, R1 illite-smectite as well as kaolinite group minerals in the groundmass. Late chlorite veins crosscut precipitates of R1 illite-smectite as well as kaolinite group minerals. Carbonates in fractures and in pseudomorphs after hornblende comprise iron-rich dolomite solid solutions ("ankerite") and calcite. Isotopic values indicate a hydrothermal-magmatic origin for the carbonate formation. The chlorite-carbonate-pyrite index (CCPI) and the Ishikawa alteration index (AI), applied to the investigated samples show significant differences (CCPI=52.7-57.8; AI=36.1-40.6) indicating their different degree of alteration. According to Nakada et al., 2005, the C13 to C16 dykes represent the feeder dyke from the latest eruption (1991-1995) whereas C8 represents an earlier dyke feeder dyke from an older eruption. Weakest alteration, which was obtained in samples C16-1-5 and C13-2-5, correlates with the alteration degree of the pristine dome rocks. The highest CCPI value was determined for sample C14-1-5 and the highest AI value was determined for sample C15-2-6. The degrees of alteration do not indicate highest alteration of the samples C8-1-2 and C8-2-1 from the older dykes.

40 CFR 264.314 - Special requirements for bulk and containerized liquids.

Code of Federal Regulations, 2014 CFR

2014-07-01

..., smectites, Fuller's earth, bentonite, calcium bentonite, montmorillonite, calcined montmorillonite.../hydroxides, alumina, lime, silica (sand), diatomaceous earth; perlite (volcanic glass); expanded volcanic... contain, hazardous waste; and (2) Placement in such owner or operator's landfill will not present a risk...

40 CFR 264.314 - Special requirements for bulk and containerized liquids.

Code of Federal Regulations, 2012 CFR

2012-07-01

..., smectites, Fuller's earth, bentonite, calcium bentonite, montmorillonite, calcined montmorillonite.../hydroxides, alumina, lime, silica (sand), diatomaceous earth; perlite (volcanic glass); expanded volcanic... contain, hazardous waste; and (2) Placement in such owner or operator's landfill will not present a risk...

40 CFR 264.314 - Special requirements for bulk and containerized liquids.

Code of Federal Regulations, 2013 CFR

2013-07-01

..., smectites, Fuller's earth, bentonite, calcium bentonite, montmorillonite, calcined montmorillonite.../hydroxides, alumina, lime, silica (sand), diatomaceous earth; perlite (volcanic glass); expanded volcanic... contain, hazardous waste; and (2) Placement in such owner or operator's landfill will not present a risk...

Mineralogy and thermal properties of clay from Slatina (Ub, Serbia)

NASA Astrophysics Data System (ADS)

Milosevic, Maja; Logar, Mihovil; Kaludjerovic, Lazar; Jelic, Ivana

2017-04-01

The "Slatina" deposit, Ub, Serbia was opened in 1965 and represents one of few deposits exploited by "Kopovi" a.d., Ub, company. Deposit is composed of clay layers belonging to Neogene sediments that are widespread transgressive over granitoid rocks of Cer mountain and Paleozoic and Mesozoic sediments. Clay is mostly of illite-montmorillonite-kaolinite type and they are generally used as ceramic materials while some of the layers are used as fire-resistant materials. In this study we present mineralogical and thermal characterization of two samples to determine their application as industrial materials. Chemical and mineral composition was determined using inductively coupled plasma optical emission spectroscopy (ICP-OES), X-ray diffraction (XRD) on powder and oriented samples, infrared spectroscopy (IR) and granulometry. Cationic exchange capacity (CEC) and specific surface area (SSA) was determined using spectrophotometry and methylene blue (MB). Thermal properties where determined by gravimetry (120, 350, 600 and 1000 oC) and differential thermal analysis (DTA). Quantitative mineral composition obtained by Rietveld refinement of combined chemical and XRD data shows that the sample 1(SC) is mainly smectite-illite (45%) and kaolinite (14%) clay with 19% of quartz, 10% feldspars and 7% of limonite, while sample 2(SV) is smectite-illite (43%) and kaolinite (11%) clay with 10% of quartz, 15% feldspars and 7% of limonite. Both samples have low content of impurities (carbonate minerals). Medium grain size (μm) goes from 1.02 (SSA = 104 m2/g) for sample 1(SC) to 0.71 (SSA = 117 m2/g) for sample 2(SV) while their CEC is 12.7 and 14.9 mmol/100g for 1(SC) and 2(SV) respectively. IR spectra of the samples shows larger amount of smectite clays with quartz and carbonate minerals for both samples which is in accordance with XRD data. DTA data shows couple of events that are endothermic. First one (100-200 oC) is associated with loss of moisture and constitutive water, second (300-400 oC) with iron hydroxide minerals, third (500-600 oC) with smectite clay content with smaller separate bands of kaolinite clays while events between 800-900 oC correspond to carbonate minerals. Loss of mass after gravimetry measurement at given temperatures shows that the samples have significant amount of water in their structure (≈3 wt% (120 oC)) with larger weight loss at 600 oC (3.06 and 3.37 wt%) while total weight loss is 9.12 and 9.08 wt% for 1(SC) and 2(SV) respectively. The studied clays from "Slatina" deposit have a medium content of smectite-illite minerals with smaller amount of kaolinite mineral together with quartz and feldspars. Based on their mineral composition and characteristics, possible application should be in different types of ceramic and construction industries. REFERENCES - M. Milošević, M. Logar, B. Dojčinović, A. Rosić and S. Erić, 2016, Diffuse reflectance spectra of methylene blue adsorbed on different types of clay samples, Clay Minerals, (2016) 5, 1-15

Visible and Near-IR Reflectance Spectra of Smectite Acquired Under Dry Conditions for Interpretation of Martian Surface Mineralogy

NASA Technical Reports Server (NTRS)

Morris, Richard V.; Achilles, Cherie N; Archer, Paul D.; Graff, Trevor G.; Agresti, David G.; Ming, Douglas W; Golden, Dadi C.; Mertzman, Stanley A.

2011-01-01

Visible and near-IR (VNIR) spectra from the MEx OMEGA and the MRO CRISM hyper-spectral imaging instruments have spectral features associated with the H2O molecule and M OH functional groups (M = Mg, Fe, Al, and Si). Mineralogical assignments of martian spectral features are made on the basis of laboratory VNIR spectra, which were often acquired under ambient (humid) conditions. Smectites like nontronite, saponite, and montmorillionite have interlayer H2O that is exchangeable with their environment, and we have acquired smectite reflectance spectra under dry environmental conditions for interpretation of martian surface mineralogy. We also obtained chemical, Moessbauer (MB), powder X-ray diffraction (XRD), and thermogravimetric (TG) data to understand variations in spectral properties. VNIR spectra were recorded in humid lab air at 25-35C, in a dynamic dry N2 atmosphere (50-150 ppmv H2O) after exposing the smectite samples (5 nontronites, 3 montmorillionites, and 1 saponite) to that atmosphere for up to approximately l000 hr each at 25-35C, approximately 105C, and approximately 215C, and after re-exposure to humid lab air. Heating at 105C and 215C for approximately 1000 hr is taken as a surrogate for geologic time scales at lower temperatures. Upon exposure to dry N2, the position and intensity of spectral features associated with M-OH were relatively insensitive to the dry environment, and the spectral features associated with H2O (e.g., approximately 1.90 micrometers) decreased in intensity and are sometimes not detectable by the end of the 215C heating step. The position and intensity of H2O spectral features recovered upon re-exposure to lab air. XRD data show interlayer collapse for the nontronites and Namontmorillionites, with the interlayer remaining collapsed for the latter after re-exposure to lab air. The interlayer did not collapse for the saponite and Ca-montmorillionite. TG data show that the concentration of H2O derived from structural OH was invariant to the dry N2 treatment for saponite and the montmorillionites, but the nontronites had additional structural OH after treatment. Upon exposure to dry N2, the VNIR spectra also acquired a red slope with decreasing albedo between approximately 0.4 and approximately 2.0 micrometers. The magnitude of the effects covaries with exposure time to dry N2 and heating temperature. Upon re-exposure to lab air, the slope and albedo do not completely recover to pre-exposure values. MB data show that these effects do not result from partial reduction of ferric to ferrous iron, and TG data show they do not result from loss of structural OH. Possible explanations include formation of small clusters of (superparamagnetic) ferric oxide and reduced smectite crystallinity. The difference in spectral properties between spectra acquired in humid lab air and under dry conditions are consequential for interpretation of CRISM and OMEGA spectra. For example, nontronite by itself and not nontronite plus ferrihydrite can account for the red spectral slope in martian spectra where nontronite is indicated by the Fe-OH spectral features.

Timescales of carbon turnover in soils with mixed crystalline mineralogies

NASA Astrophysics Data System (ADS)

Khomo, Lesego; Trumbore, Susan; Bern, Carleton R.; Chadwick, Oliver A.

2017-01-01

Organic matter-mineral associations stabilize much of the carbon (C) stored globally in soils. Metastable short-range-order (SRO) minerals such as allophane and ferrihydrite provide one mechanism for long-term stabilization of organic matter in young soil. However, in soils with few SRO minerals and a predominance of crystalline aluminosilicate or Fe (and Al) oxyhydroxide, C turnover should be governed by chemisorption with those minerals. Here, we correlate mineral composition from soils containing small amounts of SRO minerals with mean turnover time (TT) of C estimated from radiocarbon (14C) in bulk soil, free light fraction and mineral-associated organic matter. We varied the mineral amount and composition by sampling ancient soils formed on different lithologies in arid to subhumid climates in Kruger National Park (KNP), South Africa. Mineral contents in bulk soils were assessed using chemical extractions to quantify Fe oxyhydroxides and SRO minerals. Because of our interest in the role of silicate clay mineralogy, particularly smectite (2 : 1) and kaolinite (1 : 1), we separately quantified the mineralogy of the clay-sized fraction using X-ray diffraction (XRD) and measured 14C on the same fraction. Density separation demonstrated that mineral associated C accounted for 40-70 % of bulk soil organic C in A and B1 horizons for granite, nephelinite and arid-zone gabbro soils, and > 80 % in other soils. Organic matter strongly associated with the isolated clay-sized fraction represented only 9-47 % of the bulk soil C. The mean TT of C strongly associated with the clay-sized fraction increased with the amount of smectite (2 : 1 clays); in samples with > 40 % smectite it averaged 1020 ± 460 years. The C not strongly associated with clay-sized minerals, including a combination of low-density C, the C associated with minerals of sizes between 2 µm and 2 cm (including Fe oxyhydroxides as coatings), and C removed from clay-sized material by 2 % hydrogen peroxide had TTs averaging 190 ± 190 years in surface horizons. Summed over the bulk soil profile, we found that smectite content correlated with the mean TT of bulk soil C across varied lithologies. The SRO mineral content in KNP soils was generally very low, except for the soils developed on gabbros under more humid climate that also had very high Fe and C contents with a surprisingly short, mean C TTs. In younger landscapes, SRO minerals are metastable and sequester C for long timescales. We hypothesize that in the KNP, SRO minerals represent a transient stage of mineral evolution and therefore lock up C for a shorter time. Overall, we found crystalline Fe-oxyhydroxides (determined as the difference between Fe in dithionate citrate and oxalate extractions) to be the strongest predictor for soil C content, while the mean TT of soil C was best predicted from the amount of smectite, which was also related to more easily measured bulk properties such as cation exchange capacity or pH. Combined with previous research on C turnover times in 2 : 1 vs. 1 : 1 clays, our results hold promise for predicting C inventory and persistence based on intrinsic timescales of specific carbon-mineral interactions.

USING MOLECULAR PROBES TO STUDY INTERFACIAL REDOX REACTION AT FE-BEARING SMECTITES

EPA Science Inventory

The interfacial electron transfer of clay-water systems has a wide range of significance in geochemical and biogeochernical environments. However the mechanism of interfacial electron transport is poorly understood. The electron transfer mechanism at the solid-water interfaces of...

40 CFR 265.314 - Special requirements for bulk and containerized liquids.

Code of Federal Regulations, 2011 CFR

2011-07-01

... carbon (e.g., aluminosilicates, clays, smectites, Fuller's earth, bentonite, calcium bentonite... charcoal/activated carbon); or (ii) High molecular weight synthetic polymers (e.g., polyethylene, high..., polyisobutylene, ground synthetic rubber, cross-linked allylstyrene and tertiary butyl copolymers). This does not...

Nickel and cobalt distribution in the laterites of the Lomié region, south-east Cameroon

NASA Astrophysics Data System (ADS)

Yongue-Fouateu, R.; Ghogomu, R. T.; Penaye, J.; Ekodeck, G. E.; Stendal, H.; Colin, F.

2006-05-01

In the Lomié region (south-east Cameroon), strong weathering of serpentinized ultramafic rocks has produced a thick laterite cover with significant nickel and cobalt contents. The highest concentrations of these elements are located in the middle section of the laterite profiles, in the lower clay horizon, and preferentially along the slopes of the interfluves. The investigation of the composition of the laterite ores (by whole-rock analysis) and of the main components, using SEM/microprobe and XRD, reveals the presence of four main enriched facies: a non-differentiated facies, a layered smectitic facies, a quartz-rich facies and a gibbsitic nodular facies. Nickel, with generally low concentrations (less than 2% NiO), is hosted by several secondary mineral phases (goethite, Mn-oxyhydroxides and smectite locally). Cobalt is generally of higher grade (up to 0.9% CoO), and is associated with cryptocrystalline and crystallized Mn-oxyhydroxides. SEM/microprobe observations suggest that nickel and cobalt concentration in secondary minerals is due to repeated remobilization. This has also favored the formation of mineral phases, of which the best crystallized and most richly mineralized are mainly those of the asbolan-lithiophorite group. The SEM studies indicate that these mineral phases show various morphologies related to their chemical composition: poorly crystallized nipple shaped (Fe, Mn, Ni), fine cross-bedded needles (Mn, Ni) and elongated crystals (Mn, Al, Ni, Co) occur in the layered smectitic facies, while platy and needle-like forms (Mn, Al, Ni, Co) characterize the gibbsitic nodular facies. The predominantly cobaltiferous nature of the Lomié laterite ore deposit is the result of remobilizations and transformations of elements that led to the impoverishment of both the Ni-Co contents of the laterite but most importantly of Ni rather than Co.

Effects of smectite to illite transformation on the frictional strength and sliding stability of intact marine mudstones

USGS Publications Warehouse

Saffer, Demian M.; Lockner, David A.; McKiernan, Alex

2012-01-01

At subduction zones, earthquake nucleation and coseismic slip occur only within a limited depth range, known as the “seismogenic zone”. One leading hypothesis for the upper aseismic-seismic transition is that transformation of smectite to illite at ∼100–150°C triggers a change from rate-strengthening frictional behavior that allows only stable sliding, to rate weakening behavior considered a prerequisite for unstable slip. Previous studies on powdered gouges have shown that changes in clay mineralogy alone are unlikely to control this transition, but associated fabric and cementation developed during diagenesis remain possible candidates. We conducted shearing experiments designed specifically to evaluate this hypothesis, by using intact wafers of mudstone from Ocean Drilling Program Site 1174, offshore SW Japan, which have undergone progressive smectite transformation in situ. We sheared specimens along a sawcut in a triaxial configuration, oriented parallel to bedding, at normal stresses of ∼20–150 MPa and a pore pressure of 1 MPa. During shearing, we conducted velocity-stepping tests to measure the friction rate parameter (a-b). Friction coefficient ranges from 0.28–0.40 and values of (a-b) are uniformly positive; both are independent of clay transformation progress. Our work represents the most direct and comprehensive test of the clay transformation hypothesis to date, and suggests that neither illitization, nor accompanying fabric development and cementation, trigger a transition to unstable frictional behavior. We suggest that strain localization, in combination with precipitation of calcite and quartz, is a viable alternative that is consistent with both field observations and recent conceptual models of a heterogeneous seismogenic zone.

On sorption and swelling of CO 2 in clays

DOE PAGES

Busch, A.; Bertier, P.; Gensterblum, Y.; ...

2016-03-23

One well-studied technology is the geological storage of carbon dioxide (CO 2), and a number of demonstration projects around the world have proven its feasibility and challenges. Storage conformance and seal integrity are among the most important aspects, as they determine risk of leakage as well as limits for storage capacity and injectivity. By providing evidence for safe storage is critical for improving public acceptance. Most caprocks are composed of clays as dominant mineral type which can typically be illite, kaolinite, chlorite or smectite. A number of recent studies addressed the interaction between CO 2 and these different clays andmore » it was shown that clay minerals adsorb considerable quantities of CO 2. For smectite this uptake can lead to volumetric expansion followed by the generation of swelling pressures. On the one hand CO 2 adsorption traps CO 2, on the other hand swelling pressures can potentially change local stress regimes and in unfavourable situations shear-type failure is assumed to occur. Moreover, for storage in a reservoir having high clay contents the CO 2 uptake can add to storage capacity which is widely underestimated so far. Smectite-rich seals in direct contact with a dry CO 2 plume at the interface to the reservoir might dehydrate leading to dehydration cracks. Such dehydration cracks can provide pathways for CO 2 ingress and further accelerate dewatering and penetration of the seal by supercritical CO 2. At the same time, swelling may also lead to the closure of fractures or the reduction of fracture apertures, thereby improving seal integrity. Finally, the goal of this communication is to theoretically evaluate and discuss these scenarios in greater detail in terms of phenomenological mechanisms, but also in terms of potential risks or benefits for carbon storage.« less

Aflatoxin Toxicity Reduction in Feed by Enhanced Binding to Surface-Modified Clay Additives

PubMed Central

Jaynes, William F.; Zartman, Richard E.

2011-01-01

Animal feeding studies have demonstrated that clay additives, such as bentonites, can bind aflatoxins in ingested feed and reduce or eliminate the toxicity. Bentonite deposits are found throughout the world and mostly consist of expandable smectite minerals, such as montmorillonite. The surfaces of smectite minerals can be treated with organic compounds to create surface-modified clays that more readily bind some contaminants than the untreated clay. Montmorillonites treated with organic cations, such as hexadecyltrimethylammonium (HDTMA) and phenyltrimethylammonium (PTMA), more effectively remove organic contaminants, such as benzene and toluene, from water than untreated clay. Similarly, montmorillonite treated with PTMA (Kd = 24,100) retained more aflatoxin B1 (AfB1) from aqueous corn flour than untreated montmorillonite (Kd = 944). Feed additives that reduced aflatoxin toxicity in animal feeding studies adsorbed more AfB1 from aqueous corn flour than feed additives that were less effective. The organic cations HDTMA and PTMA are considered toxic and would not be suitable for clay additives used in feed or food, but other non-toxic or nutrient compounds can be used to prepare surface-modified clays. Montmorillonite (SWy) treated with choline (Kd = 13,800) and carnitine (Kd = 3960) adsorbed much more AfB1 from aqueous corn flour than the untreated clay (Kd = 944). A choline-treated clay prepared from a reduced-charge, high-charge montmorillonite (Kd = 20,100) adsorbed more AfB1 than the choline-treated high-charge montmorillonite (Kd = 1340) or the untreated montmorillonite (Kd = 293). Surface-modified clay additives prepared using low-charge smectites and nutrient or non-toxic organic compounds might be used to more effectively bind aflatoxins in contaminated feed or food and prevent toxicity. PMID:22069725

Structural stratigraphy of Austin Chalk

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

Corbett, K.P.; Friedman, M.

1983-03-01

The mechanical behavior (structural stratigraphy) of the Upper Cretaceous Austin Chalk is established from the study of fracture intensity along its outcrop trend from Dallas to San Antonio and westward to Langtry, Texas, and in the subsurface from the study of core and/or fracture identification logs from 39 wells. Three mechanical-stratigraphic units are recognized as: (1) an upper, fractured massive chalk corresponding to the Bid House Chalk Member, (2) a middle, ductile chalk-marl corresponding to the Dessau Chalk and Burditt Marl Members, and (3) a lower, fractured massive chalk corresponding to the Atco Chalk Member. Representative samples from these unitsmore » were experimentally shortened dry, at 10, 17 34, and 70-MPa confining pressure, 24/sup 0/C (75/sup 0/F), and at 2.5 x 10/sup -4/ s/sup -1/ to determine if the relative mechanical behavior observed at the surface could be extrapolated into the subsurface at different simulated depths of burial. The experimentally determined ductilities do parallel those determined from outcrop and subsurface studies. Through multiple linear regression analyses of strength versus intrinsic rock properties and environmental parameters, it appears that first porosity and then smectite-content are most strongly correlated with strength. For low-porosity specimens (9 to 13.5%) smectite present in amounts as little as 1% by volume has the highest correlation with strength accounting for 83% of its variability. SEM photomicrographs show that the clays are smeared-out along the induced shear fracture surfaces where they are greatly reduced in grain-size. These observations suggest that the smectite acts mechanically as a soft-inclusion, localizing shear failure and correspondingly weakening the material.« less

The effect of iron on montmorillonite stability. (I) Background and thermodynamic considerations

NASA Astrophysics Data System (ADS)

Wilson, James; Savage, David; Cuadros, Javier; Shibata, Masahiro; Ragnarsdottir, K. Vala

2006-01-01

It is envisaged that high-level nuclear waste (HLW) will be disposed of in underground repositories. Many proposed repository designs include steel waste canisters and bentonite backfill. Natural analogues and experimental data indicate that the montmorillonite component of the backfill could react with steel corrosion products to produce non-swelling Fe-rich phyllosilicates such as chamosite, berthierine, or Fe-rich smectite. In K-bearing systems, the alteration of montmorillonite to illite/glauconite could also be envisaged. If montmorillonite were altered to non-swelling minerals, the swelling capacity and self-healing properties of the bentonite backfill could be reduced, thereby diminishing backfill performance. The main aim of this paper was to investigate Fe-rich phyllosilicate mineral stability at the canister-backfill interface using thermodynamic modelling. Estimates of thermodynamic properties were made for Fe-rich clay minerals in order to construct approximate phase-relations for end-member/simplified mineral compositions in logarithmic activity space. Logarithmic activity diagrams (for the system Al 2O 3-FeO-Fe 2O 3-MgO-Na 2O-SiO 2-H 2O) suggest that if pore waters are supersaturated with respect to magnetite in HLW repositories, Fe(II)-rich saponite is the most likely montmorillonite alteration product (if f values are significantly lower than magnetite-hematite equilibrium). Therefore, the alteration of montmorillonite may not be detrimental to nuclear waste repositories that include Fe, as long as the swelling behaviour of the Fe-rich smectite produced is maintained. If f exceeds magnetite-hematite equilibrium, and solutions are saturated with respect to magnetite in HLW repositories, berthierine is likely to be more stable than smectite minerals. The alteration of montmorillonite to berthierine could be detrimental to the performance of HLW repositories.

Microtubules in basalt glass from Hawaii Scientific Driling Project #2 phase 1 core and Hilina slope, Hawaii: evidence of the occurrence and behavior of endolithic microorganisms.

PubMed

Walton, A W

2008-08-01

Elongate, fine tubes, approximately 1 microm wide and up to 200 microm long, extend from fractured surfaces, vesicle walls, and internal fractures into fragments of basalt glass in samples from the Hawaii Scientific Drilling Project #2 phase 1 (HSDP #2(1)) core and the Hilina slope, Hawaii. Several features indicate that these tubes are microbial endolithic microborings: the tubes resemble many described microborings from oceanic basalt glass, their formation is postdepositional but restricted to certain but different ranges of time in the two sets of samples, and they are not uniformly distributed throughout glass fragments. Microtubules record several characteristic behaviors including boring into glass, mining, seeking olivine, and avoiding plagioclase. They also are highly associated with a particular form of glass-replacing smectite. Evidence of behavior should join morphological and geochemical criteria in indicating microbial alteration of basalt glass. In some samples, steeply conical tubes, approximately 10-20 microm in diameter tapering to 1 microm and commonly filled with smectite, appear to be modifications or elaborations of the microtubules. These also curve toward olivine and are associated with replacement smectite. In HSDP #2(1) samples, microtubules initiated at margins of shards before palagonite replaced those margins and are preserved during palagonitization. In fact, microtubules appear to have provided routes that enhanced the efficiency of water's reaching of unaltered glass. In Hilina Slope samples, the microtubules appear to postdate palagonitization because they initiate at the boundary between palagonite and unaltered sideromelane. Preservation of microtubules during palagonitization in samples together with recognition of other associated characteristics representing behavior suggests that such features may be recognizable in more heavily altered ancient rocks.

XRD measurement of mean thickness, thickness distribution and strain for illite and illite-smectite crystallites by the Bertaut-Warren-Averbach technique

USGS Publications Warehouse

Drits, Victor A.; Eberl, Dennis D.; Środoń, Jan

1998-01-01

A modified version of the Bertaut-Warren-Averbach (BWA) technique (Bertaut 1949, 1950; Warren and Averbach 1950) has been developed to measure coherent scattering domain (CSD) sizes and strains in minerals by analysis of X-ray diffraction (XRD) data. This method is used to measure CSD thickness distributions for calculated and experimental XRD patterns of illites and illite-smectites (I-S). The method almost exactly recovers CSD thickness distributions for calculated illite XRD patterns. Natural I-S samples contain swelling layers that lead to nonperiodic structures in the c* direction and to XRD peaks that are broadened and made asymmetric by mixed layering. Therefore, these peaks cannot be analyzed by the BWA method. These difficulties are overcome by K-saturation and heating prior to X-ray analysis in order to form 10-Å periodic structures. BWA analysis yields the thickness distribution of mixed-layer crystals (coherently diffracting stacks of fundamental illite particles). For most I-S samples, CSD thickness distributions can be approximated by lognormal functions. Mixed-layer crystal mean thickness and expandability then can be used to calculate fundamental illite particle mean thickness. Analyses of the dehydrated, K-saturated samples indicate that basal XRD reflections are broadened by symmetrical strain that may be related to local variations in smectite interlayers caused by dehydration, and that the standard deviation of the strain increases regularly with expandability. The 001 and 002 reflections are affected only slightly by this strain and therefore are suited for CSD thickness analysis. Mean mixed-layer crystal thicknesses for dehydrated I-S measured by the BWA method are very close to those measured by an integral peak width method.

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.

Link between Indian monsoon rainfall and physical erosion in the Himalayan system during the Holocene

NASA Astrophysics Data System (ADS)

Joussain, Ronan; Liu, Zhifei; Colin, Christophe; Duchamp-Alphonse, Stéphanie; Yu, Zhaojie; Moréno, Eva; Fournier, Léa.; Zaragosi, Sébastien; Dapoigny, Arnaud; Meynadier, Laure; Bassinot, Franck

2017-09-01

Mineralogical and geochemical analyses conducted on cores located on the active channel-levee system of the northern Bengal Fan are used to establish changes in the weathering pattern and the sediment transport of the Himalayan system, and evaluate the effect of Indian summer monsoon rainfall during the Holocene. Our data indicate that during the Holocene, sediments from the northern Bengal Fan originate mainly from the G-B river system without any significant changes in the relative contribution of these rivers. From 9.8 to around 6 ka, relatively low smectite/(illite+chlorite) ratios and relatively high K/Si* ratios indicate high physical denudation rates of the Himalayan highlands together with a rapid transfer of the detrital material to the Bengal Fan. The period between 9.2 and 7 ka is associated to lower values of K/Si* and corresponds to the maximum of Indian monsoon rainfall which indicates a more important chemical weathering material that rapidly transits by the G-B river system without a long storage in the Indo-Gangetic plain. From 6.0 ka to present day, higher smectite/(illite+chlorite) ratio and lower K/Si* ratio document a gradual increase of sediments originated from the Indo-Gangetic plain, characterized by higher degree of chemical weathering. During the last 2.5 ka, the drastic increase in the smectite/(illite+chlorite) ratio could be associated to enhanced alteration of the plain soils due to anthropogenic activity. The comparison of mineralogical and geochemical data with previous reconstructions of the Indian monsoon dynamic indicates a rapid response of erosion and sediment transfer of the G-B river system to changes of monsoon rainfall intensity.

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.

Aflatoxin toxicity reduction in feed by enhanced binding to surface-modified clay additives.

PubMed

Jaynes, William F; Zartman, Richard E

2011-06-01

Animal feeding studies have demonstrated that clay additives, such as bentonites, can bind aflatoxins in ingested feed and reduce or eliminate the toxicity. Bentonite deposits are found throughout the world and mostly consist of expandable smectite minerals, such as montmorillonite. The surfaces of smectite minerals can be treated with organic compounds to create surface-modified clays that more readily bind some contaminants than the untreated clay. Montmorillonites treated with organic cations, such as hexadecyltrimethylammonium (HDTMA) and phenyltrimethylammonium (PTMA), more effectively remove organic contaminants, such as benzene and toluene, from water than untreated clay. Similarly, montmorillonite treated with PTMA (K(d) = 24,100) retained more aflatoxin B1 (AfB1) from aqueous corn flour than untreated montmorillonite (K(d) = 944). Feed additives that reduced aflatoxin toxicity in animal feeding studies adsorbed more AfB1 from aqueous corn flour than feed additives that were less effective. The organic cations HDTMA and PTMA are considered toxic and would not be suitable for clay additives used in feed or food, but other non-toxic or nutrient compounds can be used to prepare surface-modified clays. Montmorillonite (SWy) treated with choline (K(d) = 13,800) and carnitine (K(d) = 3960) adsorbed much more AfB1 from aqueous corn flour than the untreated clay (K(d) = 944). A choline-treated clay prepared from a reduced-charge, high-charge montmorillonite (K(d) = 20,100) adsorbed more AfB1 than the choline-treated high-charge montmorillonite (K(d) = 1340) or the untreated montmorillonite (K(d) = 293). Surface-modified clay additives prepared using low-charge smectites and nutrient or non-toxic organic compounds might be used to more effectively bind aflatoxins in contaminated feed or food and prevent toxicity.

Gentamicin-intercalated smectite as a new therapeutic option for Helicobacter pylori eradication.

PubMed

Jeong, Su Jin; Kim, Jie-Hyun; Jung, Da Hyun; Lee, Kyoung Hwa; Park, Soon Young; Song, Yungoo; Kang, Il-Mo; Song, Young Goo

2018-02-12

Novel antibacterial strategies against Helicobacter pylori are needed because H. pylori strains are acquiring resistance to antibiotics. We evaluated the efficacy of gentamicin-intercalated smectite hybrid (S-GEN)-based treatment regimens in a murine model of H. pylori infection. Two groups of 10 rats were administered either smectite or S-GEN to measure coverage of the gastric mucosa. To evaluate anti-H. pylori efficacy, mice were divided into eight groups of 10 mice each given different treatments, and H. pylori eradication was assessed by a Campylobacter-like organism (CLO) test and H. pylori PCR of the gastric mucosa, and H. pylori antigen and H. pylori PCR analysis of mouse faeces. The levels of proinflammatory cytokines were examined. S-GEN was retained in the gastric mucosal layer with a >60% distribution ratio for up to 1 h, and the S-GEN-based triple regimen decreased bacterial burden in vivo compared with that of untreated mice or mice treated with other regimens. The cure rates in the CLO test and H. pylori PCR from gastric mucosa were 70%, 60%, 80%, 50%, 60% and 60% in Groups III-VIII, respectively. Those for H. pylori PCR in the faeces of mice were 90% and 100% in Group III with standard therapy and Group V with triple therapy including S-GEN, respectively. S-GEN triple therapy also reduced the levels of proinflammatory cytokines. These results suggest that S-GEN is a promising and effective therapeutic agent for the treatment of H. pylori infection. © The Author(s) 2018. Published by Oxford University Press on behalf of the British Society for Antimicrobial Chemotherapy. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Environmental effect and genetic influence: a regional cancer predisposition survey in the Zonguldak region of Northwest Turkey

NASA Astrophysics Data System (ADS)

Kadir, Selahattin; Önen-Hall, A. Piril; Aydin, S. Nihal; Yakicier, Cengiz; Akarsu, Nurten; Tuncer, Murat

2008-03-01

The Cretaceous-Eocene volcano-sedimentary units of the Zonguldak region of the western Black Sea consist of subalkaline andesite and tuff, and sandstone dominated by smectite, kaolinite, accessory chlorite, illite, mordenite, and analcime associated with feldspar, quartz, opal-CT, amphibole, and calcite. Kaolinization, chloritization, sericitization, albitization, Fe-Ti-oxidation, and the presence of zeolite, epidote, and illite in andesitic rocks and tuffaceous materials developed as a result of the degradation of a glass shards matrix, enclosed feldspar, and clinopyroxene-type phenocrysts, due to alteration processes. The association of feldspar and glass with smectite and kaolinite, and the suborientation of feldspar-edged, subparallel kaolinite plates to fracture axes may exhibit an authigenic smectite or kaolinite. Increased alteration degree upward in which Al, Fe, and Ti are gained, and Si, Na, K, and Ca are depleted, is due to the alteration following possible diagenesis and hydrothermal activities. Micromorphologically, fibrous mordenite in the altered units and the presence of needle-type chrysotile in the residential buildings in which cancer cases lived were detected. In addition, the segregation pattern of cancer susceptibility in the region strongly suggested an environmental effect and a genetic influence on the increased cancer incidence in the region. The most likely diagnosis was Li-Fraumeni syndrome, which is one of the hereditary cancer predisposition syndromes; however, no mutations were observed in the p53 gene, which is the major cause of Li-Fraumeni syndrome. The micromorphology observed in the altered units in which cancer cases were detected may have a role in the expression of an unidentified gene, but does not explain alone the occurrence of cancer as a primary cause in the region.

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.

Interactions of 14C-labeled multi-walled carbon nanotubes with soil minerals in water.

PubMed

Zhang, Liwen; Petersen, Elijah J; Zhang, Wen; Chen, Yongsheng; Cabrera, Miguel; Huang, Qingguo

2012-07-01

Carbon nanotubes are often modified to be stable in the aqueous phase by adding extensive hydrophilic surface functional groups. The stability of such CNTs in water with soil or sediment is one critical factor controlling their environmental fate. We conducted a series of experiments to quantitatively assess the association between water dispersed multi-walled carbon nanotubes (MWCNTs) and three soil minerals (kaolinite, smectite, or shale) in aqueous solution under different sodium concentrations. (14)C-labeling was used in these experiments to unambiguously quantify MWCNTs. The results showed that increasing ionic strength strongly promoted the removal of MWCNTs from aqueous phase. The removal tendency is inversely correlated with the soil minerals' surface potential and directly correlated with their hydrophobicity. This removal can be interpreted by the extended Derjaguin-Landau-Verwey-Overbeek (EDLVO) theory especially for kaolinite and smectite. Shale, which contains large and insoluble organic materials, sorbed MWCNTs the most strongly. Copyright © 2012 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

Dekayir, Abdelilah; Danot, Michel; Allali, Nabil

2002-09-01

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

Initial Estimates of Optical Constants of Mars Candidate Materials

NASA Technical Reports Server (NTRS)

Rousch, Ted L.; Brown, Adrian Jon; Bishop, Janice L.; Blake, David F.; Bristow, Thomas F.

2013-01-01

Data obtained at visible and near-infrared wavelengths by OMEGA on Mars Express and CRISM on MRO provide definitive evidence for the presence of phyllosilicates and other hydrated phases on Mars. A diverse range of both Fe/Mg-OH and Al- OH-bearing phyllosilicates were identified including the smectites, nontronite, saponite, and montmorillonite. To constrain the abundances of these phyllosilicates, spectral analyses of mixtures are needed. We report on our effort to enable the quantitative evaluation of the abundance of hydrated-hydroxylated silicates when they are contained in mixtures. We include two component mixtures of hydrated/ hydroxylated silicates with each other and with two analogs for other Martian materials; pyroxene (enstatite) and palagonitic soil (an alteration product of basaltic glass, hereafter referred to as palagonite). For the hydrated-hydroxylated silicates we include saponite and montmorillonite (Mg- and Al-rich smectites). We prepared three size separates of each end-member for study: 20-45, 63-90, and 125-150 micron.

Optical Constants of Mars Candidate Materials used to Model Laboratory Reflectance Spectra of Mixtures

NASA Technical Reports Server (NTRS)

Roush, Ted L.; Brown, Adrian Jon; Blake, D.; Bristow, T.

2014-01-01

Data obtained at visible and nearinfrared wavelengths by OMEGA on MarsExpress and CRISM on MRO provide definitive evidence for the presence of phyllosilicates and other hydrated phases on Mars. A diverse range of both Fe/Mg-OH and Al- OH-bearing phyllosilicates were identified including the smectites nontronite, saponite, and montmorillonite. To constrain the abundances of these phyllosilicates, spectral analyses of mixtures are needed. We report on our effort to enable the quantitative evaluation of the abundance of hydrated-hydroxylated silicates when they are contained in mixtures. Here we focus on two component mixtures of the hydrated/ hydroxylated silicates, saponite and montmorillonite (Mg- and Al-rich smectites) with each other and with two analogs for other Martian materials; pyroxene (enstatite) and palagonitic soil (an alteration product of basaltic glass, hereafter referred to as palagonite). We prepared three size separates of each end-member for study: 20-45, 63-90, and 125-150 micron. Here we focus upon mixtures of the 63-90 m size fractions.

Geochemistry of impact glasses from the K/T boundary in Haiti - Relation to smectites and a new type of glass

NASA Technical Reports Server (NTRS)

Koeberl, Christian; Sigurdsson, Haraldur

1992-01-01

Detailed element analyses were carried out on 12 black and seven yellow glasses from the K/T boundary section at Beloc (Haiti), and of three samples from smectite mantles around black glasses. The results obtained for bulk black and yellow glasses show differences between these, confirming the results of Sigurdsson et al. (1991) and Izett (1991), and the results obtained on individual spherules and shards are in agreement with bulk data. The present data also demonstrate, for the first time, the existence of yellow glass samples with high CaO but low S contents, which might have formed by fusion of various proportions of carbonates and evaporites or carbonates alone. One of the black glasses was found to have higher than average SiO2 and K2O abundances but lower concentrations of all other major elements. This suggests the existence of a third glass type, named the high Si-K variety (HSi,K) glass.

Quantum-chemical modeling of smectite clays

NASA Technical Reports Server (NTRS)

Aronowitz, S.; Coyne, L.; Lawless, J.; Rishpon, J.

1982-01-01

A self-consistent charge extended Hueckel program is used in modeling isomorphic substitution of Al(3+) by Na(+), K(+), Mg(2+), Fe(2+), and Fe(3+) in the octahedral layer of a dioctahedral smectite clay, such as montmorillonite. Upon comparison of the energies involved in the isomorphic substitution, it is found that the order for successful substitution is as follows: Al(3+), Fe(3+), Mg(2+), Fe(2+), Na(+), which is equivalent to Ca(2+), and then K(+). This ordering is found to be consistent with experimental observation. The calculations also make it possible to determine the possible penetration of metal ions into the clay's 2:1 crystalline layer. For the cases studied, this type of penetration can occur at elevated temperatures into regions where isomorphic substitution has occurred with metal ions that bear a formal charge of less than 3+. The computed behavior of the electronic structure in the presence of isomorphic substitution is found to be similar to behavior associated with semiconductors.

Clay mineral diversity and abundance in sedimentary rocks of Gale crater, Mars

PubMed Central

Chipera, Steve J.; Hazen, Robert M.; Horgan, Briony; Hogancamp, Joanna V.; Mangold, Nicolas; Morookian, John Michael; Morris, Richard V.; Vaniman, David T.; Yen, Albert S.

2018-01-01

Clay minerals provide indicators of the evolution of aqueous conditions and possible habitats for life on ancient Mars. Analyses by the Mars Science Laboratory rover Curiosity show that ~3.5–billion year (Ga) fluvio-lacustrine mudstones in Gale crater contain up to ~28 weight % (wt %) clay minerals. We demonstrate that the species of clay minerals deduced from x-ray diffraction and evolved gas analysis show a strong paleoenvironmental dependency. While perennial lake mudstones are characterized by Fe-saponite, we find that stratigraphic intervals associated with episodic lake drying contain Al-rich, Fe3+-bearing dioctahedral smectite, with minor (3 wt %) quantities of ferripyrophyllite, interpreted as wind-blown detritus, found in candidate aeolian deposits. Our results suggest that dioctahedral smectite formed via near-surface chemical weathering driven by fluctuations in lake level and atmospheric infiltration, a process leading to the redistribution of nutrients and potentially influencing the cycling of gases that help regulate climate. PMID:29881776

THE EFFECT OF SALINITY ON THE PHOTOLYSIS OF CHRYSENE ADSORBED TO A SMECTITE CLAY. (R827397)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Polymer nanocomposites for lithium battery applications

DOEpatents

Sandi-Tapia, Giselle; Gregar, Kathleen Carrado

2006-07-18

A single ion-conducting nanocomposite of a substantially amorphous polyethylene ether and a negatively charged synthetic smectite clay useful as an electrolyte. Excess SiO₂ improves conductivity and when combined with synthetic hectorite forms superior membranes for batteries. A method of making membranes is also disclosed.

Effect of Phosphate on U(VI) Sorption to Montmorillonite: Ternary Complexation and Precipitation Barriers

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

Troyer, Lyndsay D.; Maillot, Fabien; Wang, Zheming

Phosphate addition is a potential treatment method to lower the solubility of U(VI) in soil and groundwater systems by causing U(VI) phosphate precipitation as well as enhancing adsorption. Previous work has shown that iron oxide surfaces may facilitate the nucleation of U(VI) phosphate minerals and, that under weakly acidic conditions, phosphate also enhances U(VI) adsorption to such phases. Like iron oxides, clays are important reactive phases in the subsurface but little is known about the interaction of U(VI) and phosphate with these minerals. The effect of aqueous phosphate on U(VI) binding to Wyoming montmorillonite (SWy-2) in air-equilibrated systems was investigated.more » Equilibrium U(VI) uptake to montmorillonite was determined at pH 4, 6 and 8 at discrete initial phosphate concentrations between 0 and 100 μM. The observed behavior of U(VI) indicates a transition from adsorption to precipitation with increasing total uranium and phosphate concentrations at all pH values. At the highest phosphate concentration examined at each pH value, a barrier to U(VI) phosphate nucleation is observed. At lower concentrations, phosphate has no effect on macroscopic U(VI) adsorption. To assess the mechanisms of U(VI)-phosphate interactions on smectite surfaces, U(VI) speciation was investigated under selected conditions using laser-induced fluorescence spectroscopy (LIFS) and extended X-ray absorption fine-structure (EXAFS) spectroscopy. Samples above the precipitation threshold display EXAFS and LIFS spectral signatures consistent with the autunite family of U(VI) phosphate minerals. However, at lower U(VI) concentrations, changes in LIFS spectra upon phosphate addition suggest that U(VI)-phosphate ternary surface complexes form on the montmorillonite surface at pH 4 and 6 despite the lack of a macroscopic effect on adsorption. The speciation of solid-associated U(VI) below the precipitation threshold at pH 8 is dominated by U(VI)-carbonate surface complexes. This work reveals that ternary complexation may occur without a macroscopic signature, which is attributed to phosphate not appreciably binding to smectite in the absence of U(VI), with U(VI) surface complexes serving as the sole reactive surface sites for phosphate. This study shows that phosphate does not enhance U(VI) adsorption to smectite clay minerals, unlike oxide phases, and that a barrier to homogeneous nucleation of U(VI) phosphates was not affected by the presence of the smectite surface« less

Griffith Saponite as an Analog for Clay Minerals at Yellowknife Bay in Gale Crater, Mars: A Marker for Low-temperature Hydrothermal Processes

NASA Technical Reports Server (NTRS)

Morris, R.V.; Treiman, A. H.; Agresti, D. G.; Graff, T. G.; Achilles, C. N.; Rampe, E. B.; Bristow, T. F.; Ming, D. W.; Blake, D. F.; Vaniman, D. T.;

Biological Control on Mineral Transformation in Soils ?

NASA Astrophysics Data System (ADS)

Ziegler, K.; Hsieh, J. C.; Chadwick, O. A.; Kelly, E. F.

2001-12-01

Weathering of primary minerals is commonly linked to biological processes through the production of carbonic and organic acids. Plants can also play a role in weathering by removing soluble constituents and enhancing diffusion gradients within the soil. Here we investigate the synthesis of secondary minerals and the role of plants in removing elements that act as building blocks for these minerals. In order to minimize losses from leaching, we have sampled a chronosequence of soils forming on lava flows on Hawaii Island that receive about 200 mm of rain annually and have never been subjected to high levels of rainfall. The P concentration in the soils drops from almost 3000 mg/kg on a 1.5 ky lava flow to around 1000 mg/kg on a 350 ky lava flow. This loss of P can only be ascribed to P-uptake by plants with subsequent removal through the loss of above ground biomass through fire and/or wind removal. Over the same time frame the amount of plagioclase in the soils drops from around 22% of the <2 mm soil fraction on the youngest lava flow to virtually 0% on the 350 ky flow, suggesting a substantial release of Si. Elevated silicon in arid, basaltic soil environments often leads to formation of smectite, a feature not observed along the chronosequence. In fact, plagioclase is replaced by the kaolin mineral halloysite with allophane as an apparent precursor. Kaolin minerals are associated with moderate to intense leaching environments rather than the mild leaching conditions that influence these soils. We selected an intermediate age soil profile (170 ky lava flow) to conduct an in-depth investigation of the soil mineral composition. We detected a strong dominance of halloysite, the presence of gibbsite, but no smectite. Secondary halloysite formation is preferred over smectite formation when Si activities are relatively low, and the pH is acidic rather than alkaline. Although this mineral assemblage seems to imply formation under a wetter climatic regime, the oxygen isotopic composition of the halloysite suggests formation under soil environmental conditions similar to the present. The Si concentration in grass and tree leaves in the vicinity of the soil contain between 3 and 8% Si. Loss of these leaves to the nearby ocean (either as dried or burned residue) could be responsible for considerable Si removal in a manner similar to the P-removal. The resulting Si-deficient soil-water favors the formation of halloysite over smectite as is demonstrated by construction of mineral stability diagrams using the soil-water data from the soils along the chronosequence.

Exfoliation of Layered Magnesium Aluminum Silicate Platelets in Polymer Hosts Enabled by Cation Chemistry and Temperature

DTIC Science & Technology

2010-10-21

Preprints. 14. ABSTRACT Montmorillonite -smectite clay consists of anisotropic clay platelets, generally a nanometer in thickness by hundreds of...Cation Chemistry and Temperature GregO!)’ R. Yandek, Palrick N. RUlh. Joseph M. Mabry Montmorillonite -smedite clay consists 01 anisotropic clay

Timescales of carbon turnover in soils with mixed crystalline mineralogies

USGS Publications Warehouse

Khomo, Lesego; Trumbore, Susan E.; Bern, Carleton R.; Chadwick, Oliver A.

2017-01-01

Organic matter–mineral associations stabilize much of the carbon (C) stored globally in soils. Metastable short-range-order (SRO) minerals such as allophane and ferrihydrite provide one mechanism for long-term stabilization of organic matter in young soil. However, in soils with few SRO minerals and a predominance of crystalline aluminosilicate or Fe (and Al) oxyhydroxide, C turnover should be governed by chemisorption with those minerals. Here, we correlate mineral composition from soils containing small amounts of SRO minerals with mean turnover time (TT) of C estimated from radiocarbon (14C) in bulk soil, free light fraction and mineral-associated organic matter. We varied the mineral amount and composition by sampling ancient soils formed on different lithologies in arid to subhumid climates in Kruger National Park (KNP), South Africa. Mineral contents in bulk soils were assessed using chemical extractions to quantify Fe oxyhydroxides and SRO minerals. Because of our interest in the role of silicate clay mineralogy, particularly smectite (2 : 1) and kaolinite (1 : 1), we separately quantified the mineralogy of the clay-sized fraction using X-ray diffraction (XRD) and measured 14C on the same fraction. Density separation demonstrated that mineral associated C accounted for 40–70 % of bulk soil organic C in A and B1 horizons for granite, nephelinite and arid-zone gabbro soils, and > 80 % in other soils. Organic matter strongly associated with the isolated clay-sized fraction represented only 9–47 % of the bulk soil C. The mean TT of C strongly associated with the clay-sized fraction increased with the amount of smectite (2 : 1 clays); in samples with > 40 % smectite it averaged 1020 ± 460 years. The C not strongly associated with clay-sized minerals, including a combination of low-density C, the C associated with minerals of sizes between 2 µm and 2 cm (including Fe oxyhydroxides as coatings), and C removed from clay-sized material by 2 % hydrogen peroxide had TTs averaging 190 ± 190 years in surface horizons. Summed over the bulk soil profile, we found that smectite content correlated with the mean TT of bulk soil C across varied lithologies. The SRO mineral content in KNP soils was generally very low, except for the soils developed on gabbros under more humid climate that also had very high Fe and C contents with a surprisingly short, mean C TTs. In younger landscapes, SRO minerals are metastable and sequester C for long timescales. We hypothesize that in the KNP, SRO minerals represent a transient stage of mineral evolution and therefore lock up C for a shorter time. Overall, we found crystalline Fe-oxyhydroxides (determined as the difference between Fe in dithionate citrate and oxalate extractions) to be the strongest predictor for soil C content, while the mean TT of soil C was best predicted from the amount of smectite, which was also related to more easily measured bulk properties such as cation exchange capacity or pH. Combined with previous research on C turnover times in 2 : 1 vs. 1 : 1 clays, our results hold promise for predicting C inventory and persistence based on intrinsic timescales of specific carbon–mineral interactions.

Transport of Water, Dissolved Substances, Heat and Electric Current through Shales and Clay-Rich Sediments.

DTIC Science & Technology

1984-03-20

E. Anderson reviewed what was known about the dehydrations of gypsum, smectite, halloysite , vermiculite, and the zeolite minerals. Simple...dehydrations such as those of gypsum and halloysite occur at sharply-defined temperatures and thus contribute a time-limited fluid pulse at a given point. The

Stanford-USGS shrimp-RG ion microprobe: A new approach to determining the distribution of trace elements in coal

USGS Publications Warehouse

Kolker, A.; Wooden, J.L.; Persing, H.M.; Zielinski, R.A.

2000-01-01

The distribution of Cr and other trace metals of environmental interest in a range of widely used U.S. coals was investigated using the Stanford-USGS SHRIMP-RG ion microprobe . Using the oxygen ion source, concentrations of Cr (11 to 176 ppm), V (23 to 248 ppm), Mn (2 to 149 ppm), Ni (2 to 30 ppm), and 13 other elements were determined in illite/smectite, a group of clay minerals commonly present in coal. The results confirm previous indirect or semi-quantitative determinations indicating illite/smectite to be an important host of these metals. Calibration was achieved using doped aluminosilicate-glass synthetic standards and glasses prepared from USGS rock standards. Grains for analysis were identified optically, and confirmed by 1) precursory electron microprobe analysis and wavelength-dispersive compositional mapping, and 2) SHRIMP-RG major element data obtained concurrently with trace element results. Follow-up investigations will focus on the distribution of As and other elements that are more effectively ionized with the cesium primary beam currently being tested.

Effect of soil properties on pure and formulated mesotrione adsorption onto vertisol (Limagne plane, Puy-de-Dôme, France).

PubMed

Alekseeva, Tatiana; Kolyagin, Yury; Sancelme, Martine; Besse-Hoggan, Pascale

2014-09-01

The fate of ionisable pesticides in the environment is complex as it is importantly related to many soil properties: pH, mineralogy, organic matter content and other soil characteristics. The adsorption of a weak acid herbicide, mesotrione, was studied in detail on whole and peroxide-treated vertisol topsoil and also on its granulometric fractions (clay, silt, sand) to evaluate the role of mineralogy and different organic matter pools. The soil studied is alkaline silty loam with smectite as the main clay mineral. It contains 1.7% organic carbon, mostly stabilized as a complex with smectite. Humus is of fulvic type. Mesotrione adsorption occurs on both mineral and organic constituents. Adsorption is weak and mesotrione can be easily and totally desorbed. As shown with (13)C NMR experiments, adsorption best correlates with the alkyl and carboxylic carbon content, and occurs on both bound and free organic matter. No difference of mesotrione sorption was observed with the formulation Callisto®. Copyright © 2014 Elsevier Ltd. All rights reserved.

Observations on Cretaceous abyssal hills in the northeast Pacific

USGS Publications Warehouse

Eittreim, S.L.; Piper, D.Z.; Chezar, H.; Jones, D.R.; Kaneps, A.

1984-01-01

An abyssal hills area of 50 ?? 60 km in the northeast Pacific was studied using bottom transponder navigation, closely spaced survey lines, and long-traverse oblique photography. The block-faulted north-south hills are bounded by scarps, commonly with 40?? slopes. On these steep scarps sedimentation is inhibited and pillow basalts often crop out. An ash layer of high acoustic reflectivity at about 7 m subbottom depth blankets the area. This ash occurs in multiple beds altered to phillipsite and is highly consolidated. A 24 m.y. age for the ash is based on ichthyolith dates from samples in the overlying sediments. Acoustically transparent Neogene sediments above the ash are thickest in trough bottoms and are absent or thin on steep slopes. These Neogene sediments are composed of pale-brown pelagic clays of illite, quartz, smectite, chlorite and kaolinite. Dark-brown pelagic clays, rich in smectite and amorphous iron oxides, underlie the Neogene surficial sediments. Manganese nodules cover the bottom in varying percentages. The nodules are most abundant near basement outcrops and where the subbottom ash layer is absent. ?? 1984.

Efficacy of dioctahedral smectite in acute watery diarrhea in Indian children: a randomized clinical trial.

PubMed

Mujawar, Quais Mohammad; Naganoor, Ravi; Ali, Mir Dilshad; Malagi, Naushad; Thobbi, Achyut Narayan

2012-02-01

To determine the effects and safety of dioctahedral smectite (DS) on the duration of acute watery diarrhea in children. A Randomized, open labeled, clinical controlled trial in a tertiary care hospital outpatient department (OPD) and emergency department. Participants were one hundred and seventeen children without any chronic illness between 2 and 5 years presenting to OPD, having acute watery diarrhea for <48 h with mild to moderate dehydration, not on antibiotics and requiring oral rehydration therapy. Intervention done was DS with a dose of 1.5 g thrice daily. Freshly dissolved DS in a dose of 1.5 g thrice daily for 5 days significantly shortened the duration of acute watery diarrhea in children aged 2-5 years. There were no adverse effects on the use of DS. DS was acceptable to the children, and its administration was not accompanied with any side effects. DS reduces the duration of diarrhea in Indian children and prevents a prolonged course, and therefore, may consistently reduce the costs in treatment of acute watery diarrhea.

Uranium Reduction by Fe(II) in the Presence of Montmorillonite and Nontronite.

PubMed

Tsarev, Sergey; Waite, T David; Collins, Richard N

2016-08-02

Uranium(VI) interactions with three smectites (one montmorillonite and two nontronites - NAu1 and NAu2) were examined with 0, 1, and 2 mM aqueous concentrations of Fe(II) over the pH range of 3-9.5 in a background electrolyte of 100 mM NaCl and 1 mM CaCl2 in equilibration with 400 ppmv CO2(g) ([U(VI)] = 4 μM and 0.5 g smectite/L). In the absence of Fe(II), no differences were observed in the U(VI) sorption curves for the three clay minerals. In the presence of 1 or 2 mM Fe(II), under anoxic conditions, U(VI) uptake by the smectites changed slightly between ∼pH 3 and 6; however, uranium uptake increased significantly above ∼pH 6 and was proportional to the concentration of Fe(II) added to the system, particularly at pH values >8. The uptake of Fe(II) showed a sharp edge starting from ∼pH 6.5 with 95%-100% uptake occurring at pH values >7.5, with no difference observed between the iron-rich nontronites and montmorillonite. After 3 days of reaction at pH 7.6 (i.e., above the Fe(II) "sorption" edge), U(VI) was transformed to a mixture of U(IV) and U(VI) sorption complexes, and after 14 days of reaction, 100% of the U was found to be reduced to U(IV) in the form of nanocrystalline uraninite. In contrast, U remained as sorbed species until 14 days of reaction at pH 6.5. Ferrihydrite (NAu1), lepidocrocite, and magnetite (NAu2) were detected as secondary mineralization products upon reaction of the nontronites with Fe(II) but appeared to have no effect on the partitioning or speciation of uranium.

Alteration of Basalt and Hyaloclastite in the Project Hotspot MHC-2 Core with Some Comparison to Hyaloclastites of the Hawaii Scientific Drilling Program #2 (HSDP) Core

NASA Astrophysics Data System (ADS)

Walton, A. W.; Walker, J. R.

2015-12-01

Project Hotspot's 1821m coring operation at Mountain Home Air Force Base, Idaho (MHC), sought to examine interaction of hotspot magmas with continental crust and evaluate geothermal resources. Subsurface temperature increased at a gradient of 76˚/km. Alteration was uniform and not intense over the upper part of the core and at the bottom, but differed markedly in an anomalous zone (AZ) from 1700 to 1800m. The MHC core contains diatomite, basalt lava and minor hyaloclastite. Olivine (Ol) in lavas is more-or-less altered to iddingsite. Plagioclase (Plag) has altered to smectite along cleavage planes and fractures except in the AZ, where it is intensely altered to corrensite. Clinopyroxene (CPX, pinkish in thin section) is little altered, as are apatite and opaque minerals (probably ilmenite with magnetite or pyrite in different samples). Interstitial material is converted to smectite or, in the AZ, to corrensite. Phyllosilicate lines vesicles, and calcite, zeolite and phyllosilicate fill them. Pore-lining phillipsite is common shallow in the core, with vesicle-filling analcime and heulandite at greater depth. A fibrous zeolite, probably stilbite, is also present. Hyaloclasts are altered to concentrically layered masses of smectite. MHC hyaloclastites do not display the microbial traces and palagonite ("gel-palagonite") alteration common in Hawaii Scientific Drilling Project #2 (HSDP) samples. HSDP samples do contain pore-lining phillipsite, but pore fillings are chabazite. Calcite is absent in HSDP hyaloclastites. Neither Ol nor Plag were altered in HSDP hyaloclastites. HSPD glasses are less silicic and Ti-rich than MHC lavas, containing Ol rather than CPX as a dominant mafic. However the differences in alteration of hyaloclastites probably reflect either the fact that the HSDP core was collected at temperatures equivalent to those at the top of the MHC-2 core or HSDP samples were from beds that were in modified marine pore water, rather than continental waters.

Modelling environmental factors correlated with podoconiosis: a geospatial study of non-filarial elephantiasis.

PubMed

Molla, Yordanos B; Wardrop, Nicola A; Le Blond, Jennifer S; Baxter, Peter; Newport, Melanie J; Atkinson, Peter M; Davey, Gail

2014-06-20

The precise trigger of podoconiosis - endemic non-filarial elephantiasis of the lower legs - is unknown. Epidemiological and ecological studies have linked the disease with barefoot exposure to red clay soils of volcanic origin. Histopathology investigations have demonstrated that silicon, aluminium, magnesium and iron are present in the lower limb lymph node macrophages of both patients and non-patients living barefoot on these clays. We studied the spatial variation (variations across an area) in podoconiosis prevalence and the associated environmental factors with a goal to better understanding the pathogenesis of podoconiosis. Fieldwork was conducted from June 2011 to February 2013 in 12 kebeles (administrative units) in northern Ethiopia. Geo-located prevalence data and soil samples were collected and analysed along with secondary geological, topographic, meteorological and elevation data. Soil data were analysed for chemical composition, mineralogy and particle size, and were interpolated to provide spatially continuous information. Exploratory, spatial, univariate and multivariate regression analyses of podoconiosis prevalence were conducted in relation to primary (soil) and secondary (elevation, precipitation, and geology) covariates. Podoconiosis distribution showed spatial correlation with variation in elevation and precipitation. Exploratory analysis identified that phyllosilicate minerals, particularly clay (smectite and kaolinite) and mica groups, quartz (crystalline silica), iron oxide, and zirconium were associated with podoconiosis prevalence. The final multivariate model showed that the quantities of smectite (RR = 2.76, 95% CI: 1.35, 5.73; p = 0.007), quartz (RR = 1.16, 95% CI: 1.06, 1.26; p = 0.001) and mica (RR = 1.09, 95% CI: 1.05, 1.13; p < 0.001) in the soil had positive associations with podoconiosis prevalence. More quantities of smectite, mica and quartz within the soil were associated with podoconiosis prevalence. Together with previous work indicating that these minerals may influence water absorption, potentiate infection and be toxic to human cells, the present findings suggest that these particles may play a role in the pathogenesis of podoconiosis and acute adenolymphangitis, a common cause of morbidity in podoconiosis patients.

Biogeochemical modification of Nontronite by Shewanella oneidensis MR-1: Evidence of Microbially induced Smectite-to-Illite reaction

NASA Astrophysics Data System (ADS)

Koo, T. H.; Kogure, T.; Kim, J. W.

2017-12-01

The biogeochemical modification of chemistry/structure of smectite associated with microbial Fe(III) respiration is a major process of promoting smectite-to-illite reaction (S-I reaction). Direct evidence of illitization including K-fixation and changes in Al/Si, formation of K-nontronite/illite-like structure has not been suggested systematically. Nontronite (NAu-1) was inoculated with Fe-reducing bacteria (FeRB), Shewanella oneidensis MR-1 at 30 ° with pH buffered (7.0 and 8.0) M1 medium in the anaerobic chamber, and the evidence of illitization was suggested by microscopic/spectroscopic measurements as well as aqueous chemistry in the supernatant with various incubation time. A progressive morphological change in bio-reduced notnronite (altered nontronite → K-nontronite → illite) corresponded to chemical modification in solid phase (Al/Si 0.16 to 0.28). Fe and Al contents in the supernatant increased continuously up to 70 days of incubation (3.4 to 20 and 1.7 to 13 20 mmol/mg of NAu-1, respectively) then decreased in 120 days of incubation (20 to 8 and 13 to 3 mmol/mg of NAu-1, respectively) indicating new mineral phase precipitated. Si contents showed slightly decreased in 7 days (133 to 100 mmol/mg of NAu-1) then showed fluctuated pattern (increased to 183 mmol/mg of NAu-1 in 70 days, then decreased to 102 mmol/mg of NAu-1 in 120 days of incubation). Formation of biotic silica globule within 120-day incubation supported the dissolution of bio-reduced notnronite. Indeed, modification in structure (appearance of 10-Å shoulder in X-ray diffraction profile) and formation of discrete illite-like packet (d001=1.0 nm) in the wavy bio-reduced nontronite matrix (d001=1.2-1.3 nm) strongly suggest that bio-reduced nontronite underwent the reductive dissolution and precipitated the newly formed illite

Ancient Aqueous Conditions on Mars as Inferred from Spirit and Opportunity Rover Data

NASA Astrophysics Data System (ADS)

Arvidson, R. E.

2017-12-01

The Spirit and Opportunity rover missions have added significantly to our understanding of the availability of surface and subsurface waters on Mars over a range of timescales, from the Noachian Period until the present. The most important discoveries from Spirit's traverses and measurements are focused around Home Plate in the Noachian-aged Columbia Hills, Gusev Crater. Home Plate is postulated to be a largely eroded volcanoclastic construct. Spirit's wheels excavated a variety of hydrated sulfate minerals and iron oxides just beneath the surface in the vicinity of Home Plate, likely reworked hydrothermal deposits. Spirit also explored silica-rich deposits found adjacent to Home Plate of likely hydrothermal origin, perhaps deposited as sinters. Opportunity's exploration of the Burns formation sulfate-rich sandstones that underlie Meridiani Planum provided the key observations to infer an origin as sulfate-rich muds accumulating in shallow, ephemeral lakes during the late Noachian to early Hesperian Periods. Fluvial and aeolian activity reworked the muds into sandstones, to be later cemented and altered by rising groundwaters. Opportunity's exploration of the Noachian-aged 22 km diameter Endeavour Crater, combined with mineral mapping using Mars Reconnaissance Orbiter CRISM hyperspectral data, led to the discovery and characterization of ferric smectite-bearing layered outcrops and Al-rich smectites in fractures, both in the Matijevic formation that underlies Endeavour's ejecta (Shoemaker formation). In addition, Opportunity observations led to the discovery and characterization of: (a) extensive Ca sulfate veins in the above mentioned formations and in the overlying Grasberg formation, (b) Shoemaker formation rocks excavated from a soil-filled fracture coated by sulfates and Mn oxides, and (c) extensive Fe-Mg smectites in outcrops and strings of hematite-rich pebbles in sulfate-rich soil-filled fractures in Marathon Valley. Spirit and Opportunity observations thus add to the mounting evidence for significant subsurface aqueous alteration along fractures, in addition to the sustained presence of surface water during the Noachian to early Hesperian Eras.

Geochemistry of K/T-boundary Chicxulub ejecta of NE-Mexico

NASA Astrophysics Data System (ADS)

Harting, M.; Deutsch, A.; Rickers, K.

2003-12-01

Many K/T sections all over the world contain impact spherules supposed related to the Chicxulub event. This study focus on ejecta layers in NE-Mexican profiles. We carried out systematic XRF and synchrotron radiation measurements on such spherules at the HASYLAB and ANKA facilities as well as microprobe analyses (CAMECA SX50). Area scans on tektite-like material of the Bochil section reveal a pronounced zonation in the inner part, dominated by Ba and Sr whereas secondary CaCO3 dominates in the altered margin. The composition of the spherules from the Mesa-Juan Perez section differ significantly from the Beloc (Haiti) and Bochil tektite glasses. At Mesa-Juan Perez, spherules are either extremely rich in Fe and Ca or consist of smectite, some of those carry carbonate inclusions. Yttrium, La and Ce are zoned within the smectite with concentrations below the detection limit and up to 20 æg/g The Ca-rich inclusions are enriched in Y (up to 35 æg/g) and La (18 æg/g) and, compared to the surrounding smectite, also in Ce (up to 34 æg/g). The Ce enrichment in spherules from the Mesa-Juan Perez section indicates impact-melted carbonates of the Yucatan carbonate platform as possible precursor rocks. Recent investigations focus on the chemistry of melt rock samples from the PEMEX wells Yucatan-6 and Chicxulub-1: Their average composition (mean of 250 data points in wt-percent ) is 61.6 for SiO2, 0.16 for TiO2, 18.07 for Al2O3, 0.01 for Cr2O3, 1.98 for Na2O, 1.5 for FeO, 0.05 for MnO, 0.01 for NiO, 0.31 for MgO, 9.14 for K2O, 3.44 for CaO, and 0.01 for SO2. These results are in some cases comparable to the geochemistry of ejecta glasses, e.g. from Beloc (Haiti).

Co-evolution of monsoonal precipitation in East Asia and the tropical Pacific ENSO system since 2.36 Ma: New insights from high-resolution clay mineral records in the West Philippine Sea

NASA Astrophysics Data System (ADS)

Yu, Zhaojie; Wan, Shiming; Colin, Christophe; Yan, Hong; Bonneau, Lucile; Liu, Zhifei; Song, Lina; Sun, Hanjie; Xu, Zhaokai; Jiang, Xuejun; Li, Anchun; Li, Tiegang

2016-07-01

Clay mineralogical analysis and scanning electron microscope (SEM) analysis were performed on deep-sea sediments cored on the Benham Rise (core MD06-3050) in order to reconstruct long-term evolution of East Asian Summer Monsoon (EASM) rainfall in the period since 2.36 Ma. Clay mineralogical variations are due to changes in the ratios of smectite, which derive from weathering of volcanic rocks in Luzon Island during intervals of intensive monsoon rainfall, and illite- and chlorite-rich dusts, which are transported from East Asia by winds associated with the East Asian Winter Monsoon (EAWM). Since Luzon is the main source of smectite to the Benham Rise, long-term consistent variations in the smectite/(illite + chlorite) ratio in core MD06-3050 as well as ODP site 1146 in the Northern South China Sea suggest that minor contributions of eolian dust played a role in the variability of this mineralogical ratio and indicate strengthening EASM precipitation in SE Asia during time intervals from 2360 to 1900 kyr, 1200 to 600 kyr, and after 200 kyr. The EASM rainfall record displays a 30 kyr periodicity suggesting the influence of El Niño-Southern Oscillation (ENSO). These intervals of rainfall intensification on Luzon Island are coeval with a reduction in precipitation over central China and an increase in zonal SST gradient in the equatorial Pacific Ocean, implying a reinforcement of La Niña-like conditions. In contrast, periods of reduced rainfall on Luzon Island are associated with higher precipitation in central China and a weakening zonal SST gradient in the equatorial Pacific Ocean, thereby suggesting the development of dominant El Niño-like conditions. Our study, therefore, highlights for the first time a long-term temporal and spatial co-evolution of monsoonal precipitation in East Asia and of the tropical Pacific ENSO system over the past 2.36 Ma.

Impact-Facilitated Hydrothermal Alteration in the Rim of Endeavour Crater, Mars

NASA Technical Reports Server (NTRS)

Mittlefehldt, D. W.; Schroeder, C.; Farrand, W. H.; Crumpler, L. S.; Yen, A. S.

2017-01-01

Endeavour crater, a Noachian-aged, 22 km diameter impact structure on Meridiani Planum, Mars, has been investigated by the Mars Exploration Rover Opportunuity for over 2000 sols (Mars days). The rocks of the western rim region (oldest to youngest) are: (i) the pre-impact Matijevic fm.; (ii) rim-forming Shoemaker fm. polymict impact breccias; (iii) Grasberg fm., fine-grained sediments draping the lower slopes; and (iv) Burns fm., sulfate-rich sandstones that onlap the Grasberg fm. The rim is segmented and transected by radial fracture zones. Evidence for fluid-mediated alteration includes m-scale detections of phyllosilicates from orbit, and cm-scale variations in rock/soil composition/mineralogy documented by the Opportunity instrument suite. The m-scale phyllosilicate detections include Fe(3+)-Mg and aluminous smectites that occur in patches in the Matijevic and Shoemaker fms. Rock compositions do not reveal substantial differences for smectite-bearing compared to smectite-free rocks. Interpretation: large-scale hydrothermal alteration powered by impact-deposited heat acting on limited water supplies engendered mineralogic transfomations under low water/rock, near-isochemical conditions. The cm-scale alterations, localized in fracture zones, occurred at higher water/rock as evidenced by enhanced Si and Al contents through leaching of more soluble elements, and deposition of Mg, Ni and Mn sulphates and halogen salts in soils. Visible/near infrared reflectance of narrow curvilinear red zones indicate higher nanophase ferric oxide contents and possibly hydration compared to surrounding outcrops. Broad fracture zones on the rim have reflectance features consistent with development of ferric oxide minerals. Interpretation: water fluxing through the fractures in a hydrothermal system resulting from the impact engendered alteration and leaching under high water/rock conditions. Late, localized alteration is documented by Ca-sulfate-rich veins that are not confined to fracture zones; some cross-cut the Grasberg fm. Interpretation: late fluid mobilization of soluble elements, likely in a later alteration event.

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.

Importance of weak minerals on earthquake mechanics

NASA Astrophysics Data System (ADS)

Kaneki, S.; Hirono, T.

2017-12-01

The role of weak minerals such as smectite and talc on earthquake mechanics is one of the important issues, and has been debated for recent several decades. Traditionally weak minerals in fault have been reported to weaken fault strength causing from its low frictional resistance. Furthermore, velocity-strengthening behavior of such weak mineral (talc) is considered to responsible for fault creep (aseismic slip) in the San Andreas fault. In contrast, recent studies reported that large amount of weak smectite in the Japan Trench could facilitate gigantic seismic slip during the 2011 Tohoku-oki earthquake. To investigate the role of weak minerals on rupture propagation process and magnitude of slip, we focus on the frictional properties of carbonaceous materials (CMs), which is the representative weak materials widely distributed in and around the convergent boundaries. Field observation and geochemical analyses revealed that graphitized CMs-layer is distributed along the slip surface of a fossil plate-subduction fault. Laboratory friction experiments demonstrated that pure quartz, bulk mixtures with bituminous coal (1 wt.%), and quartz with layered coal samples exhibited almost similar frictional properties (initial, yield, and dynamic friction). However, mixtures of quartz (99 wt.%) and layered graphite (1 wt.%) showed significantly lower initial and yield friction coefficient (0.31 and 0.50, respectively). Furthermore, the stress ratio S, defined as (yield stress-initial stress)/(initial stress-dynamic stress), increased in layered graphite samples (1.97) compared to quartz samples (0.14). Similar trend was observed in smectite-rich fault gouge. By referring the reported results of dynamic rupture propagation simulation using S ratio of 1.4 (typical value for the Japan Trench) and 2.0 (this study), we confirmed that higher S ratio results in smaller slip distance by approximately 20 %. On the basis of these results, we could conclude that weak minerals have lower initial/yield strength and higher S ratio, and thus restrain magnitude of slip during earthquake.

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.

High-velocity frictional properties of Alpine Fault rocks: Mechanical data, microstructural analysis, and implications for rupture propagation

NASA Astrophysics Data System (ADS)

Boulton, Carolyn; Yao, Lu; Faulkner, Daniel R.; Townend, John; Toy, Virginia G.; Sutherland, Rupert; Ma, Shengli; Shimamoto, Toshihiko

2017-04-01

The Alpine Fault in New Zealand is a major plate-bounding structure that typically slips in ∼M8 earthquakes every c. 330 years. To investigate the near-surface, high-velocity frictional behavior of surface- and borehole-derived Alpine Fault gouges and cataclasites, twenty-one rotary shear experiments were conducted at 1 MPa normal stress and 1 m/s equivalent slip velocity under both room-dry and water-saturated (wet) conditions. In the room-dry experiments, the peak friction coefficient (μp = τp/σn) of Alpine Fault cataclasites and fault gouges was consistently high (mean μp = 0.67 ± 0.07). In the wet experiments, the fault gouge peak friction coefficients were lower (mean μp = 0.20 ± 0.12) than the cataclasite peak friction coefficients (mean μp = 0.64 ± 0.04). All fault rocks exhibited very low steady-state friction coefficients (μss) (room-dry experiments mean μss = 0.16 ± 0.05; wet experiments mean μss = 0.09 ± 0.04). Of all the experiments performed, six experiments conducted on wet smectite-bearing principal slip zone (PSZ) fault gouges yielded the lowest peak friction coefficients (μp = 0.10-0.20), the lowest steady-state friction coefficients (μss = 0.03-0.09), and, commonly, the lowest specific fracture energy values (EG = 0.01-0.69 MJ/m2). Microstructures produced during room-dry and wet experiments on a smectite-bearing PSZ fault gouge were compared with microstructures in the same material recovered from the Deep Fault Drilling Project (DFDP-1) drill cores. The near-absence of localized shear bands with a strong crystallographic preferred orientation in the natural samples most resembles microstructures formed during wet experiments. Mechanical data and microstructural observations suggest that Alpine Fault ruptures propagate preferentially through water-saturated smectite-bearing fault gouges that exhibit low peak and steady-state friction coefficients.

Mild acid and alkali treated clay minerals enhance bioremediation of polycyclic aromatic hydrocarbons in long-term contaminated soil: A 14C-tracer study.

PubMed

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

2017-04-01

Bioremediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soils requires a higher microbial viability and an increased PAH bioavailability. The clay/modified clay-modulated bacterial degradation could deliver a more efficient removal of PAHs in soils depending on the bioavailability of the compounds. In this study, we modified clay minerals (smectite and palygorskite) with mild acid (HCl) and alkali (NaOH) treatments (0.5-3 M), which increased the surface area and pore volume of the products, and removed the impurities without collapsing the crystalline structure of clay minerals. In soil incubation studies, supplements with the clay products increased bacterial growth in the order: 0.5 M HCl ≥ unmodified ≥ 0.5 M NaOH ≥ 3 M NaOH ≥ 3 M HCl for smectite, and 0.5 M HCl ≥ 3 M NaOH ≥ 0.5 M NaOH ≥ 3 M HCl ≥ unmodified for palygorskite. A 14 C-tracing study showed that the mild acid/alkali-treated clay products increased the PAH biodegradation (5-8%) in the order of 0.5 M HCl ≥ unmodified > 3 M NaOH ≥ 0.5 M NaOH for smectite, and 0.5 M HCl > 0.5 M NaOH ≥ unmodified ≥ 3 M NaOH for palygorskite. The biodegradation was correlated (r = 0.81) with the bioavailable fraction of PAHs and microbial growth as affected particularly by the 0.5 M HCl and 0.5 M NaOH-treated clay minerals. These results could be pivotal in developing a clay-modulated bioremediation technology for cleaning up PAH-contaminated soils and sediments in the field. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2014-07-01

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

Mineralogy and fluid content of sediments entering the Costa Rica subduction zone - Results from Site U1414, IODP Expedition 344

NASA Astrophysics Data System (ADS)

Charpentier, D.; Buatier, M.; Kutterolf, S.; Straub, S. M.; Nascimento, D.; Millan, C.

2013-12-01

Subduction zones are characterized by the largest thrust earthquakes, as quantified by both rupture area and seismic moment release. Offshore Costa Rica, the oceanic Cocos Plate subducts under the Caribbean plate forming the southern end of the Middle America trench. A high convergence rate and almost complete subduction of incoming sediments make the Costa Rica convergent margin an extremely dynamic environment. The Costa Rica Seismogenesis Project (CRISP) is designed to understand the processes that control nucleation and seismic rupture of large earthquakes at erosional subduction zones. Site U1414 of IODP Exp.344 was drilled to investigate the material from the incoming Cocos Plate. A key parameter of incoming plate is fluid content and release because it impacts deformation within the subduction complex. The deposition, compaction and diagenesis of sedimentary rocks control the distribution of fluids, fluid pressures and fluid flow patterns within subduction zones. We therefore decided to characterize sediment composition and quantify the different types of water at Site U1414. Mineralogical investigations were performed using optical and electronic microscope observations, X Ray Diffraction (on bulk and clay fractions), Cation Exchange Capacity measurements, carbon analyses (to determine carbonate contents), and sequenced extractions in NaOH (to quantify the biogenic opal content). Fluid characteristics were approached by thermal gravimetric analyses. The entire sedimentary sequence was recovered at Site U1414 and can be divided into three major sedimentary units. The first one is a hemipelagic silty clay to clay with a gradual increase of calcareous nannofossils. The dominant mineral is smectite associated in the clay fractions with kaolinite and zeolites. Small amounts of biogenic opal have been analyzed. Other minerals like quartz, feldspar and calcite are also present. The second unit is composed of nannofossil-rich calcareous ooze. The proportion of biosilica is variable and can attain 15 wt.%. Smectite and zeolites are present in smaller amount. The third unit is a lithified sandstone. Biosilica and smectite are absent, but zeolites are still present in this unit. Fluid content that can be released varies from about 15 wt.% to 40 wt.%. In shallow levels a significant proportion is pore water fluid, whereas in deeper levels water stored within minerals comprises a greater proportion of the total fluid budget. The presence of smectite yields to fluid release by dehydration and dehydroxylation at temperatures less than approximately 100°C and 500°C respectively. Transformation of biogenic opal to diagenetic silice goes to completion at temperatures of 50-100°C. It seems to be an importance source of fluid in the second unit, whereas in unit three it is zeolite water.

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.

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;

A high-temperature hydrothermal deposit on the seabed at a Gulf of California spreading center ( Guaymas Basin).

USGS Publications Warehouse

Lonsdale, P.F.; Bischoff, J.L.; Burns, V.M.; Kastner, M.; Sweeney, R.E.

1980-01-01

A submersible dive on a turbidite-covered spreading axis in Guaymas Basin photographed and sampled extensive terraces and ledges of talc. The rock contains siliceous microfossils, smectite, and euhedral pyrrhotite as well as rather pure iron-rich talc. S and O isotopes indicate precipitation around a hydrothermal vent, at about 2800C. - Authors

Nature of the Interlayer Environment in an Organoclay Optimized for the Sequestration of Dibenzo-p-dioxin

EPA Science Inventory

A Na-smectite clay (Na-SWy-2) was exchanged with various amounts of dimethyldioctadecylammonium bromide (DODA-Br) up to twice the cation exchange capacity (CEC). The organoclay (DODA - SWy-2) with DODA-Br added at 2 X CEC exhibited a maximum 4.2 nm d-spacing and a 31.4% c...

CM-like Interplanetary Dust Particles in Lower Stratosphere During 1989 October and 1991 June/July

NASA Technical Reports Server (NTRS)

Rietmeijer, Frans J. M.

1996-01-01

The stratospheric interplanetary dust particles L2005T12 and L2011O3 are linked to CM chondrite matrix. Particle L2005T12 is dominated by tabular grains of partially dehydrated greenalite-rich serpentine. Its amorphous matrix contains abundant smectite nanocrystals and annular Fe,Ni,S units. A uniquely stratified (partial) maghemite rim occurs only on S-rich parts of the matrix. Formation of this rim and Mg depletions in the matrix occurred during atmospheric entry heating of this particle. Particle L2011O3 has large iron sulfide and magnesiowustite grains in an amorphous low-Al, ferromagnesiosilica matrix. Hydrous crystallisation of this matrix produced ultrafine-grained smectites and disseminated iron sulfides. Atmospheric entry heating of both particles is indicated by the partial iron oxide rim, vesicular sulfides, and the scatter of matrix compositions due to loss of Mg. While many uncertainties remain, the high incidence of chondritic rough particles, which include an unknown amount of CM-like particles, in the lower stratosphere during 1984, 1989, and 1991 suggests annual variations in their abundances. The timing of lower stratospheric dust samplings is critical to collect these particles.

Trace Element Geochemistry of Martian Iddingsite in the Lafayette Meteorite

NASA Technical Reports Server (NTRS)

Treiman, Allan H.; Lindstrom, David J.

1997-01-01

The Lafayette meteorite contains abundant iddingsite, a fine-grained intergrowth of smectite clay, ferrihydrite, and ionic salt minerals. Both the meteorite and iddingsite formed on Mars. Samples of iddingsite, olivine, and augite pyroxene were extracted from Lafayette and analyzed for trace elements by instrumental neutron activation. Our results are comparable to independent analyses by electron and ion microbeam methods. Abundances of most elements in the iddingsite do not covary significantly. The iddingsite is extremely rich in Hg, which is probably terrestrial contamination. For the elements Si, Al, Fe, Mn, Ni, Co, and Zn, the composition of the iddingsite is close to a mixture of approximately 50% Lafayette olivine + approximately 40% Lafayette siliceous glass + approximately 1O% water. Concordant behavior among these elements is not compatible with element fractionations between smectite and water, but the hydrous nature and petrographic setting of the iddingsite clearly suggest an aqueous origin. These inferences are both consistent, however, with deposition of the iddingsite originally as a silicate gel, which then crystallized (neoformed) nearly isochemically. The iddingsite contains significantly more magnesium than implied by the model, which may suggest that the altering solutions were rich in Mg(2+).

Permeability-Porosity Relationships of Subduction Zone Sediments

NASA Astrophysics Data System (ADS)

Gamage, K.; Screaton, E.; Bekins, B.; Aiello, I.

2008-12-01

Permeability-porosity relationships for sediments from Northern Barbados, Costa Rica, Nankai, and Peru subduction zones were examined based on their sediment type and grain size distribution. Greater correlation was observed between permeability and porosity for siliciclastic sediments, diatom oozes, and nannofossil chalk than for nannofossil oozes. For siliciclastic sediments, grouping of sediments by clay content yields relationships that are generally consistent with results from other marine settings and suggest decreasing permeability for a given porosity as clay content increases. Correction of measured porosities for smectite content generally improves the quality of permeability-porosity relationships. The relationship between permeability and porosity for diatom oozes may be controlled by the amount of clay present in the ooze, causing diatom oozes to behave similarly to siliciclastic sediments. For a given porosity the nannofossil oozes have higher permeability values by 1.5 orders of magnitude than the siliciclastic sediments. However, the use of a permeability-porosity relation may not be appropriate for unconsolidated carbonates such as nannofossil oozes. This study provided insight to the effects of porosity correction for smectite, variations in lithology and grain size in permeability-porosity relationships. However, further progress in delineating controls on permeability will require more careful and better documented permeability tests on characterized samples.

Adsorption of a textile dye "Indanthrene Blue RS (C.I. Vat Blue 4)" from aqueous solutions onto smectite-rich clayey rock.

PubMed

Chaari, Islem; Feki, Mongi; Medhioub, Mounir; Bouzid, Jalel; Fakhfakh, Emna; Jamoussi, Fakher

2009-12-30

The adsorption of a textile dye, namely, Indanthrene Blue RS (C.I. Vat Blue 4) onto smectite-rich clayey rock (AYD) and its sulphuric acid-activated products (AYDS) in aqueous solution was studied in a batch system with respect to contact time, pH, and temperature. The adsorbents employed were characterized by X-ray diffraction, infrared spectroscopy and specific surface area, cation exchange capacity and point of zero charge were also estimated. The effect of contact time on dye adsorption showed that the equilibrium was reached after a contact time of 40 min for the both adsorbents. The optimum pH for dye retention was found 6.0 for AYDS and 7.3 for AYD. The equilibrium adsorption data were analysed using the Langmuir and Freundlich isotherms. The adsorption capacities (Q(m)) for AYD and AYDS were found 13.92 mg/g and 17.85 mg/g, respectively. The effect of temperature on the adsorption was also investigated; adsorption of Indanthrene Blue RS is an endothermic process. This study demonstrates that all the considered adsorbents can be used as an alternative emerging technology for water treatment.

Experimental alteration of artificial and natural impact melt rock from the Chesapeake Bay impact structure

USGS Publications Warehouse

Declercq, J.; Dypvik, H.; Aagaard, Per; Jahren, J.; Ferrell, R.E.; Horton, J. Wright

2009-01-01

The alteration or transformation of impact melt rock to clay minerals, particularly smectite, has been recognized in several impact structures (e.g., Ries, Chicxulub, Mj??lnir). We studied the experimental alteration of two natural impact melt rocks from suevite clasts that were recovered from drill cores into the Chesapeake Bay impact structure and two synthetic glasses. These experiments were conducted at hydrothermal temperature (265 ??C) in order to reproduce conditions found in meltbearing deposits in the first thousand years after deposition. The experimental results were compared to geochemical modeling (PHREEQC) of the same alteration and to original mineral assemblages in the natural melt rock samples. In the alteration experiments, clay minerals formed on the surfaces of the melt particles and as fine-grained suspended material. Authigenic expanding clay minerals (saponite and Ca-smectite) and vermiculite/chlorite (clinochlore) were identified in addition to analcime. Ferripyrophyllite was formed in three of four experiments. Comparable minerals were predicted in the PHREEQC modeling. A comparison between the phases formed in our experiments and those in the cores suggests that the natural alteration occurred under hydrothermal conditions similar to those reproduced in the experiment. ?? 2009 The Geological Society of America.

Carbon dioxide intercalation in Na-fluorohectorite clay at near-ambient conditions

NASA Astrophysics Data System (ADS)

Fossum, Jon Otto; Hemmen, Henrik; Rolseth, Erlend G.; Fonseca, Davi; Lindbo Hansen, Elisabeth; Plivelic, Tomas

2012-02-01

A molecular dynamics study by Cygan et al.[1] shows the possibility of intercalation and retention of CO2 in smectite clays at 37 ^oC and 200 bar, which suggests that clay minerals may prove suitable for carbon capture and carbon dioxide sequestration. In this work we show from x-ray diffraction measurements that gaseous CO2 intercalates into the interlayer space of the synthetic smectite clay Na-fluorohectorite. The mean interlayer distance of the clay when CO2 is intercalated is 12.5 å at -20 C and 15 bar. The magnitude of the expansion of the interlayer upon intercalation is indistinguishable from that of the dehydrated-monohydrated intercalation of H2O, but this possibility is ruled out by careful repeating the measurements exposing the clay to nitrogen gas. The dynamics of the CO2 intercalation process displays a higher intercalation rate at increased pressure, and the rate is several orders of magnitude slower than that of water or vapor at ambient pressure and temperature.[4pt] [1] Cygan, R. T.; Romanov, V. N.; Myshakin, E. M. Natural materials for carbon capture; Techincal report SAND2010-7217; Sandia National Laboratories: Albuquerque, New Mexico, November, 2010.

3-D interpretation of short-period magnetotelluric data at Furnas Volcano, Azores Islands

NASA Astrophysics Data System (ADS)

Hogg, C.; Kiyan, D.; Rath, V.; Byrdina, S.; Vandemeulebrouck, J.; Revil, A.; Viveiros, F.; Carmo, R.; Silva, C.; Ferreira, T.

2018-04-01

Accurate geophysical imaging of shallow subsurface features provides crucial constraints on understanding the dynamics of volcanic systems. At Furnas Volcano (Azores), intense circulation of volcanic fluids at depth leading to high CO2 outgassing and flank destabilization poses considerable threat to the local population. Presented is a novel 3-D electrical resistivity model developed from 39 magnetotelluric soundings that images the hydrothermal system of the Furnas Volcano to a depth of 1 km. The resistivity model images two conductive zones, one at 100 m and another at 500 m depth, separated by a resistive layer. The shallow conductor has conductivity less than 1 S m-1, which can be explained by clay mineral surface conduction with a mass fraction of at least 20 per cent smectite. The deeper conductor extends across the majority of the survey area. This deeper conductor is located at depths where smectite is generally replaced by chlorite and we interpret it as aqueous fluids near the boiling point and infer temperatures of at least 240 °C. The less conductive layer found between these conductors is probably steam-dominated, and coincides within the mixed-clay zone found in many volcanic hydrothermal systems.

Characteristics, extent and origin of hydrothermal alteration at Mount Rainier Volcano, Cascades Arc, USA: Implications for debris-flow hazards and mineral deposits

USGS Publications Warehouse

John, D.A.; Sisson, T.W.; Breit, G.N.; Rye, R.O.; Vallance, J.W.

2008-01-01

Hydrothermal alteration at Mount Rainier waxed and waned over the 500,000-year episodic growth of the edifice. Hydrothermal minerals and their stable-isotope compositions in samples collected from outcrop and as clasts from Holocene debris-flow deposits identify three distinct hypogene argillic/advanced argillic hydrothermal environments: magmatic-hydrothermal, steam-heated, and magmatic steam (fumarolic), with minor superimposed supergene alteration. The 3.8??km3 Osceola Mudflow (5600??y BP) and coeval phreatomagmatic F tephra contain the highest temperature and most deeply formed hydrothermal minerals. Relatively deeply formed magmatic-hydrothermal alteration minerals and associations in clasts include quartz (residual silica), quartz-alunite, quartz-topaz, quartz-pyrophyllite, quartz-dickite/kaolinite, and quartz-illite (all with pyrite). Clasts of smectite-pyrite and steam-heated opal-alunite-kaolinite are also common in the Osceola Mudflow. In contrast, the Paradise lahar, formed by collapse of the summit or near-summit of the edifice at about the same time, contains only smectite-pyrite and near-surface steam-heated and fumarolic alteration minerals. Younger debris-flow deposits on the west side of the volcano (Round Pass and distal Electron Mudflows) contain only low-temperature smectite-pyrite assemblages, whereas the proximal Electron Mudflow and a < 100??y BP rock avalanche on Tahoma Glacier also contain magmatic-hydrothermal alteration minerals that are exposed in the avalanche headwall of Sunset Amphitheater, reflecting progressive incision into deeper near-conduit alteration products that formed at higher temperatures. The pre-Osceola Mudflow alteration geometry is inferred to have consisted of a narrow feeder zone of intense magmatic-hydrothermal alteration limited to near the conduit of the volcano, which graded outward to more widely distributed, but weak, smectite-pyrite alteration within 1??km of the edifice axis, developed chiefly in porous breccias. The edifice was capped by a steam-heated alteration zone, most of which resulted from condensation of fumarolic vapor and oxidation of H2S in the unsaturated zone above the water table. Weakly developed smectite-pyrite alteration extended into the west and east flanks of the edifice, spatially associated with dikes that are localized in those sectors; other edifice flanks lack dikes and associated alteration. The Osceola collapse removed most of the altered core and upper east flank of the volcano, but intensely altered rocks remain on the uppermost west flank. Major conclusions of this study are that: (1) Hydrothermal-mineral assemblages and distributions at Mount Rainier can be understood in the framework of hydrothermal processes and environments developed from studies of ore deposits formed in analogous settings. (2) Frequent eruptions supplied sufficient hot magmatic fluid to alter the upper interior of the volcano hydrothermally, despite the consistently deep (??? 8??km) magma reservoir which may have precluded formation of economic mineral deposits within or at shallow depths beneath Mount Rainier. The absence of indicator equilibrium alteration-mineral assemblages in the debris flows that effectively expose the volcano to a depth of 1-1.5??km also suggests a low potential for significant high-sulfidation epithermal or porphyry-type mineral deposits at depth. (3) Despite the long and complex history of the volcano, intensely altered collapse-prone rocks were spatially restricted to near the volcano's conduit system and summit, and short distances onto the upper east and west flanks, due to the necessary supply of reactive components carried by ascending magmatic fluids. (4) Intensely altered rocks were removed from the summit, east flank, and edifice interior by the Osceola collapse, but remain on the upper west flank in the Sunset Amphitheater area and present a continuing collapse hazard. (5) Visually conspicuous rocks on the lower east and mid-to-lower

Frictional processes in smectite-rich gouges sheared at slow to high slip rates

NASA Astrophysics Data System (ADS)

Aretusini, Stefano; Mittempergher, Silvia; Gualtieri, Alessandro; Di Toro, Giulio

2015-04-01

The slipping zones of shallow sections of megathrusts and of large landslides are often smectite-rich (e.g., montmorillonite type). Consequently, similar "frictional" processes operating at high slip rates (> 1 m/s) might be responsible of the large slips estimated in megathrust (50 m for the 2011 Tohoku Mw 9.1 earthquake) and measured in large landslides (500 m for the 1963 Vajont slide, Italy). At present, only rotary shear apparatuses can reproduce simultaneously the large slips and slip rates of these events. Noteworthy, the frictional processes proposed so far (thermal and thermochemical pressurization, etc.) remain rather obscure. Here we present preliminary results obtained with the ROtary Shear Apparatus (ROSA) installed at Padua University. Thirty-one experiments were performed at ambient conditions on pure end-members of (1) smectite-rich standard powders (STx-1b: ~68 wt% Ca-montmorillonite, ~30 wt% opal-CT and ~2 wt% quartz), (2) quartz powders (qtz) and (3) on 80:20 = Stx-1b:qtz mixtures. The gouges were sandwiched between two (1) hollow (25/15 mm external/internal diameter) or (2) solid (25 mm in diameter) stainless-steel made cylinders and confined by inner and outer Teflon rings (only outer for solid cylinders). Gouges were sheared at a normal stress of 5 MPa, slip rates V from 300 μm/s to 1.5 m/s and total slip of 3 m. The deformed gouges were investigated with quantitative (Rietveld method with internal standard) X-ray powder diffraction (XRPD) and Scanning Electron Microscopy (SEM). In the smectite-rich standard endmember, (1) for 300 μm/s ≤ V ≤ 0.1 m/s, initial friction coefficient (μi) was 0.6±0.05 whereas the steady-state friction coefficient (μss) was velocity and slip strengthening (μss 0.85±0.05), (2) for 0.1 m/s < V < 0.3 m/s, velocity and slip neutral (μi = μss = 0.62±0.08) and (3) for V > 0.8 m/s, velocity and slip weakening (μi = 0.7±0.1 and μss = 0.25±0.05). In the 80:20 Stx-1b:qtz mixtures, (1) for 300 μm/s ≤ V ≤ 0.1 m/s, μi ranged was 0.7±0.05 and increased with slip to μss = 0.77±0.02 (slip-strengthening behavior), (2) for V = 0.1 m/s velocity and slip neutral (μi = μss = 0.77±0.02) and (3) for V ≥ 0.3 m/s the friction coefficient was velocity and slip weakening with μss = 0.32±0.02 for V = 1.5 m/s. The Rietveld analysis of the smectite-rich standard endmember showed (1) the insensitivity of the amount of the amorphous fraction with frictional work and (2) the shift and broadening of both the (001) and (110) peaks of Ca-montmorillonite with increasing frictional work (i.e., product of shear stress with slip, here from 5.2 Jm-2 to 11.8 Jm-2). Instead, mineralogical and lattice changes were unrelated to the frictional work rate (i.e., product of shear stress with slip rate). Strain localization in the gouge layer was observed for V ≥ 0.3 m/s (SEM investigations); for V < 0.3 m/s, strain was distributed and the gouge layer pervasively foliated. We conclude that the degree of amorphization of the sheared gouges was not responsible of the measured frictional weakening; instead, weakening was concomitant to strain localization.

Domes, Ash and Dust - Controls on soil genesis in a montane catchment of the Valles Caldera, New Mexico

NASA Astrophysics Data System (ADS)

Rasmussen, C.; Meding, S. M.; Vazquez, A.; Chorover, J.

2011-12-01

Soil genesis in volcanic terrain may be controlled by complex assemblages of parent materials and local topography. The objective of this work was to quantify topographic and parent material controls on soil and catchment evolution in a mixed conifer, montane catchment in the Valles Caldera, New Mexico, as part of the Jemez River Basin Critical Zone Observatory. The field site is a 16 ha catchment at an elevation of 3,000 m, with a frigid soil temperature regime (0-8*C), ustic soil moisture regime with bimodal precipitation of winter snowfall and convective summer rainfall (880 mm/yr), and an overstory dominated by spruce and fir with dense grass cover in open areas. The catchment is located on the resurgent Redondo Dome that uplifted shortly after the last major eruption of the Valles Caldera 1.2 My ago. The dome includes a complex assemblage of pre-eruptive caldera materials and extant sedimentary rocks embedded within a welded, hydrothermally altered rhyolitic tuff. We sampled a transect of seven soil profiles spanning the dominant east-west aspect of the catchment across a catena with profiles located in summit, backslope, footslope, and toeslope positions. Soil morphology was described in the field and soil samples analyzed using a range of geochemical and mineralogical techniques including quantitative and qualitative x-ray diffraction of bulk samples and particle size fractions, elemental analysis by x-ray fluorescence, and laser particle size analysis. The data indicated strong landscape position control on soil drainage, grading from well-drained summits to poorly-drained toeslope positions based on the presence/absence of redoximorphic features. The drainage patterns were coupled with downslope thickening of dark, organic matter rich surface horizons, likely a function of both in situ organic matter production and downslope colluvial transport of carbon rich surface materials. Mineralogical and geochemical data indicated clear within profile lithologic discontinuities in backslope, footslope and toeslope positions that suggest post dome resurgence ash deposition and redistribution via physical erosion. Additionally, the majority of sites contained a modern dust signal in the upper 5 to 10 cm of the soil profile based on Ti:Zr, mica content, and particle size distribution. The dominant weathering patterns include feldspar transformation to kaolinite and alteration of volcanic glass and/or 2:1 primary minerals to smectite. Smectite is a combination of both authigenic smectite formed during hydrothermal alteration of the tuff and neogenic smectite as suggested by Si-rich soil solution and surface waters. The data indicate a sequence of dome uplift followed by periods of pedogenesis and ash input, subsequent ash redistribution via physical erosion, and modern mass input via eolian dust. The timing and magnitude of these events and impacts on chemical weathering are the subjects of ongoing model and measurement activities.

Domes, Ash and Dust - Controls on soil genesis in a montane catchment of the Valles Caldera, New Mexico

NASA Astrophysics Data System (ADS)

Rasmussen, C.; Meding, S. M.; Vazquez, A.; Chorover, J.

2012-12-01

Soil genesis in volcanic terrain may be controlled by complex assemblages of parent materials and local topography. The objective of this work was to quantify topographic and parent material controls on soil and catchment evolution in a mixed conifer, montane catchment in the Valles Caldera, New Mexico, as part of the Jemez River Basin Critical Zone Observatory. The field site is a 16 ha catchment at an elevation of 3,000 m, with a frigid soil temperature regime (0-8 *C), ustic soil moisture regime with bimodal precipitation of winter snowfall and convective summer rainfall (880 mm yr-1), and an overstory dominated by spruce and fir with dense grass cover in open areas. The catchment is located on the resurgent Redondo Dome that uplifted shortly after the last major eruption of the Valles Caldera 1.2 My ago. The dome includes a complex assemblage of pre-eruptive caldera materials and extant sedimentary rocks embedded within a welded, hydrothermally altered rhyolitic tuff. We sampled a transect of seven soil profiles spanning the dominant east-west aspect of the catchment across a catena with profiles located in summit, backslope, footslope, and toeslope positions. Soil morphology was described in the field and soil samples analyzed using a range of geochemical and mineralogical techniques including quantitative and qualitative x-ray diffraction of bulk samples and particle size fractions, elemental analysis by x-ray fluorescence, and laser particle size analysis. The data indicated strong landscape position control on soil drainage, grading from well-drained summits to poorly-drained toeslope positions based on the presence/absence of redoximorphic features. The drainage patterns were coupled with downslope thickening of dark, organic matter rich surface horizons, likely a function of both in situ organic matter production and downslope colluvial transport of carbon rich surface materials. Mineralogical and geochemical data indicated clear within profile lithologic discontinuities in backslope, footslope and toeslope positions that suggest post dome resurgence ash deposition and redistribution via physical erosion. Additionally, the majority of sites contained a modern dust signal in the upper 5 to 10 cm of the soil profile based on Ti:Zr, mica content, and particle size distribution. The dominant weathering patterns include feldspar transformation to kaolinite and alteration of volcanic glass and/or 2:1 primary minerals to smectite. Smectite is a combination of both authigenic smectite formed during hydrothermal alteration of the tuff and neogenic smectite as suggested by Si-rich soil solution and surface waters. The data indicate a sequence of dome uplift followed by periods of pedogenesis and ash input, subsequent ash redistribution via physical erosion, and modern mass input via eolian dust. The timing and magnitude of these events and impacts on chemical weathering are the subjects of ongoing model and measurement activities.

Episodic fluid flow in the Nankai accretionary complex: Timescale, geochemistry, flow rates, and fluid budget

USGS Publications Warehouse

Saffer, D.M.; Bekins, B.A.

1998-01-01

Down-hole geochemical anomalies encountered in active accretionary systems can be used to constrain the timing, rates, and localization of fluid flow. Here we combine a coupled flow and solute transport model with a kinetic model for smectite dehydration to better understand and quantify fluid flow in the Nankai accretionary complex offshore of Japan. Compaction of sediments and clay dehydration provide fluid sources which drive the model flow system. We explicitly include the consolidation rate of underthrust sediments in our calculations to evaluate the impact that variations in this unknown quantity have on pressure and chloride distribution. Sensitivity analysis of steady state pressure solutions constrains bulk and flow conduit permeabilities. Steady state simulations with 30% smectite in the incoming sedimentary sequence result in minimum chloride concentrations at site 808 of 550 mM, but measured chlorinity is as low as 447 mM. We simulate the transient effects of hydrofracture or a strain event by assuming an instantaneous permeability increase of 3-4 orders of magnitude along a flow conduit (in this case the de??collement), using steady state results as initial conditions. Transient results with an increase in de??collement permeability from 10-16 m2 to 10-13 m2 and 20% smectite reproduce the observed chloride profile at site 808 after 80-160 kyr. Modeled chloride concentrations are highly sensitive to the consolidation rate of underthrust sediments, such that rapid compaction of underthrust material leads to increased freshening. Pressures within the de??collement during transient simulations rise rapidly to a significant fraction of lithostatic and remain high for at least 160 kyr, providing a mechanism for maintaining high permeability. Flow rates at the deformation front for transient simulations are in good agreement with direct measurements, but steady state flow rates are 2-3 orders of magnitude smaller than observed. Fluid budget calculations indicate that nearly 71% of the incoming water in the sediments leaves the accretionary wedge via diffuse flow out the seafloor, 0-5% escapes by focused flow along the de??collement, and roughly 1% is subducted. Copyright 1998 by the American Geophysical Union.

Modelling environmental factors correlated with podoconiosis: a geospatial study of non-filarial elephantiasis

PubMed Central

2014-01-01

Introduction The precise trigger of podoconiosis — endemic non-filarial elephantiasis of the lower legs — is unknown. Epidemiological and ecological studies have linked the disease with barefoot exposure to red clay soils of volcanic origin. Histopathology investigations have demonstrated that silicon, aluminium, magnesium and iron are present in the lower limb lymph node macrophages of both patients and non-patients living barefoot on these clays. We studied the spatial variation (variations across an area) in podoconiosis prevalence and the associated environmental factors with a goal to better understanding the pathogenesis of podoconiosis. Methods Fieldwork was conducted from June 2011 to February 2013 in 12 kebeles (administrative units) in northern Ethiopia. Geo-located prevalence data and soil samples were collected and analysed along with secondary geological, topographic, meteorological and elevation data. Soil data were analysed for chemical composition, mineralogy and particle size, and were interpolated to provide spatially continuous information. Exploratory, spatial, univariate and multivariate regression analyses of podoconiosis prevalence were conducted in relation to primary (soil) and secondary (elevation, precipitation, and geology) covariates. Results Podoconiosis distribution showed spatial correlation with variation in elevation and precipitation. Exploratory analysis identified that phyllosilicate minerals, particularly clay (smectite and kaolinite) and mica groups, quartz (crystalline silica), iron oxide, and zirconium were associated with podoconiosis prevalence. The final multivariate model showed that the quantities of smectite (RR = 2.76, 95% CI: 1.35, 5.73; p = 0.007), quartz (RR = 1.16, 95% CI: 1.06, 1.26; p = 0.001) and mica (RR = 1.09, 95% CI: 1.05, 1.13; p < 0.001) in the soil had positive associations with podoconiosis prevalence. Conclusions More quantities of smectite, mica and quartz within the soil were associated with podoconiosis prevalence. Together with previous work indicating that these minerals may influence water absorption, potentiate infection and be toxic to human cells, the present findings suggest that these particles may play a role in the pathogenesis of podoconiosis and acute adenolymphangitis, a common cause of morbidity in podoconiosis patients. PMID:24946801

Structure and clay mineralogy: borehole images, log interpretation and sample analyses at Site C0002 Nankai Trough accretionary prism

NASA Astrophysics Data System (ADS)

Jurado, Maria Jose; Schleicher, Anja

2015-04-01

Our research focused on the characterization of fracture and fault structures from the deep Nankai Trough accretionary prism in Japan. Logging Data and cuttings samples from the two most recent International Ocean Discovery Program (IODP) Expeditions 338 and 348 of the NanTroSEIZE project were analyzed by Logging While Drilling (LWD) oriented images, geophysical logs and clay mineralogy. Both expeditions took place at Site C0002, but whereas Hole C0002F (Expedition 338) was drilled down to 2004.5 mbsf, Hole C0002N and C0002P (Expedition 348) reached a depth of 2325.5 mbsf and 3058.8 mbsf respectively. The structural interpretation of borehole imaging data illustrates the deformation within the fractured and faulted sections of the accretionary prism. All drill holes show distinct areas of intense fracturing and faulting within a very clay-dominated lithology. Here, smectite and illite are the most common clay minerals, but the properties and the role they may play in influencing the fractures, faults and folds in the accretionary prism is still not well understood. When comparing clay mineralogy and fracture/fault areas in hole C0002F (Expedition 338), a trend in the abundance of illite and smectite, and in particular the swelling behavior of smectite is recognizable. In general, the log data provided a good correlation with the actual mineralogy and the relative abundance of clay. Ongoing postcruise preliminary research on hole C0002 N and C0002P (Expedition 348) should confirm these results. The relationship between fracture and fault structures and the changes in clay mineralogy could be explained by the deformation of specific areas with different compaction features, fluid-rock interaction processes, but could also be related to beginning diagenetic processes related to depth. Our results show the integration of logging data and cutting sample analyses as a valuable tool for characterization of petrophysical and mineralogical changes of the structures of the Nankai accretionary prism. This is critical for our understanding of clay-fluid interaction and mechanical properties duing fault displacements and seismogenesis.

Long-term variations of clay mineral composition in the Andaman Sea (IODP Exp. 353 Site U1447): preliminary result

NASA Astrophysics Data System (ADS)

Lee, J.; Khim, B. K.; Cho, H. G.; Kim, S.; 353 Scientists, I. E.

2016-12-01

Clay mineral studies in the Bengal Fan have allowed the reconstruction of the erosional history of the Himalayan-Tibetan complex since the Early Miocene. Several factors such as climate change and tectonic activity are important for the erosion rate of the Himalaya-Tibet complex. IODP Expedition 353 Site U1447 (10°47.4'N, 93°00'E; 1391 mbsl) was drilled on a ridge 45 km offshore Little Andaman Island in the Andaman Sea, penetrating to total depths of 738 m. Riverine sediments supplied mainly by the Irrawaddy and Salween (draining the Indo-Burman Ranges; smectite-rich) and the Ganga/Brahmaputra (draining the Himalaya; illite-rich) via the surface currents have been known to deposit in the Andaman Sea. We measured clay minerals of 38 sediment samples collected from 150 to 737 m CSF-A at Site U1447 in order to reveal long-term variation patterns of clay minerals and their controlling factors. Age reconstruction of Site U1447 aided by shipboard biostratigraphic and paleomagnetic data defined the study interval spanning from the Late Miocene ( 10 Ma) to Early Pleistocene ( 1.25 Ma). At this interval, clay minerals consist mainly of smectite (28-61% with an average of 47%) followed by illite (20-41% with an average of 29%), kaolinite (9-19% with an average of 14%), and chlorite (5-15% with an average of 10%). Variation of clay mineral compositions is divided into three stages; almost consistent variations of all clay minerals (from 750 to 570 m CSF-A; 10.0 to 7.5 Ma), gradual decrease of smectite and increase of illite and chlorite (from 570 to 400 m CSF-A; 7.5 to 4.5 Ma), and great fluctuation of all clay minerals (from 400 to 150 m CSF-A; 4.5 to 1.1 Ma). Such long-term clay mineral changes may be related to provenance switches, tectonic evolution of the source regions, climatic variations, degree of volcanism with basin evolution, sedimentation history by sea level changes or some combination of these factors.

The central uplift of Elorza Crater: Insights into its geology and possible relationships to the Valles Marineris and Tharsis regions

NASA Astrophysics Data System (ADS)

Hopkins, R. T.; Tornabene, L. L.; Osinski, G. R.

2017-03-01

The majority of hydrated silicate occurrences on Mars are associated with impact craters (Ehlmann et al., 2011; Carter et al., 2013). Three formation mechanisms have been suggested to account for this correlation: (1) aqueous alteration occurred pre-impact, and was subsequently exposed via the impact (pre-impact; Bibring et al., 2006; Ehlmann et al., 2011), (2) heat generated from the impact facilitated the formation of a hydrothermal system, leading to alteration products (syn-impact; e.g. Marzo et al., 2010; Osinski et al., 2013), and/or (3) altered materials were deposited after crater formation, or formed within the crater well after the impact had taken place (post-impact). In this study, we analyze the central uplift of Elorza Crater, a ∼40 km diameter impact crater located ∼300 km north of Valles Marineris. To determine whether hydrated minerals found within the uplift were generated pre-, syn-, or post-impact, we used a data synthesis approach, utilizing High Resolution Imaging Science Experiment (HiRISE), Compact Reconnaissance Imaging Spectrometer for Mars (CRISM), Context Camera (CTX), and Thermal Emission Imaging System (THEMIS) imagery. Opaline silica is observed in two locations on the southwestern side of the uplift and is interpreted to have been pre-existing or formed via hydrothermal alteration due to stratigraphic relationships with the overlying impact melt unit. Both Fe/Mg smectite and low-calcium pyroxene (LCP) are found throughout the uplift. Bedrock exposures on the northern wall of Coprates Chasma containing Fe/Mg smectite and LCP suggest an uplifted origin for these units. In all cases, although a pre-existing origin is probable, it is difficult to rule out the possibility of an impact-generated hydrothermal origin. Using the observed stratigraphy exposed in Coprates Chasma and bedrock exposures analyzed in nearby craters, we were able to constrain the pre-impact stratigraphy around Elorza. The near-subsurface consists of Hesperian-aged, discontinuous lava/ash deposits that may be interposed with opaline silica-bearing deposits, overlying Noachian basement consisting of smectite-bearing bedrock and LCP- bearing light-toned fractured bedrock.

Fingerprinting Persistent Turbidity in Sheep Creek Reservoir, Owhyee, Nevada

NASA Astrophysics Data System (ADS)

Ransom, R. N.; Hooper, R. L.; Kerner, D.; Nicols, S.

2007-12-01

Sheep Creek Reservoir near Owyhee, NV is historically a quality rainbow trout fishery. Persistent high-turbidity has been an issue since a major storm event in 2005 resulted in surface water runoff into the Reservoir. The high turbidity is adversely impacting the quality of the fishery. Initial turbidity measurements in 2005 were upwards of 80NTU and these numbers have only decreased to 30NTU over the past two summers. Field parameters indicate the turbidity is associated with high total suspended solids (TSS) and not algae. Five water samples collected from around the reservoir during June, 2007 indicated uniform TSS values in the range of 5 to 12mg/L and oriented powder x-ray diffraction(XRD) and transmission electron microscopy(TEM) analyses of suspended sediment shows very uniform suspended particulate mineralogy including smectite, mixed layer illite/smectite (I/S), discrete illite, lesser amounts of kaolin, sub-micron quartz and feldspar. Diatoms represent a ubiquitous but minor component of the suspended solids. Six soil samples collected from possible source areas around the reservoir were analyzed using both XRD and TEM to see if a source area for the suspended solids could be unambiguously identified. Soils on the east side of the reservoir contain smectite and mixed layer I/S but very little of the other clays. The less than 2 micron size fraction from soils collected from a playa on the topographic bench immediately to the west of the reservoir show a mineralogic finger-print essentially identical to the current suspended sediment. The suspended sediment probably originates on the bench to the west of the reservoir and cascades into the reservoir over the topographic break during extreme storm events. The topographic relief, short travel distance and lack of a suitable vegetated buffer zone to the west are all consistent with a primary persistent suspended sediment source from the west. Identification of the sediment source allows for design of a cost effective remediation plan that includes minimizing future loading of the reservoir with soils capable of producing extended turbidity.

Hydrothermal Alteration of the Mt Unzen Conduit (Shimabara/Japan)

NASA Astrophysics Data System (ADS)

Yilmaz, T. I.; Mayer, K.; Hess, K. U.; Janots, E.; Gilg, H. A.; Dingwell, D. B.

2016-12-01

Investigations were carried out on hydrothermally altered coherent dacitic dykes samples from (USDP-4) drill core at Mt Unzen stratovolcano (Shimabara/Japan). XRF, XRD, EMPA, and C-O-isotope analysis led to insights concerning chemistry, mineralogy, and intensity of alteration as well as the origin of carbonate-precipitating fluids. Additionally a textural characterization of the occurring replacement features in the magma conduit zone was performed. The occurrence of the main secondary phases such as chlorite, pyrite, carbonates, and R1 (Reichweite parameter) illite-smectite indicate a weak to moderate propylitic to phyllic hydrothermal alteration. The dacitic samples of the dykes show different hydrothermal alteration features: (i) carbonate pseudomorphs after hornblende as well as core and zonal textures due to replacement of plagioclase by R1 illite-smectite, (ii) colloform banded fracture fillings and fillings in dissolution vugs, and (iii) chlorite and R1 illite-smectite in the groundmass. Carbonates in fractures comprise iron-rich dolomite solid solutions ("ankerite") and calcite. Isotopic values of d13Cvpdb = -4.59 ± 0.6‰ and d18Ovpdb = -21.73 ± 0.5‰ indicate a hydrothermal-magmatic origin for the carbonate formation. The chlorite-carbonate-pyrite index (CCPI) and the Ishikawa alteration index (AI), applied to the investigated samples show significant differences (CCPI=52.7-57.8; AI=36.1-40.6) indicating their different degree of alteration. According to Nakada et al., 2005, the C13 to C16 dykes represent the feeder dyke from the latest eruption (1991-1995) whereas C8 represents an earlier dyke feeder dyke from an older eruption. Weakest conduit alteration, which was obtained in samples C16-1-5 and C13-2-5, correlates with the alteration degree of the pristine dome rocks. Highest CCPI value was determined for sample C14-1-5 and the highest AI value was determined for sample C15-2-6. The degrees of alteration do not indicate highest alteration of the samples C8-1-2 and C8-2-1 from the older dykes.

The Effect of Authigenic Phyllosilicate Growth on the Mechanical Behaviour of Upper Crustal Faults

NASA Astrophysics Data System (ADS)

Evans, S.; Holdsworth, R.; Imber, J.; Marco, S.; Weinberger, R.; De Paola, N.

2014-12-01

Deformation at shallow crustal depths is dominated by brittle processes, but it is increasingly recognised that diffusive mass transfer (DMT) processes and "ductile" folding also play a significant role in fault zone development. We present data from exhumed sections (<5 km depth) of the southern Dead Sea Fault System, Israel, an active continental transform fault that has accumulated 105 km of sinistral displacement since the Miocene. The faults juxtapose various wall rock lithologies (crystalline basement, carbonate and clastic cover), but the studied sections all have phyllosilicate-rich fault cores. Damage zones show a range of deformation mechanisms including pulverisation, pressure-solution and cataclasis. Our results show that fault cores comprise three distinct types of fault gouge (alongside coarser-grained cataclasite): cataclastic gouge that is mineralogically similar to wall rock compositions; authigenic gouge that is dominated by Mg-rich smectite not present in adjacent formations; and mechanically entrained, folded shale gouge that is almost identical in mineralogy to a local shale protolith. Microstructural observations suggest authigenic gouge is the result of DMT processes, following an earlier phase of gouge formation through microfracturing and cataclasis. The low abundance of carbonate within fault cores suggests its dissolution is a contributing factor in authigenic smectite precipitation. Such mineralogical transformations may lead to significant changes in the frictional properties of fault zones, from materials of relatively high frictional strength (quartz, feldspars, dolomite, where μ = 0.6 - 0.85) to those with much lower frictional strengths, such as smectite (where μ can be as low as 0.15). We demonstrate how the physical properties of faults may evolve over time when conditions allow precipitation of weak-phases in addition to brittle deformation, which may facilitate ingress of fluid into fault cores and enhance phyllosilicate development. The presence of both pulverisation textures and microfolds suggests interaction of these deformation styles may lead to changes in overall fault behaviour, from velocity-weakening and seismogenic where brittle processes dominate, to velocity-strengthening and aseismic when sufficient weak material has accumulated.

Multidecadal persistence of organic matter in soils: insights from spatially resolved investigations at the submicrometer scale

NASA Astrophysics Data System (ADS)

Lutfalla, Suzanne; Barré, Pierre; Bernard, Sylvain; Le Guillou, Corentin; Alléon, Julien; Chenu, Claire

2016-04-01

Better understanding the mechanisms responsible for the pluri-decadal persistence of carbon in soils requires well constraining the dynamics, the distribution and the chemical nature of both the soil organic carbon (SOC) and the associated mineral phases. The question we address in this work is whether different mineral species lead to different organo-mineral interactions and stabilize different quantities of SOM and different types of SOC. Here, benefiting from the unique opportunity offered by an INRA long term bare fallow (LTBF) experiment having started in 1928 in Versailles (France), we report the in-situ characterization of SOC dynamics in four clay fractions of this silty loam soil (total clays [TC, <2μm], coarse clays [CC, 0.2-2μm], intermediate clays [IC, 0.05-0.2μm] and fine clays [FC, 0-0.05μm]). The IC and FC fractions only contain smectite and illite/smectite mixed-layered clay minerals while the CC fraction also contains illite and kaolinite. In the absence of any carbon input, the plant-free LTBF clay fractions from Versailles progressively lost SOC during the first 50 years of the experiment, until they reached a seemingly stable concentration. Of note, the investigated clay fractions did not lose the same amount of SOC and do not exhibit the same final carbon concentrations. The decrease of the organic C:N ratios with LTBF duration corresponds to a progressive enrichment in N-rich SOC for all fractions which can be attributed to microbial material. Even though the speciation of SOC appears to only slightly evolve with LTBF duration, an enrichment in carboxyl and carbonyl groups is revealed by bulk-scale C-NEXAFS data for SOC from all clay fractions. In addition, STXM-based NEXAFS investigations at the submicrometer scale reveal three types of SOC-clay assemblages in addition to clay-free SOC and organic-free clays. While SOC appears mostly adsorbed onto clay surfaces within the IC and FC fractions, other protection mechanisms occur within the CC fraction. Altogether, the present study suggests that smectite have more efficient protection capabilities than those of illite and kaolinite.

The Effects of Iron Oxidation State on Clay Swelling,

DTIC Science & Technology

1983-03-07

swelling, montmorillonite , nontronite, smectite, water, DLVO theory, surface charge, dissolution, methods, aluminum, silicon, inert atmosphere. 2G...that many physical properties of bulk water are changed when it is adsorbed between layers of Na4- montmorillonite (e.g., Oster and Low, 1964; Kolaian...Na+- montmorillonite accounted for about 13% of the total water content in the free-swelling state. We can therefore express the total water content

Process for the preparation of organoclays

DOEpatents

Chaiko, David J.

2003-01-01

A method for preparing organoclays from smectites for use as rheological control agents and in the preparation of nanocomposites. Typically, the clay is dispersed in water, and a substantially monomolecular layer of a water soluble polymer is applied to the surfaces of the clay. A surfactant is also applied to the clay to modify the surface hydrophilic/hydrophobic balance of the clay, and the organoclay is separated out for subsequent use.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Diatoms in late Quaternary sediment from the Orca Basin

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

Klas, M.; Burckle, L.H.

1985-01-01

Diatoms and clays were studied in core EN32-PC6 from the Orca Basin. This core contains oxygen isotope evidence for increased melt-water outflow from the Mississippi River during the post-Wisconsin deglaciation. Diatoms are present in two intervals: the period of increased melt-water outflow at about 15,000 to 12,000 years BP and during the past 5000 years. The earlier interval (the melt-water spike) contains fresh and brackish water diatoms and open ocean forms that prefer lower salinities while the youngest interval is characterized by open ocean forms. The melt-water spike interval also contains fewer reworked Cretaceous and Paleogene coccoliths and has littlemore » or no quartz. A decrease in smectite in the core at about 22,000 years BP may be related to a similar decrease in the Morton loess due to the blocking and diversion of the ancient Mississippi by the advancing Woodfordian glacier of the Lake Michigan lobe. After this diversion, the Mississippi took its present-day course and continued to take outwash away from the receding glacier. In Orca Basin sediments, this is indicated by an increase in smectite. The interval of the melt-water spike seems to be characterized by increased rainfall and sheet flooding.« less

One-dimensional pore pressure diffusion of different grain-fluid mixtures

NASA Astrophysics Data System (ADS)

von der Thannen, Magdalena; Kaitna, Roland

2015-04-01

During the release and the flow of fully saturated debris, non-hydrostatic fluid pressure can build up and probably dissipate during the event. This excess fluid pressure has a strong influence on the flow and deposition behaviour of debris flows. Therefore, we investigate the influence of mixture composition on the dissipation of non-hydrostatic fluid pressures. For this we use a cylindrical pipe of acrylic glass with installed pore water pressure sensors in different heights and measure the evolution of the pore water pressure over time. Several mixtures with variable content of fine sediment (silt and clay) and variable content of coarse sediment (with fixed relative fractions of grains between 2 and 32 mm) are tested. For the fines two types of clay (smectite and kaolinite) and loam (Stoober Lehm) are used. The analysis is based on the one-dimensional consolidation theory which uses a diffusion coefficient D to model the decay of excess fluid pressure over time. Starting from artificially induced super-hydrostatic fluid pressures, we find dissipation coefficients ranging from 10-5 m²/s for liquid mixtures to 10-8 m²/s for viscous mixtures. The results for kaolinite and smectite are quite similar. For our limited number of mixtures the effect of fines content is more pronounced than the effect of different amounts of coarse particles.

Geological and geotechnical characteristics of Metro Manila volcanic soils and their suitability for landfill soil liner

NASA Astrophysics Data System (ADS)

Mendoza, Edna Patricia; Catane, Sandra; Pascua, Chelo; Zarco, Mark Albert

2010-05-01

Due to the Philippines's island-arc setting, andesitic tuff and volcanic ash constitute two-thirds of the country's agricultural land. In situ weathering of these volcanic sediments produces volcanic soils. Metro Manila volcanic soils were studied to determine their suitability for landfill soil liner. The soils were analyzed using XRD and XRF, and were tested for geotechnical properties. The results show the presence of the smectite group, a swelling variety of clay. The smectite-type clays are weathering products of volcanic glasses which are dominant components of the parental rocks. The high amounts of Al2O3 indicate an Al-rich type of soil. The clay species is either di- or tri-octahedral type, which points to montmorillonite as the main clay species. Swelling clay lowers the permeability of soils and reduces the infiltration and lateral movement of leachates in the ground. Also, geotechnical tests revealed moderate to high plasticity indices and low hydraulic conductivity values. The study shows that the physicochemical characteristics of volcanic soils meet the criteria for a soil liner for future sanitary landfill projects as mandated by RA 9003, a recently ratified solid waste management act of the Philippines. Being widespread, volcanic soils can be viewed as an important resource of the country.

Evidence for montmorillonite or its compositional equivalent in Columbia Hills, Mars

USGS Publications Warehouse

Clark, B. C.; Arvidson, R. E.; Gellert, Ralf; Morris, R.V.; Ming, D. W.; Richter, L.; Ruff, S.W.; Michalski, J.R.; Farrand, W. H.; Yen, A. S.; Herkenhoff, K. E.; Li, R.; Squyres, S. W.; Schroder, C.; Klingelhofer, G.; Bell, J.F.

2007-01-01

During its exploration of the Columbia Hills, the Mars Exploration Rover "Spirit" encountered several similar samples that are distinctly different from Martian meteorites and known Gusev crater soils, rocks, and sediments. Occurring in a variety of contexts and locations, these "Independence class" samples are rough-textured, iron-poor (equivalent FeO ??? 4 wt%), have high Al/Si ratios, and often contain unexpectedly high concentrations of one or more minor or trace elements (including Cr, Ni, Cu, Sr, and Y). Apart from accessory minerals, the major component common to these samples has a compositional profile of major and minor elements which is similar to the smectite montmorillonite, implicating this mineral, or its compositional equivalent. Infrared thermal emission spectra do not indicate the presence of crystalline smectite. One of these samples was found spatially associated with a ferric sulfate-enriched soil horizon, possibly indicating a genetic relationship between these disparate types of materials. Compared to the nearby Wishstone and Watchtower class rocks, major aqueous alteration involving mineral dissolution and mobilization with consequent depletions of certain elements is implied for this setting and may be undetectable by remote sensing from orbit because of the small scale of the occurrences and obscuration by mantling with soil and dust. Copyright 2007 by the American Geophysical Union.

A mechanism of basal spacing reduction in sodium smectitic clay materials in contact with DNAPL wastes.

PubMed

Ayral-Cinar, Derya; Otero-Diaz, Margarita; Demond, Avery H

2016-09-01

There has been concern regarding the possible attack of clays in aquitards, slurry walls and landfill liners by dense nonaqueous phase liquid (DNAPL) wastes, resulting in cracking. Despite the fact that a reduction in basal spacing in sodium smectitic clay materials has been linked to cracking, no plausible mechanism by which this reduction occurs in contact with waste DNAPLs has been formulated. To elucidate a mechanism, screening studies were conducted that showed that the combination of an anionic surfactant (AOT), a nonionic surfactant (TritonX-100) and a chlorinated solvent, tetrachloroethylene (PCE), could replicate the basal spacing reduction and cracking behavior of water-saturated bentonite caused by two waste DNAPLs obtained from the field. FTIR measurements of this system showed a displacement of the HOH bending band of water symptomatic of desiccation. Sorption measurements showed that the uptake of AOT by bentonite increased eight fold in the presence of TritonX-100 and PCE. The evidence presented here supports a mechanism of syneresis, involving the extraction of water from the interlayer space of the clay through the synergistic sorption of a nonionic and anionic surfactant mixture. It is speculated that the solvation of water in reverse micellar aggregates is the process driving the syneresis. Copyright © 2016. Published by Elsevier Ltd.

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.

The efficacy of bamboo charcoal in comparison with smectite to reduce the detrimental effect of aflatoxin B1 on in vitro rumen fermentation of a hay-rich feed mixture.

PubMed

Jiang, Ya-Hui; Wang, Ping; Yang, Hong-Jian; Chen, Ying

2014-07-10

Two commercial materials, a bamboo charcoal (BC) and a smectite clay (SC), were assessed in vitro with aflatoxin B1 (AFB1) in an equilibrium adsorption test. The adsorption capacity and proportion adsorbed (0.381 μg/mg, 0.955) for BC were greater than for SC (0.372 μg/mg, 0.931). The effects of in vitro ruminal fermentation of hay-rich feed incubated with 1.0 μg/mL AFB1 for 0-10 g/L doses of BC and SC were measured at 39 °C for 72 h. The BC and SC binders increased AFB1 loss at dosages ≥1.0 g/L (p < 0.0001). Average AFB1 loss (p < 0.0001) was greater for SC (0.904) than BC (0.881). Both SC and SC addition increased in vitro dry matter loss, and the average dry matter losses were similar. Asymptotic gas volume and volatile fatty acid production were greater for BC than for SC (p < 0.0001). Thus, BC may be as effective as SC in removing aflatoxin B1's detrimental effects on rumen degradability and fermentation under the occurrence of microbial aflatoxin degradation.

The Efficacy of Bamboo Charcoal in Comparison with Smectite to Reduce the Detrimental Effect of Aflatoxin B1 on In Vitro Rumen Fermentation of a Hay-Rich Feed Mixture

PubMed Central

Jiang, Ya-Hui; Wang, Ping; Yang, Hong-Jian; Chen, Ying

2014-01-01

Two commercial materials, a bamboo charcoal (BC) and a smectite clay (SC), were assessed in vitro with aflatoxin B1 (AFB1) in an equilibrium adsorption test. The adsorption capacity and proportion adsorbed (0.381 μg/mg, 0.955) for BC were greater than for SC (0.372 μg/mg, 0.931). The effects of in vitro ruminal fermentation of hay-rich feed incubated with 1.0 μg/mL AFB1 for 0–10 g/L doses of BC and SC were measured at 39 °C for 72 h. The BC and SC binders increased AFB1 loss at dosages ≥1.0 g/L (p < 0.0001). Average AFB1 loss (p < 0.0001) was greater for SC (0.904) than BC (0.881). Both SC and SC addition increased in vitro dry matter loss, and the average dry matter losses were similar. Asymptotic gas volume and volatile fatty acid production were greater for BC than for SC (p < 0.0001). Thus, BC may be as effective as SC in removing aflatoxin B1’s detrimental effects on rumen degradability and fermentation under the occurrence of microbial aflatoxin degradation. PMID:25014194

Transmission electron microscope analyses of alteration phases in martian meteorite MIL 090032

NASA Astrophysics Data System (ADS)

Hallis, L. J.; Ishii, H. A.; Bradley, J. P.; Taylor, G. J.

2014-06-01

The nakhlite group of martian meteorites found in the Antarctic contain varying abundances of both martian and terrestrial secondary alteration phases. The aim of this study was to use transmission electron microscopy (TEM) to compare martian and terrestrial alteration embodied within a single nakhlite martian meteorite find - MIL 090032. Martian alteration veins in MIL 090032 are composed of poorly ordered Fe-smectite phyllosilicate. This poorly-ordered smectite appears to be equivalent to the nanocrystalline phyllosilicate/hydrated amorphous gel phase previously described in the martian alteration veins of other nakhlites. Chemical differences in this nanocrystalline phyllosilicate between different nakhlites imply localised alteration, which occurred close to the martian surface in MIL 090032. Both structurally and compositionally the nakhlite nanocrystalline phyllosilicate shows similarities to the amorphous/poorly ordered phase recently discovered in martian soil by the Mars Curiosity Rover at Rocknest, Gale Crater. Terrestrially derived alteration phases in MIL 090032 include jarosite and gypsum, amorphous silicates, and Fe-oxides and hydroxides. Similarities between the mineralogy and chemistry of the MIL 090032 terrestrial and martian alteration phases suggest the alteration conditions on Mars were similar to those in the Antarctic. At both sites a small amount of fluid at low temperatures infiltrated the rock and became acidic as a result of the conversion of Fe2+ to Fe3+ under oxidising conditions.

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

NASA Technical Reports Server (NTRS)

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

2012-01-01

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

Structure and Dynamics of Confined Water and CO2 in Clays under Supercritical Conditions

NASA Astrophysics Data System (ADS)

Glezakou, V.; Lee, M.; Schaef, T.; Loring, J.; Davidson, C.; McGrail, P.

2013-12-01

Carbon dioxide (CO2) driven enhanced gas recovery (EGR) from depleted fractured shale gas reservoirs has the potential for producing economic benefits and providing long term storage options for anthropogenic derived CO2 emissions. However key scientific processes related to CO2:CH4 exchange rates, mineral volume changes, organic mobility, and mineral stability in the presence of acid gas injections are not well understood. In this paper, we conduct atomistic simulations to examine interactions occurring between model clay minerals and supercritical CO2 equilibrated with water or brines to identify parameters controlling adsorption and desorption of gases. Integrated within these simulations are results derived from a set of newly developed experimental techniques designed to characterize physico-chemical reactions at reservoir conditions. In a series of cell optimizations under pressures relevant to sequestration scenarios, molecular simulations within the NVT and NPT ensembles with varying water/CO2 ratios showed a range of interlayer expansion for specific cation-saturated smectites. In conjunction with experimental in situ high pressure x-ray diffraction (HXRD), semi-quantitative concentrations of interlayer H2O and CO2 were established. For example, Ca saturated smectites maintaining sub-single to single hydration states (<1W to 1W), expand approximately 1.7-2.0 Å when exposed to anhydrous supercritical CO2. In contrast, for single to double hydration states (1W-2W), the simulations indicate formation of a quasi-single, metastable state, leading to a reduced interlayer spacing. Partial dehydration of the interlayer spacing while in contact with CO2 is due to a reduction of the interlayer cation coordination number. Structural analysis of the intercalated species shows an increase in the hydrogen bonding between waters during CO2 intercalation coincident with a decrease in the coordination population around the cations. Power spectra reveal rotationally constrained CO2 molecules over the silica layer of the Ca-smectite surface due to the formation of a two dimensional supercritical CO2 network at lower pressures, expanding to three-dimensions as the water content increases. Diffusion coefficients of the interlayer species determined from the molecular trajectories show dependence on the presence of CO2 and hydration state. In agreement with modeling studies, direct observations of volume changes were observed during in situ HXRD experiments when exposure of a 2W Ca-smectite to supercritical CO2 at 50 °C and 90 bar produced a decrease in the interlayer spacing. In addition to intercalation, surface adsorption and desorption are equally important interactions occurring with clay minerals in the presence of supercritical CO2. Processes related to surface condensation of CO2 were examined through a series of modeling exercises and in situ spectroscopic measurements. Results showed that adsorbed CO2 concentrations were low when no water was adsorbed to the clay, but dramatically increased to a maximum when the clay was at ~1W. With continued water adsorption, CO2 concentrations decreased as the water outcompeted CO2 for adsorption/intercalation sites.

Composition, structure and properties of sediment thermal springs of Kamchatka

NASA Astrophysics Data System (ADS)

Shanina, Violetta; Smolyakov, Pavel; Parfenov, Oleg

2016-04-01

The paper deals with the physical and mechanical properties sediment thermal fields Mutnovsky, Lower Koshelevo and Bannyh (Kamchatka). This multi-component soils, mineral and chemical composition of which depends on the formation factors (pH, temperature, salinity of water, composition and structure of the host volcanic rocks). Samples Lower Koshelevo sediment thermal sources differ in the following composition: smectite, kaolinite, kaolinite-smectite mixed-mineral. Samples of sediment thermal springs Mutnovsky volcano in accordance with the X-ray analysis has the following composition: volcanic glass, crystalline sulfur, plagioclase, smectite, illite-smectite mixed, illite, chlorite, quartz, cristobalite, pyrite, melanterite, kaolinite. Natural moisture content samples of sediment thermal springs from 45 to 121%, hygroscopic moisture content of 1.3 to 3.7%. A large amount of native sulfur (up to 92%) and the presence of amorphous material gives low values of density of solid particles (up to 2.1 g/cm3) samples Mutnovskii thermal field. The values of the density of solids sediment Koshelevo and Bannyh hot springs close to those of the main components of mineral densities (up to 2.6-3.0 g/cm3). The results of the particle size distribution and microaggregate analysis of sediment thermal springs Lower Koshelevo field shows that the predominance observed of particles with a diameter from 0.05 mm to 0.25 mm, the coefficient of soil heterogeneity heterogeneous. In the bottom sediments of the thermal springs of the volcano Mutnovsky poorly traced predominance of one faction. Most prevalent fraction with particle size 0.01 - 0.05 mm. When analyzing the content in the soil microaggregates their content is shifted towards particles with a diameter of 0.25 mm. The contents of a large number of large (1-10 mm), porous rock fragments, due to the deposition of pyroclastic material from the eruptions of the last century. Present in large amounts rounded crystals of native sulfur associated with the rise of mixed solutions, formed at the boundary of secondary boil through faults to the surface thermal boiler (Bortnikova et al., 2009). Calculated flow index and plasticity, shows the classification in accordance with GOST 25100-2011. From these figures it is clear that all the sediments are sandy loam and are in a fluid state. A clear relationship between temperature, pH and particle size distribution of sediment thermal springs can not be traced, great importance is the geological evolution of the volcanic activity, hydrogeological conditions and the time factor. Therefore, samples with a currently active Mutnovsky volcano - sandy loam, sediments of the thermal springs Koshelevo fields are often to loams. The bottom sediments of thermal springs from the territory of the Lower Koshelevo thermal field in a natural occurrence in a state of higher yield strength, so they are an unstable surface, which may cause landslides. The bottom sediments of thermal springs are low explored subject of engineering geology, it is important to examine their properties to simulate the conditions of formation and the development of dangerous processes.

Anomalously high porosity in subduction inputs to the Nankai Trough (SW Japan) potentially caused by volcanic ash and pumice

NASA Astrophysics Data System (ADS)

Huepers, A.; Ikari, M.; Underwood, M.; Kopf, A.

2013-12-01

At convergent margins, the sedimentary section seaward of the trench on the subducting oceanic lithosphere provides the source material for accretionary prisms and eventually becomes the host rock of the plate boundary megathrust. The mechanical properties of the sediments seaward of the subduction zone have therefore a first order control on subduction zone forearc mechanics and hydrogeology. At the Nankai Trough (SW Japan) the majority of sediment approaching the subduction zone is clay-rich. Scientific drilling expeditions in the framework of the Ocean Drilling Program (ODP) and the Integrated Ocean Drilling Program (IODP) have revealed an anomalous zone of high porosity in a major lithologic unit known as the Upper Shikoku Basin facies (USB), which is associated with elevated volcanic ash content and high amounts of silica in the interstitial water. The existence of the high porosity zone has previously been associated with advanced silica cementation, driven by the dual diagenetic transition of opal-A to opal-CT, and opal-CT to quartz. However, temperature estimates from recent drilling expeditions offshore the Kii peninsula reveal different in situ temperatures at the proposed diagenetic boundary in the Shikoku Basin. Furthermore, laboratory measurements using core samples from the USB show that cohesive strength is not elevated in the high porosity zone, suggesting that a process other than cementation may be responsible. The USB sediment is characterized by abundant volcanic ash and pumice, therefore the high porosity zone in the USB may be closely linked to the mechanical behavior of this phase. We conducted consolidation tests in the range 0.1 to 8 MPa effective vertical stress on artificial ash-smectite and pumice-smectite mixtures, as well as intact and remolded natural samples from the IODP Sites C0011 and C0012 to investigate the role of the volcanic constituent on porosity loss with progressive burial. Our results show that both remolded and intact natural samples have high porosities of up to ~71 to 75% at a vertical effective stress of 0.1 MPa, which decreases to 39 to 49% at 8 MPa vertical effective stress. The behavior of the remolded samples is in good accordance with compiled in-situ porosity vs. depth profiles from the high porosity zone. This suggests that cementation is not the cause for the anomalously high porosity. The consolidation tests on the artificial samples document that pure ash and pumice samples are highly resistant to consolidation. Between 0.1 to 8 MPa vertical effective stress, the porosity decreases from 51 to 47% for the ash sample and 60% to 46% for the pumice sample. The higher initial porosity in the pumice may be explained by a porous internal grain structure that allows storage of additional water. Mixtures with smectite are characterized by higher compressibility and higher porosity. For a mixture of 80% smectite and 20% pumice the porosity decreases from 65% to 39%, similar to that of the natural samples. Our results suggest that the high porosity zone is caused by the bulk mechanical behavior of pumice in the USB.

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

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

Bishop, Michael E.; Dong, Hailiang; Kukkadapu, Ravi K.

2011-07-01

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

The I/S-to-illite reaction in the late stage diagenesis

USGS Publications Warehouse

Lanson, B.; Champion, D.

1991-01-01

XRF analyses of individual grains show that the I/S minerals become more illitic (near mica composition) with depth, but they always contain a portion of a smectite component, that is, silica-rich, low layer charge component. Both lath I/S and hexagonal illite minerals appear to grow by adding illite layers of the same composition (0.9 potassium atoms and a slight celadonite, phengite component) onto original crystallites. -from Authors

Program and Abstracts for Clay Minerals Society 28th Annual Meeting

NASA Technical Reports Server (NTRS)

1991-01-01

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

Characteristics, extent and origin of hydrothermal alteration at Mount Rainier Volcano, Cascades Arc, USA: Implications for debris-flow hazards and mineral deposits

NASA Astrophysics Data System (ADS)

John, David A.; Sisson, Thomas W.; Breit, George N.; Rye, Robert O.; Vallance, James W.

2008-08-01

Hydrothermal alteration at Mount Rainier waxed and waned over the 500,000-year episodic growth of the edifice. Hydrothermal minerals and their stable-isotope compositions in samples collected from outcrop and as clasts from Holocene debris-flow deposits identify three distinct hypogene argillic/advanced argillic hydrothermal environments: magmatic-hydrothermal, steam-heated, and magmatic steam (fumarolic), with minor superimposed supergene alteration. The 3.8 km 3 Osceola Mudflow (5600 y BP) and coeval phreatomagmatic F tephra contain the highest temperature and most deeply formed hydrothermal minerals. Relatively deeply formed magmatic-hydrothermal alteration minerals and associations in clasts include quartz (residual silica), quartz-alunite, quartz-topaz, quartz-pyrophyllite, quartz-dickite/kaolinite, and quartz-illite (all with pyrite). Clasts of smectite-pyrite and steam-heated opal-alunite-kaolinite are also common in the Osceola Mudflow. In contrast, the Paradise lahar, formed by collapse of the summit or near-summit of the edifice at about the same time, contains only smectite-pyrite and near-surface steam-heated and fumarolic alteration minerals. Younger debris-flow deposits on the west side of the volcano (Round Pass and distal Electron Mudflows) contain only low-temperature smectite-pyrite assemblages, whereas the proximal Electron Mudflow and a < 100 y BP rock avalanche on Tahoma Glacier also contain magmatic-hydrothermal alteration minerals that are exposed in the avalanche headwall of Sunset Amphitheater, reflecting progressive incision into deeper near-conduit alteration products that formed at higher temperatures. The pre-Osceola Mudflow alteration geometry is inferred to have consisted of a narrow feeder zone of intense magmatic-hydrothermal alteration limited to near the conduit of the volcano, which graded outward to more widely distributed, but weak, smectite-pyrite alteration within 1 km of the edifice axis, developed chiefly in porous breccias. The edifice was capped by a steam-heated alteration zone, most of which resulted from condensation of fumarolic vapor and oxidation of H 2S in the unsaturated zone above the water table. Weakly developed smectite-pyrite alteration extended into the west and east flanks of the edifice, spatially associated with dikes that are localized in those sectors; other edifice flanks lack dikes and associated alteration. The Osceola collapse removed most of the altered core and upper east flank of the volcano, but intensely altered rocks remain on the uppermost west flank. Major conclusions of this study are that: (1) Hydrothermal-mineral assemblages and distributions at Mount Rainier can be understood in the framework of hydrothermal processes and environments developed from studies of ore deposits formed in analogous settings. (2) Frequent eruptions supplied sufficient hot magmatic fluid to alter the upper interior of the volcano hydrothermally, despite the consistently deep (≥ 8 km) magma reservoir which may have precluded formation of economic mineral deposits within or at shallow depths beneath Mount Rainier. The absence of indicator equilibrium alteration-mineral assemblages in the debris flows that effectively expose the volcano to a depth of 1-1.5 km also suggests a low potential for significant high-sulfidation epithermal or porphyry-type mineral deposits at depth. (3) Despite the long and complex history of the volcano, intensely altered collapse-prone rocks were spatially restricted to near the volcano's conduit system and summit, and short distances onto the upper east and west flanks, due to the necessary supply of reactive components carried by ascending magmatic fluids. (4) Intensely altered rocks were removed from the summit, east flank, and edifice interior by the Osceola collapse, but remain on the upper west flank in the Sunset Amphitheater area and present a continuing collapse hazard. (5) Visually conspicuous rocks on the lower east and mid-to-lower west flanks are not intensely altered and probably have not significantly weakened the rock, and thus do not present significant collapse hazards. (6) Alteration developed most intensely within breccia units, because of their high permeability and porosity. Volcanoes with abundant near-conduit upper-edifice breccias are prone to alteration increasing the possibility of collapse, whereas those that are breccia-poor (e.g., massive domes) are less prone to alteration.

Hydrothermal alteration of a rhyolitic hyaloclastite from Ponza Island, Italy

NASA Astrophysics Data System (ADS)

Ylagan, Robert F.; Altaner, Stephen P.; Pozzuoli, Antonio

1996-12-01

A rhyolitic hyaloclastite from Ponza island, Italy, has been hydrothermally altered producing four distinct alteration zones based on XRD and field textures: (1) non-pervasive argillic zone; (2) propylitic zone; (3) silicic zone; and (4) sericitic zone. The unaltered hyaloclastite is a volcanic breccia with clasts of vesiculated obsidian in a matrix of predominantly pumice lapilli. Incomplete alteration of the hyaloclastite resulted in the non pervasive argillic zone, characterized by smectite and disordered opal-CT. Obsidian clasts, some pumice lapilli, and pyrogenic plagioclase and biotite are unaltered. Smectite has an irregular flakey morphology, although euhedral particles are occasionally observed. The propylitic zone is characterized by mixed-layer illite/smectite (I/S) with 10 to 85% illite (I), mordenite, opal-C and authigenic K-feldspar (akspar). The matrix of the hyaloclastite is completely altered and obsidian clasts are silicified; however, plagioclase and biotite phenocrysts remain unaltered. Flakey I/S replaces pumice, and mordenite, akspar and silica line and fill pores. I/S particles are composed predominantly of subequant plates and euhedral laths. The silicic zone is characterized by highly illitic I/S with ≥ 90% I, quartz, akspar and occasional albite. In this zone the matrix and clasts are completely altered, and pyrogenic plagioclase shows significant alteration. Illitic I/S has a euhedral lath-like morphology. In the sericitic zone the hyaloclastite altered primarily to illitic I/S with ≥ 66% I, quartz, and minor akspar and pyrite. Clay minerals completely replace pyrogenic feldspars and little evidence remains of the original hyaloclastite texture. Unlike other zones, illitic I/S is fibrous and pure illite samples are composed of euhedral laths and hexagonal plates. The temperatures of hydrothermal alteration likely ranged from 30 to 90 °C for the argillic zone, from 110 to 160 °C for the propylitic zone, from 160 to 270 °C for the silicic zone, and were possibly as high as 300 °C for the sericitic zone. The four zones occur as linear bands that increase in intensity north of the bentonite mine at Cala dell'Acqua. The alteration zones have two orientations and may be structurally controlled by E-W- and NE-SW-trending faulting which is consistent with the dominant structural trends of the Pontine archipelago. Finally, hydrothermal alteration most likely involved seawater based on the geologic evolution of Ponza.

The Status of Water in Swelling Shales: An Insight from the Water Retention Properties of the Callovo-Oxfordian Claystone

NASA Astrophysics Data System (ADS)

Menaceur, Hamza; Delage, Pierre; Tang, Anh Minh; Talandier, Jean

2016-12-01

The Callovo-Oxfordian (COx) claystone is considered in France as a possible host rock for the disposal of high-level long-lived radioactive waste at great depth. During the operational phase, the walls of the galleries and of the disposal cells will be successively subjected to desaturation induced by ventilation followed by resaturation once the galleries are closed. To better understand this phenomenon, a sound understanding of the water retention properties of the COx claystone is necessary. Following a previous study by the same group, this paper presents an investigation of microstructure changes in COx claystone under suction changes. Microstructure was investigated by means of mercury intrusion porosimetry tests on freeze-dried specimens previously submitted to various suctions. Along the drying path, the initial microstructure, characterised by a well-classified unimodal pore population around a mean diameter value of 32 nm, slightly changed with the same shape of the PSD curve and slightly moved towards smaller diameters (27-28 nm) at suctions of 150 and 331 MPa, respectively. The infra-porosity too small to be intruded by mercury (diameter smaller than 5.5 nm) reduced from 4.3 to 3.3 %. Oven drying reduced the mean diameter to 20 nm and the infra-porosity to 1 %. Wetting up to 9 MPa suction leads to saturation with no significant change in the PSD curve, whereas wetting at zero suction gave rise to the appearance of a large pore population resulting from the development of cracks with width of several micrometres, together with an enlargement of the initial pore population above the mean diameter. The concepts describing the step hydration of smectites (by the successive placement within the clay platelets along the smectite faces of 1, 2, 3 and 4 layers of water molecules with respect to the suction applied) appeared relevant to better understand the changes in microstructure of the COx claystone under suction changes. This also allowed to better define the status of water in claystones and shales containing smectite, with a distinction made between the water adsorbed within the clay platelets, and the free inter-platelet water involved in hydromechanical couplings through changes in pore pressure and water transfers.

Reconstruction of Ancestral Hydrothermal Systems on Mount Rainier Using Hydrothermally Altered Rocks in Holocene Debris Flows and Tephras

NASA Astrophysics Data System (ADS)

John, D. A.; Breit, G. N.; Sisson, T. W.; Vallance, J. W.; Rye, R. O.

2005-12-01

Mount Rainier is the result of episodic stages of edifice growth during periods of high eruptive activity and edifice destruction during periods of relative magmatic quiescence over the past 500 kyr. Edifice destruction occurred both by slow erosion and by catastrophic collapses, some of which were strongly influenced by hydrothermal alteration. Several large-volume Holocene debris-flow deposits contain abundant clasts of hydrothermally altered rocks, most notably the 4-km3 clay-rich Osceola Mudflow which formed by collapse of the northeast side and upper 1000+ m of the edifice about 5600 ya and flowed >120 km downstream into Puget Sound. Mineral assemblages and stable isotope data of hydrothermal alteration products in Holocene debris-flow deposits indicate formation in distinct hydrothermal environments, including magmatic-hydrothermal, steam-heated (including a large fumarolic component), magmatic steam (including a possible fumarolic component), and supergene. The Osceola Mudflow and phreatic components of coeval tephras contain the highest-temperature and inferred most deeply formed alteration minerals; assemblages include magmatic-hydrothermal quartz-alunite, quartz-topaz, quartz-pyrophyllite and quartz-illite (all +pyrite), in addition to steam-heated opal-alunite-kaolinite and abundant smectite-pyrite. In contrast, the Paradise lahar, which formed by a collapse of the surficial upper south side of the edifice, contains only steam-heated assemblages including those formed largely above the water table from condensation of fumarolic vapor (opal-alunite-jarosite). Younger debris-flow deposits on the west side of the volcano (Round Pass lahar and Electron Mudflow) contain only smectite-pyrite alteration, whereas an early 20th century rock avalanche on Tahoma Glacier also contains magmatic-hydrothermal alteration that is exposed in the avalanche headwall of Sunset Amphitheater. Mineralogy and isotopic composition of the alteration phases, geologic and geophysical data, as well as analog fossil hydrothermal systems in volcanoes elsewhere, constrain hydrothermal alteration geometry on the pre-Osceola-collapse edifice of Mount Rainier. Relatively narrow zones of acid magmatic-hydrothermal alteration in the central core of the volcano grade to more widely distributed smectite-pyrite alteration farther out on the upper flanks, capped by steam-heated alteration with a large component of alteration resulting from condensation of fumarolic vapor above the water table. Alteration was polygenetic in zones formed episodically, and was strongly controlled by fluxes of heat and magmatic fluid and by local permeability.

U.S. Geological survey program on toxic waste--ground-water contamination; proceedings of the Second technical meeting, Cape Cod, Massachusetts, October 21-25, 1985

USGS Publications Warehouse

Ragone, S.E.

1988-01-01

This study characterizes the clay minerals in sediments associated with a plume of creosote-contaminated groundwater. The plume of contaminated groundwater near Pensacola, FL, is in shallow, permeable, Miocene to Holocene quartz sand and flows southward toward Pensacola Bay. Clay-size fractions were separated from 41 cores, chiefly split-spoon samples at 13 drill sites. The most striking feature of the chemical analyses of the clay fractions from uncontaminated site 2 and contaminated sites 4,5,6, and 7 is the variability of iron oxide (species in some samples as Fe2O3); total iron oxide abundance is lowest (2.5%) in uncontaminated sample 2-40, but is > 4.5% (4.5 to 8.5%) in the remaining assemblages. One feature suggesting interaction between the indigenous clays and the waste plume is the presence of nontronite-rich smectite. Nontronite commonly has been identified as the product of hydrothermal alteration and deep-sea weathering of submarine basalts; it is not a common constituent of Cenozoic Gulf Coast sediments. At the Pensacola site, relatively abundant nontronitic smectite is confined to contaminated sands or associated muds; it is least abundant or absent in sands and muds peripheral to the waste plume. The geochemistry of the waste plume, its substantial dissolved, (chiefly ferrous iron), mildly acidic (pH 5-6), and low redox composition, provides an environment similar to that previously determined for the low-temperature synthesis of nontronite. Data from clay-size fractions confirm conclusions that neoformed pyrite in some grain coatings occurs in an assemblage with excess iron over that required in the pyrite. Continuing studies to evaluate these tentative conclusions include: (1) chemical analysis of clay fractions from remaining sites to further examine the apparent relation between iron content and abundance of nontronitic smectite; (2) clay separation and analysis, and pore fluid extraction (squeezing or ultracentrifugation) and analysis from a continuous core through the mud lens to determine pore fluid composition (presence or absence of waste fluid), and character of associated clay minerals; and (3) clay separation and analysis in both permeable sands and the intervening mud lens that are clearly outside the limits of the waste plume to further document the effects of the plume. (See also W90-00022) (Lantz-PTT)

Microstructures Indicate Large Influence of Temperature and Fluid Pressure on the Reactivation of the Alpine Fault, New Zealand

NASA Astrophysics Data System (ADS)

Schuck, B.; Janssen, C.; Schleicher, A.; Toy, V.; Dresen, G.

2017-12-01

The transpressional Alpine Fault within New Zealand's South Island is the major structure that accommodates relative motion between the Pacific and the Australian Plates. It has been intensively studied, because it is late in its 291-year seismic cycle (Cochran et al., 2017; doi: 10.1016/j.epsl.2017.02.026), is likely to generate large (i.e. MW > 8) earthquakes, thus presents the biggest seismic hazard in the region. However, because it is severely misoriented in the present-day stress field for reactivation (Boese et al., 2013; doi: 10.1016/j.epsl.2013.06.030), supra-lithostatic fluid-pressures are required for rupture nucleation. We have analyzed microstructures (SEM and TEM), geochemistry (ICP-OES) and mineralogy (XRD) of outcrop samples of the fault core to investigate the influence of fluids on the geomechanical behavior of the fault. Fluid-related alteration is pervasive within 20 m of the principal slip zone (PSZ) (Sutherland et al., 2012; doi: 10.1130/G33614.1), which is an incohesive, cemented and repeatedly reworked fault gouge mostly consisting of a fine-grained matrix composed of comminuted detrital quartz and feldspar as well as authigenic chlorite and calcite. Authigenic phases seal the PSZ for interseismic cross-fault fluid flow and enable fluid pressure to build-up. Notable, smectite, previously considered to significantly influence propagation of Alpine Fault ruptures, is not present in these samples. Undeformed, euhedral chlorite grains suggest that the processes leading to fault sealing are not only active at greater depths but also close to the surface. The absence of smectite and the presence of undeformed chlorite at very shallow depths can be attributed to the fault's high geothermal gradient of > 120 °C km-1 (Sutherland et al., 2012; doi:10.1038/nature22355), which gives temperature conditions unfavorable for smectite to be stable and fostering chlorite growth. A pervasive network of anastomosing calcite veins in the fault core, depicting mutual cross-cutting relations, attests for episodic fluid flow and mineralization within the PSZ. We interpret these as microstructural evidence for transient fault core permeability resulting from rupture nucleation due to supra-lithostatic fluid pressures following during fault-valve behavior.

Spectroscopic study of the dehydration and/or dehydroxylation of phyllosilicate and zeolite minerals

NASA Astrophysics Data System (ADS)

Che, Congcong; Glotch, Timothy D.; Bish, David L.; Michalski, Joseph R.; Xu, Wenqian

2011-05-01

Phyllosilicates on Mars mapped by infrared spectroscopic techniques could have been affected by dehydration and/or dehydroxylation associated with chemical weathering in hyperarid conditions, volcanism or shock heating associated with meteor impact. The effects of heat-induced dehydration and/or dehydroxylation on the infrared spectra of 14 phyllosilicates from four structural groups (kaolinite, smectite, sepiolite-palygorskite, and chlorite) and two natural zeolites are reported here. Pressed powders of size-separated phyllosilicate and natural zeolite samples were heated incrementally from 100°C to 900°C, cooled to room temperature, and measured using multiple spectroscopic techniques: midinfrared (400-4000 cm-1) attenuated total reflectance, midinfrared reflectance (400-1400 cm-1), and far-infrared reflectance (50-600 cm-1) spectroscopies. Correlated thermogravimetric analysis and X-ray diffraction data were also acquired in order to clarify the thermal transformation of each sample. For phyllosilicate samples, the OH stretching (˜3600 cm-1), OH bending (˜590-950 cm-1), and/or H2O bending (˜1630 cm-1) bands all become very weak or completely disappear upon heating to temperatures > 500°C. The spectral changes associated with SiO4 vibrations (˜1000 cm-1 and ˜500 cm-1) show large variations depending on the compositions and structures of phyllosilicates. The thermal behavior of phyllosilicate IR spectra is also affected by the type of octahedral cations. For example, spectral features of Al3+-rich smectites are more stable than those of Fe3+-rich smectites. The high-temperature (>800°C) spectral changes of trioctahedral Mg2+-rich phyllosilicates such as hectorite, saponite, and sepiolite result primarily from crystallization of enstatite. Phyllosilicates with moderate Mg2+ concentration (e.g., palygorskite, clinochlore) and dioctahedral montmorillonites (e.g., SAz-1 and SCa-3) with partial Mg2+-for-Al3+ substitution all have new spectral feature developed at ˜900 cm-1 upon heating to 800°C. Compared with phyllosilicates, spectral features of two natural zeolites, clinoptilolite and mordenite, are less affected by thermal treatments. Even after heating to 900°C, the IR spectral features attributed to Si (Al)-O stretching and bending vibration modes do not show significant differences from those of unheated zeolites.

Climatic and palaeoceanographic changes during the Pliensbachian (Early Jurassic) inferred from clay mineralogy and stable isotope (C-O) geochemistry (NW Europe)

NASA Astrophysics Data System (ADS)

Bougeault, Cédric; Pellenard, Pierre; Deconinck, Jean-François; Hesselbo, Stephen P.; Dommergues, Jean-Louis; Bruneau, Ludovic; Cocquerez, Théophile; Laffont, Rémi; Huret, Emilia; Thibault, Nicolas

2017-02-01

The Early Jurassic was broadly a greenhouse climate period that was punctuated by short warm and cold climatic events, positive and negative excursions of carbon isotopes, and episodes of enhanced organic matter burial. Clay minerals from Pliensbachian sediments recovered from two boreholes in the Paris Basin, are used here as proxies of detrital supplies, runoff conditions, and palaeoceanographic changes. The combined use of these minerals with stable isotope data (C-O) from bulk carbonates and organic matter allows palaeoclimatic reconstructions to be refined for the Pliensbachian. Kaolinite/illite ratio is discussed as a reliable proxy of the hydrological cycle and runoff from landmasses. Three periods of enhanced runoff are recognised within the Pliensbachian. The first one at the Sinemurian-Pliensbachian transition shows a significant increase of kaolinite concomitant with the negative carbon isotope excursion at the so-called Sinemurian Pliensbachian Boundary Event (SPBE). The Early/Late Pliensbachian transition was also characterised by more humid conditions. This warm interval is associated with a major change in oceanic circulation during the Davoei Zone, likely triggered by sea-level rise; the newly created palaeogeography, notably the flooding of the London-Brabant Massif, allowed boreal detrital supplies, including kaolinite and chlorite, to be exported to the Paris Basin. The last event of enhanced runoff occurred during the late Pliensbachian (Subnodosus Subzone of the Margaritatus Zone), which occurred also during a warm period, favouring organic matter production and preservation. Our study highlights the major role of the London Brabant Massif in influencing oceanic circulation of the NW European area, as a topographic barrier (emerged lands) during periods of lowstand sea-level and its flooding during period of high sea-level. This massif was the unique source of smectite in the Paris Basin. Two episodes of smectite-rich sedimentation ('smectite events'), coincide with regressive intervals, indicating emersion of the London Brabant Massif and thus suggesting that an amplitude of sea-level change high enough to be linked to glacio-eustasy. This mechanism is consistent with sedimentological and geochemical evidences of continental ice growth notably during the Latest Pliensbachian (Spinatum Zone), and possibly during the Early Pliensbachian (late Jamesoni/early Ibex Zones).

A Quantitative Geochemical, Mineralogical and Physical Study of Some Selected Rock Weathering Profiles from Brazil

DTIC Science & Technology

1977-08-17

weather to gibbsite (plus or minus iron oxides) in well-drained, and smectite in poorly-drained, environments. Kaolinite found in the vicinity of quartz...rock and completely weathered saprolite. Quartz-rich rock types exhibit wide, gradational weathered zones and usually form kaolinite or halloysite in...free rocks is either formed by re-silication of gibbsite , or is of secondary origin (transported). Texture of the rock (aphanitic vs. phaneric) has

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

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

PubMed Central

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

2015-01-01

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

Impact of hydrothermal alteration on time-dependent tunnel deformation in Neogene volcanic rock sequence in Japan: Petrology, Geochemistry and Geophysical investigation

NASA Astrophysics Data System (ADS)

Yamazaki, S.; Okazaki, K.; Niwa, H.; Arai, T.; Murayama, H.; Kurahashi, T.; Ito, Y.

2017-12-01

Time-dependent tunnel deformation is one of remaining geological problems for mountain tunneling. As a case study of time-dependent tunnel deformation, we investigated petrographical, mineral and chemical compositions of boring core samples and seismic exploration along a tunnel that constructed into Neogene volcanic rock sequence of andesite to dacite pyroclastic rocks and massive lavas with mafic enclaves. The tunnel has two zones of floor heaving that deformed time-dependently about 2 month after the tunnel excavation. The core samples around the deformed zones are characterized secondary mineral assemblages of smectite, cristobalite, tridymite, sulfides (pyrite and marcasite) and partially or completely reacted carbonates (calcite and siderite), which were formed by hydrothermal alteration under neutral to acidic condition below about 100 °C. The core samples also showed localized deterioration, such as crack formation and expansion, which occurred from few days to months after the drilling. The deterioration could be explained as a result of the cyclic physical and chemical weathering process with the oxidation of sulfide minerals, dissolution of carbonate mineral cementation and volumetric expantion of smectite. This weathering process is considered as a key factor for time-dependent tunnel deformation in the hydrothermally altered volcanic rocks. The zones of time-dependent deformation along a tunnel route can be predicted by the variations of whole-rock chemical compositions such as Na, Ca, Sr, Ba and S.

Corrosion of high-level radioactive waste iron-canisters in contact with bentonite.

PubMed

Kaufhold, Stephan; Hassel, Achim Walter; Sanders, Daniel; Dohrmann, Reiner

2015-03-21

Several countries favor the encapsulation of high-level radioactive waste (HLRW) in iron or steel canisters surrounded by highly compacted bentonite. In the present study the corrosion of iron in contact with different bentonites was investigated. The corrosion product was a 1:1 Fe layer silicate already described in literature (sometimes referred to as berthierine). Seven exposition test series (60 °C, 5 months) showed slightly less corrosion for the Na-bentonites compared to the Ca-bentonites. Two independent exposition tests with iron pellets and 38 different bentonites clearly proved the role of the layer charge density of the swelling clay minerals (smectites). Bentonites with high charged smectites are less corrosive than bentonites dominated by low charged ones. The type of counterion is additionally important because it determines the density of the gel and hence the solid/liquid ratio at the contact to the canister. The present study proves that the integrity of the multibarrier-system is seriously affected by the choice of the bentonite buffer encasing the metal canisters in most of the concepts. In some tests the formation of a patina was observed consisting of Fe-silicate. Up to now it is not clear why and how the patina formed. It, however, may be relevant as a corrosion inhibitor. Copyright © 2014 Elsevier B.V. All rights reserved.

Multiple techniques for mineral identification of terrestrial evaporites relevant to Mars exploration

NASA Astrophysics Data System (ADS)

Stivaletta, N.; Dellisanti, F.; D'Elia, M.; Fonti, S.; Mancarella, F.

2013-05-01

Sulfates, commonly found in evaporite deposits, were observed on Mars surface during orbital remote sensing and surface exploration. In terrestrial environments, evaporite precipitation creates excellent microniches for microbial colonization, especially in desert areas. Deposits comprised of gypsum, calcite, quartz and silicate deposits (phyllosilicates, feldspars) from Sahara Desert in southern Tunisia contain endolithic colonies just below the rock surface. Previous optical observations verified the presence of microbial communities and, as described in this paper, spectral visible analyses have led to identification of chlorophylls belonging to photosynthetic bacteria. Spectral analyses in the infrared region have clearly detected the presence of gypsum and phyllosilicates (mainly illite and/or smectite), as well as traces of calcite, but not quartz. X-ray diffraction (XRD) analysis has identified the dominant presence of gypsum as well as that of other secondary minerals such as quartz, feldspars and Mg-Al-rich phyllosilicates, such as chlorite, illite and smectite. The occurrence of a small quantity of calcite in all the samples was also highlighted by the loss of CO2 by thermal analysis (TG-DTA). A normative calculation using XRD, thermal data and X-ray fluorescence (XRF) analysis has permitted to obtain the mineralogical concentration of the minerals occurring in the samples. The combination of multiple techniques provides information about the mineralogy of rocks and hence indication of environments suitable for supporting microbial life on Mars surface.

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.

Experimental Study of Cement - Sandstone/Shale - Brine - CO2 Interactions

PubMed Central

2011-01-01

Background Reactive-transport simulation is a tool that is being used to estimate long-term trapping of CO2, and wellbore and cap rock integrity for geologic CO2 storage. We reacted end member components of a heterolithic sandstone and shale unit that forms the upper section of the In Salah Gas Project carbon storage reservoir in Krechba, Algeria with supercritical CO2, brine, and with/without cement at reservoir conditions to develop experimentally constrained geochemical models for use in reactive transport simulations. Results We observe marked changes in solution composition when CO2 reacted with cement, sandstone, and shale components at reservoir conditions. The geochemical model for the reaction of sandstone and shale with CO2 and brine is a simple one in which albite, chlorite, illite and carbonate minerals partially dissolve and boehmite, smectite, and amorphous silica precipitate. The geochemical model for the wellbore environment is also fairly simple, in which alkaline cements and rock react with CO2-rich brines to form an Fe containing calcite, amorphous silica, smectite and boehmite or amorphous Al(OH)3. Conclusions Our research shows that relatively simple geochemical models can describe the dominant reactions that are likely to occur when CO2 is stored in deep saline aquifers sealed with overlying shale cap rocks, as well as the dominant reactions for cement carbonation at the wellbore interface. PMID:22078161

[Effects of Long-term Implementation of the Flow-Sediment Regulation Scheme on Grain and Clay Compositions of Inshore Sediments in the Yellow River Estuary].

PubMed

Wang, Miao-miao; Sun, Zhi-gao; Lu, Xiao-ning; Wang, Wei; Wang, Chuan-yuan

2015-04-01

Based on the laser particle size and X-ray diffraction (XRD) analysis, 28 sediment samples collected from the inshore region of the Yellow River estuary in October 2013 were determined to discuss the influence of long-term implementation of the flow-sediment regulation scheme (FSRS, initiated in 2002) on the distributions of grain size and clay components (smectite, illite, kaolinite and chlorite) in sediments. Results showed that, after the FSRS was implemented for more than 10 years, although the proportion of sand in inshore sediments of the Yellow River estuary was higher (average value, 23.5%) than those in sediments of the Bohai Sea and the Yellow River, silt was predominated (average value, 59.1%) and clay components were relatively low (average value, 17.4%). The clay components in sediments of the inshore region in the Yellow River estuary were close with those in the Yellow River. The situation was greatly changed due to the implementation of FSRS since 2002, and the clay components were in the order of illite > smectite > chlorite > kaolinite. This study also indicated that, compared to large-scale investigation in Bohai Sea, the local study on the inshore region of the Yellow River estuary was more favorable for revealing the effects of long-term implementation of the FSRS on sedimentation environment of the Yellow River estuary.

Water Structure and Dynamics in Smectites: X-ray Diffraction and 2 H NMR Spectroscopy of Mg–, Ca–, Sr–, Na–, Cs–, and Pb–Hectorite

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

Reddy, U. Venkateswara; Bowers, Geoffrey M.; Loganathan, Narasimhan

2016-04-06

Variable-temperature X-ray diffraction and 2H NMR spectroscopy of the smectite mineral, hectorite, containing interlayer Na +, K +, Cs +, Mg 2+, Ca 2+, Sr 2+, and Pb 2+ equilibrated at 43% relative humidity (RH) and mixed with 2H 2O to form a paste provide a comprehensive picture of the structural environments and dynamics of interlayer 2H 2O and the relationships of these properties to interlayer hydration state, the hydration energy and polarizability of the cation, temperature, and the formation of ice-1h in the interparticle pores. The variation in basal spacing shown by the XRD data correlates well with themore » 2H NMR behavior, and the XRD data show for the first time in hectorites that crystallization of interparticle ice-1h causes a decrease in the interlayer spacing, likely due to removal of interlayer 2H 2O. The variation of the 2H NMR behavior of all the samples with decreasing temperature reflects decreasing frequencies of motion for the rotation of the 2H 2O molecules around their dipoles, reorientation of the 2H 2O molecules, and exchange of the 2H 2O molecules between interlayer sites coordinated to and not coordinated to the cations.« less

Discovery and Description of Giant Submarine Smectite Cones on the Seafloor in Eyjafjordur, Northern Iceland, and a Novel Thermal Microbial Habitat

PubMed Central

Marteinsson, Viggó Thór; Kristjánsson, Jakob K.; Kristmannsdóttir, Hrefna; Dahlkvist, Maria; Sæmundsson, Kristján; Hannington, Mark; Pétursdóttir, Sólveig K.; Geptner, Alfred; Stoffers, Peter

2001-01-01

With the submersible JAGO and by scuba diving we discovered three remarkable geothermal cones, rising 33, 25, and 45 m from the seafloor at a depth of 65 m in Eyjafjordur, northern Iceland. The greatest geothermal activity was on the highest cone, which discharged up to 50 liters of freshwater per s at 72°C and pH 10.0. The cones were built up from precipitated smectite, formed by mixing of the hot SiO2-rich geothermal fluid with the cold Mg-rich seawater. By connecting a rubber hose to one outflow, about 240 liters of pure geothermal fluids was concentrated through a 0.2-μm-pore-size filter. Among 50 thermophilic isolates, we found members of Bacillus and Thermonema and a new unidentified low-G+C gram-positive member of the Bacteria as well as one member of the Archaea, Desulfurococcus mobilis. Analysis of small-subunit rRNA genes PCR amplified and cloned directly from environmental DNA showed that 41 out of 45 Bacteria sequences belonged to members of the Aquificales, whereas all of the 10 Archaea sequences belonged to the Korarchaeota. The physiological characteristics of isolates from different parts of the cones indicate a completely freshwater habitat, supporting the possibility of subterranean transmittance of terrestrial organisms. PMID:11157250

Reduction of structural Fe(III) in nontronite by methanogen Methanosarcina barkeri

USGS Publications Warehouse

Liu, D.; Dong, Hailiang H.; Bishop, M.E.; Wang, Hongfang; Agrawal, A.; Tritschler, S.; Eberl, D.D.; Xie, S.

2011-01-01

Clay minerals and methanogens are ubiquitous and co-exist in anoxic environments, yet it is unclear whether methanogens are able to reduce structural Fe(III) in clay minerals. In this study, the ability of methanogen Methanosarcina barkeri to reduce structural Fe(III) in iron-rich smectite (nontronite NAu-2) and the relationship between iron reduction and methanogenesis were investigated. Bioreduction experiments were conducted in growth medium using three types of substrate: H2/CO2, methanol, and acetate. Time course methane production and hydrogen consumption were measured by gas chromatography. M. barkeri was able to reduce structural Fe(III) in NAu-2 with H2/CO2 and methanol as substrate, but not with acetate. The extent of bioreduction, as measured by the 1,10-phenanthroline method, was 7-13% with H2/CO2 as substrate, depending on nontronite concentration (5-10g/L). The extent was higher when methanol was used as a substrate, reaching 25-33%. Methanogenesis was inhibited by Fe(III) reduction in the H2/CO2 culture, but enhanced when methanol was used. High charge smectite and biogenic silica formed as a result of bioreduction. Our results suggest that methanogens may play an important role in biogeochemical cycling of iron in clay minerals and may have important implications for the global methane budget. ?? 2010 Elsevier Ltd.

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.

Immobilization of soil cadmium using combined amendments of illite/smectite clay with bone chars.

PubMed

Li, Hong; Ou, Jieyong; Wang, Xuedong; Yan, Zengguang; Zhou, Youya

2018-05-12

The widespread use of cadmium (Cd)-containing organic fertilizers is a source of heavy metal inputs to agricultural soils in suburban areas. Therefore, the research and development of new materials and technologies for the remediation of Cd-contaminated soil is of great significance and has the potential to guarantee the safety of agricultural products and the protection of human health. We performed pot experiments to determine the potential of combined amendments of illite/smectite (I/S) clay with bone chars for the remediation of Cd-contaminated agricultural soils in a suburban area of Beijing, China. The results showed that both diethylene triamine pentaacetic acid (DTPA)-extractable Cd in soil and the Cd in Brassica chinensis were significantly decreased by the application of 1, 2, or 5% combined amendments with various I/S and bone char (BC) ratios. The higher proportions of BC used in the combined amendments resulted in a better immobilization of soil Cd. The application of the 5% amendment that combined I/S with either pig or cattle BC resulted in the best immobilization. All of the combined amendments, regardless of the composition and ratio of the components, had no negative effects on the growth of B. chinensis. Therefore, it was concluded that combined amendments of I/S and BC have a good potential for remediating Cd-contaminated soils.

Clay mineralogical and geochemical proxies of the East Asian summer monsoon evolution in the South China Sea during Late Quaternary

PubMed Central

Chen, Quan; Liu, Zhifei; Kissel, Catherine

2017-01-01

The East Asian summer monsoon controls the climatic regime of an extended region through temperature and precipitation changes. As the East Asian summer monsoon is primarily driven by the northern hemisphere summer insolation, such meteorological variables are expected to significantly change on the orbital timescale, influencing the composition of terrestrial sediments in terms of both mineralogy and geochemistry. Here we present clay mineralogy and major element composition of Core MD12-3432 retrieved from the northern South China Sea, and we investigate their relationship with the East Asian summer monsoon evolution over the last 400 ka. The variability of smectite/(illite + chlorite) ratio presents a predominant precession periodicity, synchronous with the northern hemisphere summer insolation changes and therefore with that of the East Asian summer monsoon. Variations in K2O/Al2O3 are characterized by eccentricity cycles, increasing during interglacials when the East Asian summer monsoon is enhanced. Based on the knowledge of sediment provenances, we suggest that these two proxies in the South China Sea are linked to the East Asian summer monsoon evolution with different mechanisms, which are (1) contemporaneous chemical weathering intensity in Luzon for smectite/(illite + chlorite) ratio and (2) river denudation intensity for K2O/Al2O3 ratio of bulk sediment. PMID:28176842

Clay mineralogical and geochemical proxies of the East Asian summer monsoon evolution in the South China Sea during Late Quaternary.

PubMed

Chen, Quan; Liu, Zhifei; Kissel, Catherine

2017-02-08

The East Asian summer monsoon controls the climatic regime of an extended region through temperature and precipitation changes. As the East Asian summer monsoon is primarily driven by the northern hemisphere summer insolation, such meteorological variables are expected to significantly change on the orbital timescale, influencing the composition of terrestrial sediments in terms of both mineralogy and geochemistry. Here we present clay mineralogy and major element composition of Core MD12-3432 retrieved from the northern South China Sea, and we investigate their relationship with the East Asian summer monsoon evolution over the last 400 ka. The variability of smectite/(illite + chlorite) ratio presents a predominant precession periodicity, synchronous with the northern hemisphere summer insolation changes and therefore with that of the East Asian summer monsoon. Variations in K 2 O/Al 2 O 3 are characterized by eccentricity cycles, increasing during interglacials when the East Asian summer monsoon is enhanced. Based on the knowledge of sediment provenances, we suggest that these two proxies in the South China Sea are linked to the East Asian summer monsoon evolution with different mechanisms, which are (1) contemporaneous chemical weathering intensity in Luzon for smectite/(illite + chlorite) ratio and (2) river denudation intensity for K 2 O/Al 2 O 3 ratio of bulk sediment.

Zeolites in Eocene basaltic pillow lavas of the Siletz River Volcanics, Central Coast Range, Oregon

USGS Publications Warehouse

Keith, Terry E.C.; Staplese, Lloyd W.

1985-01-01

Zeolites and associated minerals occur in a tholeiitic basaltic pillow lava sequence that makes up part of the Eocene Siletz River Volcanics in the central Coast Range, Oregon. Regional zoning of zeolite assemblages is not apparent; the zeolites formed in joints, fractures, and interstices, although most occur in central cavities of basalt pillows. The zeolites and associated minerals identified, in general order of paragenetic sequence, are smectite, pyrite, calcite (small spheres), thomsonite, natrolite, analcime, scolecite, mesolite, stilbite, heulandite, apophyllite, chahazite, mordenite, calcite (scalenohedra and twinned rhombohedra), laumontite, and amethystine quartz. Common three-mineral assemblages are: natrolite-analcime-sfilbite, stilbite-heulandite-chabazite, stilbite-apophyllie-chabazite, and natrolite-mesolite-laumontite.Alteration of basaltic glass, which was initially abundant, appears to have been an important factor in formation of the zeolites. Isotopic data suggest that zeolitization occurred during a low-temperature (60 ~ 70°C submarine hydrothermal event, or by reactions of cold (~ 10°C meteoric water with basalt over a long time. The occurrence of different mineral assemblages in cavities of adjacent basalt pillows indicates that these minerals crystallized in dosed systems that were isolated as fractures and joints were sealed by deposition of smectite and early zeolites. Although the total chemical composition of the mineral assemblages in cavities is similar, different mineral species formed because of the sensitivity of zeolite minerals to slight variations in physical and chemical conditions within individual cavities.

NMR and Electrochemical Investigation of the Transport Properties of Methanol and Water in Nafion and Clay-Nanocomposites Membranes for DMFCs

PubMed Central

Nicotera, Isabella; Angjeli, Kristina; Coppola, Luigi; Aricò, Antonino S.; Baglio, Vincenzo

2012-01-01

Water and methanol transport behavior, solvents adsorption and electrochemical properties of filler-free Nafion and nanocomposites based on two smectite clays, were investigated using impedance spectroscopy, DMFC tests and NMR methods, including spin-lattice relaxation and pulsed-gradient spin-echo (PGSE) diffusion under variable temperature conditions. Synthetic (Laponite) and natural (Swy-2) smectite clays, with different structural and physical parameters, were incorporated into the Nafion for the creation of exfoliated nanocomposites. Transport mechanism of water and methanol appears to be influenced from the dimensions of the dispersed platelike silicate layers as well as from their cation exchange capacity (CEC). The details of the NMR results and the effect of the methanol solution concentration are discussed. Clays particles, and in particular Swy-2, demonstrate to be a potential physical barrier for methanol cross-over, reducing the methanol diffusion with an evident blocking effect yet nevertheless ensuring a high water mobility up to 130 °C and for several hours, proving the exceptional water retention property of these materials and their possible use in the DMFCs applications. Electrochemical behavior is investigated by cell resistance and polarization measurements. From these analyses it is derived that the addition of clay materials to recast Nafion decreases the ohmic losses at high temperatures extending in this way the operating range of a direct methanol fuel cell. PMID:24958179

Geological and technological characterization of the Late Jurassic-Early Cretaceous clay deposits (Jebel Ammar, northeastern Tunisia) for ceramic industry

NASA Astrophysics Data System (ADS)

Ben M'barek-Jemaï, Moufida; Sdiri, Ali; Ben Salah, Imed; Ben Aissa, Lassaad; Bouaziz, Samir; Duplay, Joelle

2017-05-01

Late Jurassic-Lower Cretaceous clays of the Jebel Ammar study site were used as raw materials for potential applications in ceramic industry. Physico-chemical characterization of the collected samples was performed using atomic absorption spectroscopy, X-ray diffraction, thermogravimetry and dilatometry (Bugot's curve). Geotechnical study was also undertaken by the assessment of plasticity and liquidity limits. It was found that high concentrations of silica, alumina with SiO2/Al2O3 ratio characterized the studied clays; its high amounts of CaO and Fe2O3 in the Late Jurassic clays indicated their calcareous nature. In addition, technological tests indicated moderate to low plasticity values for the Late Jurassic and Lower Cretaceous clays, respectively. Clay fraction (<2 μm) reached 50% of the natural clay in some cases. Mineralogical analysis showed that Jurassic clays were dominated by smectite, illite and kaolinite, as clay mineral species; calcite was the main associated mineral. Lower Cretaceous clays were mainly composed of abundant illite accompanied by well-crystallized smectite and kaolinite. Kaolinite gradually increased upwards, reaching 70% of the total clay fraction (i.e. <2 μm). Quartz, calcite and feldspar were the main non-clay minerals. Based on these analyses, the clays meet technological requirements that would allow their use in the ceramic industry and for the manufacturing of ceramic tiles.

Heterogeneous photo-Fenton decolorization of Orange II over Al-pillared Fe-smectite: response surface approach, degradation pathway, and toxicity evaluation.

PubMed

Li, Huiyuan; Li, Yanli; Xiang, Luojing; Huang, Qianqian; Qiu, Juanjuan; Zhang, Hui; Sivaiah, Matte Venkata; Baron, Fabien; Barrault, Joel; Petit, Sabine; Valange, Sabine

2015-04-28

A ferric smectite clay material was synthesized and further intercalated with Al2O3 pillars for the first time with the aim of evaluating its ability to be used as heterogeneous catalyst for the photo-Fenton decolorization of azo dye Orange II. UV irradiation was found to enhance the activity of the catalyst in the heterogeneous photo-Fenton process. Catalyst loading of 0.5g/L and hydrogen peroxide concentration of 13.5mM yielded a remarkable color removal, accompanied by excellent catalyst stability. The decolorization of Orange II followed the pseudo-first-order kinetics for initial dye concentrations from 20 to 160mg/L. The central composite design (CCD) based on the response surface methodology (RSM) was applied to evaluate the effects of several operating parameters, namely initial pH, catalyst loading and hydrogen peroxide concentration, on the decolorization efficiency. The RSM model was derived and the response surface plots were developed based on the results. Moreover, the main intermediate products were separated and identified using gas chromatography-mass spectrometry (GC-MS) and a possible degradation pathway was proposed accordingly. The acute toxicity experiments illustrated that the Daphniamagna immobilization rate continuously decreased during 150min reaction, indicating that the effluent was suitable for sequential biological treatment. Copyright © 2015 Elsevier B.V. All rights reserved.

Dechlorination of chlorinated phenols by subnanoscale Pd 0 /Fe 0 intercalated in smectite: pathway, reactivity, and selectivity.

PubMed

Jia, Hanzhong; Wang, Chuanyi

2015-12-30

Smectite clay was employed as templated matrix to prepare subnanoscale Pd(0)/Fe(0) particles, and their components as well as intercalated architectures were well characterized by X-ray energy dispersive spectroscopy (X-EDS) and X-ray diffraction (XRD). Furthermore, as-prepared Pd(0)/Fe(0) subnanoscale nanoparticles were evaluated for their dechlorination effect using chlorinated phenols as model molecules. As a result, pentachlorophenol (PCP) is selectively transformed to phenol in a stepwise dechlorination pathway within 6h, and the dechlorination rate constants show linearly relationship with contents of Pd as its loadings <0.065%. Comparing with PCP, other chlorinated phenols display similar degradation pattern but within much shorter time frame. The dechlorination rate of chlorinated phenols increases with decreasing in number of -Cl attached to aromatic ring, which can be predicted by the total charge of the aromatic ring, exhibiting an inversely linear relationship with the dechlorination rates. While the selectivity of dechlorination depends on the charges associated with the individual aromatic carbon. Chloro-functional groups at the ortho-position are easier to be dechlorinated than that at meta- and para- positions yielding primarily 3,4,5-TCP as intermediate from PCP, further to phenol. The effective dechlorination warrants their potential utilizations in development of in-situ remediation technologies for organic pollutants in contaminated water. Copyright © 2015 Elsevier B.V. All rights reserved.

Molecular dynamics simulations of the electrical double layer on smectite surfaces contacting concentrated mixed electrolyte (NaCl-CaCl2) solutions.

PubMed

Bourg, Ian C; Sposito, Garrison

2011-08-15

We report new molecular dynamics results elucidating the structure of the electrical double layer (EDL) on smectite surfaces contacting mixed NaCl-CaCl(2) electrolyte solutions in the range of concentrations relevant to pore waters in geologic repositories for CO(2) or high-level radioactive waste (0.34-1.83 mol(c) dm(-3)). Our results confirm the existence of three distinct ion adsorption planes (0-, β-, and d-planes), often assumed in EDL models, but with two important qualifications: (1) the location of the β- and d-planes are independent of ionic strength or ion type and (2) "indifferent electrolyte" ions can occupy all three planes. Charge inversion occurred in the diffuse ion swarm because of the affinity of the clay surface for CaCl(+) ion pairs. Therefore, at concentrations ≥0.34 mol(c) dm(-3), properties arising from long-range electrostatics at interfaces (electrophoresis, electro-osmosis, co-ion exclusion, colloidal aggregation) will not be correctly predicted by most EDL models. Co-ion exclusion, typically neglected by surface speciation models, balanced a large part of the clay mineral structural charge in the more concentrated solutions. Water molecules and ions diffused relatively rapidly even in the first statistical water monolayer, contradicting reports of rigid "ice-like" structures for water on clay mineral surfaces. Published by Elsevier Inc.

Nontronite Stability in Near-Surface Sediments

NASA Astrophysics Data System (ADS)

Home, C.; Baker, L.

2015-12-01

The purpose of this study is to examine how long nontronite clays persist in soil, by studying samples collected from a sediment cone weathering out of crack in a basalt outcrop near Moscow Idaho. Nontronite, a dioctahedral ferric smectite clay, is a frequent weathering product of basaltic rocks. However, it is rarely described in surface soils, even in basaltic terrains. At our field site, nontronite formed by basalt weathering is eroding from cracks in the basalt and forming small talus cones. We are examining samples collected from a trench and several soil cores to determine the clay mineralogy at different depths in the talus cone. Bulk and clay mineralogy is being determined using X-ray Diffractometry (XRD) analysis and Fourier Transform Infrared Spectroscopy (FT-IR) analysis. Bulk chemical analyses, and selective extractions with acid oxalate and citrate-bicarbonate-dithionite reagents, are being used to analyze Fe mineralogy and amorphous constituents. Preliminary observations suggest that iron mineralogy may vary with depth in the sediments, and that older, deeper sediments may contain more Fe in oxide phases. We hypothesize that nontronite in the sediments is decomposing over time to form low-Fe smectites + Fe oxides. The results of this study will help determine whether nontronite is stable to erosion and redeposition in a surficial environment, as well as the timescale of its possible decomposition. These results may be useful in assessing proposed models of nontronite transport and redeposition on Mars.

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.

Clot-Inducing Minerals Versus Plasma Protein Dressing for Topical Treatment of External Bleeding in the Presence of Coagulopathy

DTIC Science & Technology

2010-11-01

results using human blood samples.14–16 Therefore, this study was performed to analyze the hemostatic efficacy of WS in coagulopathic subjects and to... zeolite ). Smectite is used in industries as filler in paints and rubber products and as a sealer and plasticizer in civil engineering for tunnel...180 minutes or until death. Angiography using the computed tomography method was performed on survivors, and local tissues were collected for

Definitive Mineralogy from the Mars Science Laboratory Chemin Instrument

NASA Technical Reports Server (NTRS)

Yen, A. S.; Bish, D. L.; Blake, D. F.; Vaniman, D. T.; Treiman, A. H.; Ming, D. W.; Morris, Richard V.; Farmer, J. D.; Downs, R. T.; Chipera, S. J.;

Effect of illite particle shape on cesium sorption

USGS Publications Warehouse

Rajec, Pavol; Šucha, Vladimír; Eberl, Dennis D.; Środoń, Jan; Elsass, Françoise E.

1999-01-01

Samples containing illite and illite-smectite, having different crystal shapes (plates, “barrels”, and filaments), were selected for sorption experiments with cesium. There is a positive correlation between total surface area and Cs-sorption capacity, but no correlation between total surface area and the distribution coefficient, Kd. Generally Kd increases with the edge surface area, although “hairy” (filamentous) illite does not fit this pattern, possibly because elongation of crystals along one axis reduces the number of specific sorption sites.

Implications of abundant hygroscopic minerals in the Martian regolith

NASA Technical Reports Server (NTRS)

Clark, B. C.

1978-01-01

Converging lines of evidence suggest that a significant portion of the Martian surface fines may consist of salts and smectite clays. Salts can form stoichiometric hydrates as well as eutectic solutions with depressed freezing points; clays contain bound water of constitution and adsorb significant quantities of water from the vapor phase. The formation of ice may be suppressed by these minerals in some regions on Mars, and their presence in abundance would imply important consequences for atmospheric and geologic processes and the prospects for exobiology.

The formation of illite from nontronite by mesophilic and thermophilic bacterial reaction

USGS Publications Warehouse

Jaisi, Deb P.; Eberl, Dennis D.; Dong, Hailiang; Kim, Jinwook

2011-01-01

The formation of illite through the smectite-to-illite (S-I) reaction is considered to be one of the most important mineral reactions occurring during diagenesis. In biologically catalyzed systems, however, this transformation has been suggested to be rapid and to bypass the high temperature and long time requirements. To understand the factors that promote the S-I reaction, the present study focused on the effects of pH, temperature, solution chemistry, and aging on the S-I reaction in microbially mediated systems. Fe(III)-reduction experiments were performed in both growth and non-growth media with two types of bacteria: mesophilic (Shewanella putrefaciens CN32) and thermophilic (Thermus scotoductus SA-01). Reductive dissolution of NAu-2 was observed and the formation of illite in treatment with thermophilic SA-01 was indicated by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). A basic pH (8.4) and high temperature (65°C) were the most favorable conditions for the formation of illite. A long incubation time was also found to enhance the formation of illite. K-nontronite (non-permanent fixation of K) was also detected and differentiated from the discrete illite in the XRD profiles. These results collectively suggested that the formation of illite associated with the biologically catalyzed smectite-to-illite reaction pathway may bypass the prolonged time and high temperature required for the S-I reaction in the absence of microbial activity.

Acid activation of upper Eocene Ca-bentonite for soybean oil clarification.

PubMed

Chakroun, Salima; Herchi, Mongi; Mechti, Wafa; Gaied, Mohamed Essghaier

2017-10-01

In central Tunisia, many upper Eocene outcrops supply smectitic claystone which are characterized by several analytical techniques (calcimetry, XRD, SediGraph, chemical analysis, surface area, etc.). Beidellite is the main mineral detected by the XRD method. Representative raw samples M1, taken from Henchir Souar (Zaghouan, Tunisia), were acid activated in order to improve their physicochemical properties. This study consists in optimizing the activation conditions with HCl 3 N by varying the following parameters: time (2, 4, and 6 h) and temperature (25, 50, 75, and 90 °C). The characterization by XRD and chemical analysis was carried out on the samples (M1, activated for 2 and 6 h at 75 °C), showing a structural modification of the clay by reduction of intensity reflection 001 order of smectite and dissolution of metal ions (Al 3+ , Fe 3+ , and Mg 2+ ) from clay structure. Optimum condition for soybean oil clarification is obtained using a variety of amount raw clays (0.5, 0.75, and 1%). Thus, the best clarification yield is given at 0.75% of clay, showing a capacity of about 55%. Various forms of activated materials were used with a 75% proportion to leach soybean oil. Results were compared with commercial bentonite (Tonsil) having surface area (378 m 2 /g). The activated sample M1 during 4 h at 75 °C possesses a decolorizing capacity of about 85% greater than the oil treated by Tonsil in laboratory (58%).

The use of fortified soil-clay as on-site system for domestic wastewater purification.

PubMed

Oladoja, N A; Ademoroti, C M A

2006-02-01

The quest for simple, low-cost and high-performance decentralized wastewater treatment system for domestic application in developing nations necessitated this study. Clay samples collected from different deposits in Nigeria were characterized by studying the mineralogical and geochemical composition using X-ray diffraction (XRD) and atomic absorption spectroscopy (AAS), respectively. Three major clay minerals of kaolinite, illite and smectite were identified. The geochemical studies showed the abundance of SiO2, Al2O3 and H2O+ in each of the clay samples. Performance efficiency studies were conducted to determine the best combination ratio of pebbles/soil-clay. Soil-clay fortified by pebbles in combination ratios of 1:3 (i.e. pebbles:soil-clay = 1:3 (w/w) showed the optimum water purification, while the combination 3:1 gave the least. The flow rate studies showed that the wastewater had a longer residence time in non-fortified soil-clay than in fortified soil-clay. Two modes of treatment methods were employed-single and double column treatment methods (SCT and DCT). The two methods gave effluents of good quality characteristics, but those from the DCT were of better quality. The quality of effluents also varies from one clay type to another. The quality of effluents from media containing smectite clay mineral was better than those from other columns. Repeated usage of the fortified clay column showed a decrease of pH, TS and DO, and an increase of COD when monitored over a period of 10 days.

SAM-Like Evolved Gas Analyses of Phyllosilicate Minerals and Applications to SAM Analyses of the Sheepbed Mudstone, Gale Crater, Mars

NASA Technical Reports Server (NTRS)

McAdam, A. C.; Franz, H. B.; Mahaffy, P. R.; Eigenbrode, J. L.; Stern, J. C.; Brunner, B.; Sutter, B.; Archer, P. D.; Ming , D. W.; Morris, R. V.;

From illite/smectite clay to mesoporous silicate adsorbent for efficient removal of chlortetracycline from water.

PubMed

Wang, Wenbo; Tian, Guangyan; Zong, Li; Zhou, Yanmin; Kang, Yuru; Wang, Qin; Wang, Aiqin

2017-01-01

A series of mesoporous silicate adsorbents with superior adsorption performance for hazardous chlortetracycline (CTC) were sucessfully prepared via a facile one-pot hydrothermal reaction using low-cost illite/smectite (IS) clay, sodium silicate and magnesium sulfate as the starting materials. In this process, IS clay was "teared up" and then "rebuilt" as new porous silicate adsorbent with high specific surface area of 363.52m 2 /g (about 8.7 folds higher than that of IS clay) and very negative Zeta potential (-34.5mV). The inert SiOSi (Mg, Al) bonds in crystal framework of IS were broken to form Si(Al) O - groups with good adsorption activity, which greatly increased the adsorption sites served for holding much CTC molecules. Systematic evaluation on adsorption properties reveals the optimal silicate adsorbent can adsorb 408.81mg/g of CTC (only 159.7mg/g for raw IS clay) and remove 99.3% (only 46.5% for raw IS clay) of CTC from 100mg/L initial solution (pH3.51; adsorption temperature 30°C; adsorbent dosage, 3g/L). The adsorption behaviors of CTC onto the adsorbent follows the Langmuir isotherm model, Temkin equation and pseudo second-order kinetic model. The mesopore adsorption, electrostatic attraction and chemical association mainly contribute to the enhanced adsorption properties. As a whole, the high-efficient silicate adsorbent could be candidates to remove CTC from the wastewater with high amounts of CTC. Copyright © 2016. Published by Elsevier B.V.

Interactive priming of biochar and labile organic matter mineralization in a smectite-rich soil.

PubMed

Keith, Alexandra; Singh, Balwant; Singh, Bhupinder Pal

2011-11-15

Biochar is considered as an attractive tool for long-term carbon (C) storage in soil. However, there is limited knowledge about the effect of labile organic matter (LOM) on biochar-C mineralization in soil or the vice versa. An incubation experiment (20 °C) was conducted for 120 days to quantify the interactive priming effects of biochar-C and LOM-C mineralization in a smectitic clayey soil. Sugar cane residue (source of LOM) at a rate of 0, 1, 2, and 4% (w/w) in combination with two wood biochars (450 and 550 °C) at a rate of 2% (w/w) were applied to the soil. The use of biochars (~ -36‰) and LOM (-12.7‰) or soil (-14.3‰) with isotopically distinct δ(13)C values allowed the quantification of C mineralized from biochar and LOM/soil. A small fraction (0.4-1.1%) of the applied biochar-C was mineralized, and the mineralization of biochar-C increased significantly with increasing application rates of LOM, especially during the early stages of incubation. Concurrently, biochar application reduced the mineralization of LOM-C, and the magnitude of this effect increased with increasing rate of LOM addition. Over time, the interactive priming of biochar-C and LOM-C mineralization was stabilized. Biochar application possesses a considerable merit for long-term soil C-sequestration, and it has a stabilizing effect on LOM in soil.

Photophysical and antibacterial properties of complex systems based on smectite, a cationic surfactant and methylene blue.

PubMed

Donauerová, Alena; Bujdák, Juraj; Smolinská, Miroslava; Bujdáková, Helena

2015-10-01

Solid or colloidal materials with embedded photosensitizers are promising agents from the medical or environmental perspective, where the direct use of photoactive solutions appears to be problematic. Colloids based on layered silicates of the saponite (Sap) and montmorillonite (Mon) type, including those modified with dodecylammonium cations (C12) and photosensitizer--methylene blue (MB) were studied. Two representatives of bacteria, namely Enterobacter cloacae and Escherichia coli, were selected for this work. A spectral study showed that MB solutions and also colloids with Sap including C12 exhibited the highest photoactivities. The antimicrobial properties of the smectite colloids were not directly linked to the photoactivity of the adsorbed MB cations. They were also influenced by other parameters, such as light vs. dark conditions, the spectrum, power and duration of the light used for the irradiation; growth phases, and the pre-treatment of microorganisms. Both the photoactivity and antimicrobial properties of the colloids were improved upon pre-modification with C12. Significantly higher antimicrobial properties were observed for the colloids based on Mon with MB in the form of molecular aggregates without significant photoactivities. The MB/Mon colloids, both modified and non-modified with C12 cations, exhibited higher antimicrobial effects than pure MB solution. Besides the direct effect of photosensitization, the surface properties of the silicate particles likely played a crucial role in the interactions with microorganisms. Copyright © 2015 Elsevier B.V. All rights reserved.

A Study of Olivine Alteration to Iddingsite Using Raman Spectroscopy

NASA Technical Reports Server (NTRS)

Kuebler, K. E.; Wang, Alian; Haskin, L. A.; Jolliff, B. L.

2003-01-01

A crucial task of Mars surface science is to determine past environmental conditions, especially aqueous environments and their nature. Identification of mineral alteration by water is one way to do this. Recent work interprets TES spectra as indicating altered basalt on Mars. Olivine, a primary basaltic mineral, is easily altered by aqueous solutions. Alteration assemblages of olivine may be specific to deuteric, hydrothermal, surface water, or metamorphic environments. Raman spectra are produced by molecular vibrations and provide direct means for studying and identifying alteration products. Here, we present a combined study of changes in the chemical composition and Raman spectra of an olivine as it alters to iddingsite. Iddingsite is found in some SNC meteorites and is presumably present on Mars. The term 'iddingsite' has been used as a catch-all term to describe reddish alteration products of olivine, although some authors ascribe a narrower definition: an angstrom-scale intergrowth of goethite and smectite (presumably saponite) formed in an oxidizing and fluid-rich environment. Alteration conserves Fe (albeit oxidized) but requires addition of Al and H2O and removal of Mg and Si. The smectite that forms may be removed by continued alteration. Dehydration of the goethite forms hematite. Our purpose is to study the mineral assemblage, determine the structural and chemical variability of the components with respect to the degree of alteration, and to find spectral indicators of alteration that will be useful during in-situ analyses on Mars.

Mineralogy of a perudic Andosol in central Java, Indonesia

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

Van Ranst, Eric; Utami, S. R.; Verdoodt, A.

2008-02-15

We studied the mineralogy of a perudic Andosol developed on the Dieng Tephra Sequence in central Java, Indonesia. The objective was to confirm the presence and determine the origin and stability of 2:1 and interlayered 2:1 phyllosilicates in well-drained Andosols. This was and still is a debated topic in the literature. Total elemental and selective dissolution, as well as microscopic and X-ray diffraction analyses, were performed on the soil samples collected from this site. These analyses confirmed that andic properties were present in the soil samples. The allophane content determined by selective dissolution was 3-4% in the A horizons, andmore » increased to 12-18% in the deeper subsoil horizons. In addition, the clay fraction contained dioctahedral smectite, hydroxy-Al-interlayered 2:1 minerals (HIS), Al-chlorite, kaolinite, pyrophyllite, mica, cristobalite and some gibbsite. The silt and sand fractions were rich in plagioclase and pyroxene. The 2:1 minerals (smectite and pyrophyllite), as well as chlorite and kaolinite were of hydrothermal origin and were incorporated in the tephra during volcanic eruption. Besides desilication during dissolution of unstable minerals, Al interlayering of 2:1 layer silicates was most likely the most prominent pedogenic process. Although hydroxy-Al polymeric interlayers would normally stabilize the 2:1 clay phases, the strong weakening, and even disappearance of the characteristic XRD peaks, indicated instability of these minerals in the upper A horizons due to the perudic and intensive leaching conditions.« less

Effect of minerals on accumulation of Cs by fungus Saccaromyces cerevisiae.

PubMed

Ohnuki, Toshihiko; Sakamoto, Fuminori; Yamasaki, Shinya; Kozai, Naofumi; Shiotsu, Hiroyuki; Utsunomiya, Satoshi; Watanabe, Naoko; Kozaki, Tamotsu

2015-06-01

The accumulation of Cs by unicellular fungus of Saccharomyces cerevisiae in the presence of minerals has been studied to elucidate the role of microorganisms in the migration of radioactive Cs in the environment. Two different types of experiments were employed: experiments using stable Cs to examine the effect of a carbon source on the accumulation of Cs, and accumulation experiments of radioactive Cs from agar medium containing (137)Cs and zeolite, vermiculite, phlogopite, smectite, mica, or illite as mineral supplements. In the former type of experiments, the Cs-accumulated cells were analyzed by scanning electron microscopy equipped with energy dispersive X-ray analysis (SEM-EDS). In the latter type, the radioactivity in the yeast cells was measured by an autoradiography technique. When a carbon source was present, higher amounts of Cs accumulated in the cells than in the resting condition without a carbon source. Analyses with SEM-EDS showed that no mineral formed on the cell surface. These results indicate that the yeast cells accumulate Cs by adsorption on the cell surface and intracellular accumulation. In the presence of minerals in the agar medium, the radioactivity in the yeast cells was in the order of mica > smectite, illite > vermiculite, phlogopite, zeolite. This order is inversely correlated to the ratio of the concentration of radioactive Cs between the minerals and the medium solution. These results strongly suggest that the yeast accumulates radioactive Cs competitively with minerals. Copyright © 2015 Elsevier Ltd. All rights reserved.

Mineralogical Composition of Particle-Size Fractions of Solonetzes from the North Crimean Lowland

NASA Astrophysics Data System (ADS)

Chizhikova, N. P.; Khitrov, N. B.; Tronza, G. E.; Kol'tsov, S. A.; Varlamov, E. B.; Chechetko, E. S.; Churilin, N. A.

2017-12-01

Data on the mineralogical composition of clay (<1 μm), fine silt (1-5 μm), medium silt (5-10 μm), and coarser (>10 μm) fractions of meadow solonchakous solonetzes (Calcic Gypsic Salic Stagnic Solonetz (Albic, Siltic, Columnic, Cutanic, Differentic)) developing from loesslike loam and clay in the North Crimean Lowland are presented. Fractions >5 μm constitute nearly 50% of the soil mass and are characterized by the same mineralogical composition in the entire profile; they consist of quartz, plagioclases, potassium feldspars, and micas (biotite and muscovite). The eluvial-illuvial redistribution of clay in the course of solonetzic process is accompanied by changes in the portion of mixed-layer minerals and hydromicas in the upper part of the profile; a larger part of the smectitic phase is transformed into the superdisperse state. In the eluvial SEL horizon and in the illuvial BSN horizon, the clay fraction is impoverished in smectitic phase and enriched in trioctahedral hydromicas. Upon calculation of the content of clay minerals per bulk soil mass, the distribution of mixed-layer minerals is either eluvial, or eluvial-illuvial, whereas the distribution of hydromicas has an illuvial pattern without distinct eluvial minimum in the SEL horizons. The eluvial-illuvial distribution pattern of clay minerals in solonetzes of the North Crimean Lowland is compared with the distribution pattern of clay minerals in solonetzes of the West Siberian Lowland. Coefficients characterizing differentiation of solonetzes by the contents of particular mineral components are suggested.

Paleoclimatic significance of chemical weathering in loess-derived paleosols of subarctic central Alaska

USGS Publications Warehouse

Muhs, D.R.; Ager, T.A.; Skipp, G.; Beann, J.; Budahn, J.; McGeehin, J.P.

2008-01-01

Chemical weathering in soils has not been studied extensively in high-latitude regions. Loess sequences with modern soils and paleosols are present in much of subarctic Alaska, and allow an assessment of present and past chemical weathering. Five sections were studied in detail in the Fairbanks, Alaska, area. Paleosols likely date to mid-Pleistocene interglacials, the last interglacial, and early-to-mid-Wisconsin interstadiale. Ratios of mobile (Na, Ca, Mg, Si) to immobile (Ti or Zr) elements indicate that modern soils and most interstadial and interglacial paleosols are characterized by significant chemical weathering. Na2O/TiO2 is lower in modern soils and most paleosols compared to parent loess, indicating depletion of plagioclase. In the clay fraction, smectite is present in Tanana and Yukon River source sediments, but is absent or poorly expressed in modern soils and paleosols, indicating depletion of this mineral also. Loss of both plagioclase and smectite is well expressed in soils and paleosols as lower SiO 2/TiO2. Carbonates are present in the river source sediments, but based on CaO/TiO2, they are depleted in soils and most paleosols (with one exception in the early-to-mid-Wisconsin period). Thus, most soil-forming intervals during past interglacial and interstadial periods in Alaska had climatic regimes that were at least as favorable to mineral weathering as today, and suggest boreal forest or acidic tundra vegetation. ?? 2008 Regents of the University of Colorado.

Contrasting origin of two clay-rich debris flows at Cayambe Volcanic Complex, Ecuador

NASA Astrophysics Data System (ADS)

Detienne, M.; Delmelle, P.; Guevara, A.; Samaniego, P.; Opfergelt, S.; Mothes, P. A.

2017-04-01

We investigate the sedimentological and mineralogical properties of a debris flow deposit west of Cayambe Volcanic Complex, an ice-clad edifice in Ecuador. The deposit exhibits a matrix facies containing up to 16 wt% of clays. However, the stratigraphic relationship of the deposit with respect to the Canguahua Formation, a widespread indurated volcaniclastic material in the Ecuadorian inter-Andean Valley, and the deposit alteration mineralogy differ depending on location. Thus, two different deposits are identified. The Río Granobles debris flow deposit ( 1 km3) is characterised by the alteration mineral assemblage smectite + jarosite, and sulphur isotopic analyses point to a supergene hydrothermal alteration environment. This deposit probably derives from a debris avalanche initiated before 14-21 ka by collapse of a hydrothermally altered rock mass from the volcano summit. In contrast, the alteration mineralogy of the second debris flow deposit, which may itself comprise more than one unit, is dominated by halloysite + smectite and relates to a shallower and more recent (<13 ky) mass movement of high-altitude (>3200 m) volcanic soils. Our study reinforces the significance of hydrothermal alteration in weakening volcano flanks and in favouring rapid transformation of a volcanic debris avalanche into a clay-rich debris flow. It also demonstrates that mineralogical analysis provides crucial information for resolving the origin of a debris flow deposit in volcanic terrains. Finally, we posit that slope instability, promoted by ongoing subglacial hydrothermal alteration, remains a significant hazard at Cayambe Volcanic Complex.

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

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.

Initiation and development of slickenlined surfaces in clay-rich material of the Nankai Trough accretionary prism

NASA Astrophysics Data System (ADS)

Crespo-Blanc, Ana; Schleicher, Anja

2016-04-01

During the International Ocean Discovery Program (IODP) Expedition 348, which is part of the Nankai Trough Seismogenic Zone Experiment (stage 3), the drilling vessel Chikyu advanced the deep riser hole at Site C0002, located 80 km offshore of the Kii Peninsula (Japan), from a depth of 860 meters below sea floor (mbsf) to 3058.5 mbsf. Underlying the Kumano Basin sediments, the Nankai accretionary prism appears, below 975.5 mbsf. It accreted during Upper Miocene to Pliocene times and is formed mainly by turbiditic silty claystone with rarely observed sandstone intercalations. Cuttings from both the 1-4 mm and >4 mm size fractions were investigated, showing slickenlined surfaces and deformation bands together with carbonate veins throughout the entire section from 1045.5 until 3058.5 mbsf. A scaly fabric is increasingly observed below approximately 2400 mbsf. Clay-rich cuttings were selected at different depth for specific SEM-EDS analysis, in order to investigate the initiation and development of the slickenlined surfaces, from both a structural and mineralogical point of view. Two end-members of the slickenlined surface types were observed: a) isolated smooth and uniform planes, between 20 and 50 μm long, formed by single grains of smectite with marked lineations and frequently jagged boundaries and b) microfaults (longer than 100 μm) with sharp boundaries to the undeformed rock, formed by aggregates of illite and smectite and with a well-developed lineation. In transition between these two end-member types, planes that are apparently unconnected draw a single plane and show subparallel lineations. Concerning the orientation of the slickenlines, it seems to be coherent with that observed in an array of conjugated faults, i.e. all the slickenlines belong to the same plane, in turn sub-perpendicular to the intersection of conjugated planes. These observations suggest that the slickenlined surfaces initiated along single grains of smectite and that with increasing deformation, the planes coherently oriented connected all together until the formation of a mature slickenline surface (microfault). It must be stressed that the described geometry was observed at any depth and the same process of formation seem to be valid for the whole drilled section of the Nankai accretionary prism. Acknowledgements: This research used samples provided by IODP. Grants RNM-215 and 451 ("Junta de Andalucía", Spain) and CGL2013-46368-P ("Ministerio de Economía y Competitividad", Spain) supported this study.

The origins of Late Quaternary debris avalanche and debris flow deposits from Cofre de Perote volcano, México

USGS Publications Warehouse

Diaz-Castellon, Rodolfo; Hubbard, Bernard E.; Carrasco-Nunez, Gerardo; Rodríguez-Vargas, José Luis

2012-01-01

Cofre de Perote volcano is a compound, shield-like volcano located in the northeastern Trans-Mexican volcanic belt. Large debris avalanche and lahar deposits are associated with the evolution of Cofre. The two best preserved of these debris-avalanche and debris-flow deposits are the ∼42 ka “Los Pescados debris flow” deposit and the ∼11–13 ka “Xico avalanche” deposit, both of which display contrasting morphological and textural characteristics, source materials, origins and emplacement environments. Laboratory X-ray diffraction and visible-infrared reflectance spectroscopy were used to identify the most abundant clay, sulfate, ferric-iron, and silica minerals in the deposits, which were either related to hydrothermal alteration or chemical weathering processes. Cloud-free Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) remote sensing imagery, supporting EO-1 Hyperion image spectra, and field ground truth samples were used to map the mineralogy and distribution of hydrothermally altered rocks on the modern summit of Cofre de Perote. The results were then compared to minerals identified in the two debris-avalanche and debris-flow deposits in order to assess possible source materials and origins for the two deposits.The older Los Pescados debris-flow deposit contains mostly halloysite and hydrous silica minerals, which match the dominant mineralogy of soils and weathered volcanic deposit in the surrounding flanks of Cofre de Perote. Its source materials were most likely derived from initially noncohesive or clay-poor flows, which subsequently bulked with clay-rich valley soils and alluvium in a manner similar to lahars from Nevado del Ruiz in 1985, but on a larger scale. The younger Xico avalanche deposit contains abundant smectite, jarosite, kaolinite, gypsum, and mixed-layered illite/smectite, which are either definitely or most likely of hydrothermal alteration origin. Smectite in particular appears to be the most abundant and spectrally dominant mineral in summit ground truth samples, ASTER mapping results, Xico avalanche deposit, and an older (pre-Xico avalanche) deposit derived from collapse(s) of ancestral Cofre de Perote edifice. However, both Xico avalanche and Los Pescados debris flow deposits show some evidence of secondary, postemplacement weathering and induration, which is evident by the presence of gibbsite, and hydroxyl interlayered minerals, in addition to recently formed halloysite and hydrous silica (i.e., indurating) cements. Field-based, visible infrared image spectroscopy (VIS/IR) spectral measurements offer the possibility of distinguishing primary minerals of hydrothermal alteration origin in debris-avalanche and debris-flow deposits from those produced either by in situ chemical weathering or bulked from weathered source materials.

Hollow Nodules Gas Escape Sedimentary Structures in Lacustrine Deposits on Earth and Gale Crater

NASA Astrophysics Data System (ADS)

Bonaccorsi, R.; Willson, D.; Fairen, A. G.; Baker, L.; McKay, C.; Zent, A.; Mahaffy, P. R.

2015-12-01

Curiosity's Mastcam and MAHLI instruments in Gale Crater (GC) imaged mm-sized circular rimmed hollow nodules (HNs) (Figure 1A), pitting the Sheepbed mudstone of Yellowknife Bay Formation [1,2]. HNs are significantly smaller than the solid nodules within the outcrop, with an external mean diameter of 1.2 mm and an interior one of 0.7 mm [2] Several formation mechanisms of HNs have been discussed, such as: (1) Diagenetic dissolution of soluble mineral phases; or, (2) Gas bubbles released shortly after sediment deposition [1-3]. In an ephemeral pond in Ubehebe Crater (Death Valley, CA) we observed the formation of hollow nodule sedimentary structures produced by gas bubbles (Figure 1C) preserved in smectite-rich mud that are strikingly similar to those imaged in GC (Figure 1A). This finding supports the gas bubble hypothesis [2]. Ubehebe Crater (UC) surface sediment hollow nodules were sampled, imaged, and their internal diameter measured (200 hollow structures) showing similar shape, distribution, and composition to those imaged by Curiosity in GC. UC in-situ observations suggest the gas bubbles were generated within the slightly reducing ephemerally submerged mud. These intra-crater deposits remain otherwise extremely dry year round, i.e., Air_rH ~2-5%; ground H2O wt%: 1-2%; Summer air/ground T: 45-48ºC/67-70ºC [4-5]. Data from the Sample Analysis at Mars (SAM), CheMin, and ChemCam instruments onboard the rover revealed that HNs-bearing mudstone are rich in smectite clay e.g., ~18-20% [6,7] deposited in a neutral to mildly alkaline environment, capturing a period when the surface was potentially habitable [1]. The UC HNs-hosting deposits are also rich in smectite clays (~30%) and occur in an ephemeral shallow freshwater setting [4-5]. If present, surface hollow nodules are easy to find in dry clay-rich mud in lacustrine sediments, so they could represent a new indicator of ephemeral but habitable/inhabited environments on both Earth and early Mars. References: [1] Grotzinger J.P. et al. (2014), Science 343, 124277. [2] Stack et al. (2014) JGR,Planets 119343. [4] Bonaccorsi R. et al. (2012) AGU Fall Meeting, Abstract #P11B-1839. [5] Bonaccorsi, R. et al. (2014) AGU Fall Meeting, Paper #EP53A-3632. [6] McLennan, S.M. et al. (2014) Science 343, 1244734. [7] Ming D.W. et al. (2014) Science, 343, 1245267.

Spatially resolved nanoscale observations of soil carbon multidecadal persistence

NASA Astrophysics Data System (ADS)

Lutfalla, S.; Chenu, C.; Bernard, S.; Le Guillou, C.; Barré, P.

2015-12-01

Assessing how mineral surfaces, especially at small scale, can protect soil organic carbon (SOC) from biodegradation is crucial. The question we address in this work is whether different mineral species lead to different organo-mineral interactions and stabilize different quantities of SOM and different types of SOC. Here we used the unique opportunity offered by long term bare fallows (BF) to study in situ C dynamics in several fine fractions of a silty loam soil. With no vegetation i.e. no external input of fresh C, the plant-free soil of the Versailles 42 Plots (INRA, France) has been progressively enriched in persistent SOC during the 80 years of BF. Contrasted mineral phases of the clay size fraction were isolated by size fractionation on samples from 5 different dates (0, 10, 22, 52, and 79 years after the beginning of the BF, four field replicates per date). Four fractions were studied: total clays (< 2 μm), and three sub fractions in the clay (fine clay: 0 - 0.05 μm, intermediate clay: 0.05 - 0.2 μm, and coarse clay: 0.2 - 2 μm). X-ray diffraction analyses showed contrasted mineralogies in the fine and intermediate clay (smectite and mixed layered illite/smectite) as opposed to the coarse clay (smectite, illite, kaolinite and mixed layered I/S). We performed CHN elemental analysis and synchrotron based spectroscopy and microscopy (NEXAFS bulk and STXM at the carbon K edge of 280 eV, CLS Saskatoon, Canada) to study the dynamics, the distribution and the chemical speciation of the SOC in these fractions. The quantity of C appears to be stabilized after 50 years of BF, even though the dynamics are different for the three clay fractions. Indeed, coarse and intermediate clays have the same final C content but coarse clays lose more C. Fine clay experiences the highest C losses and displays the highest final C content suggesting that fine clays contained more labile C and more persistent C. In all fractions, C:N ratios are really low (below 8) and are decreasing with time, evidencing the dominant presence of microbial SOC. STXM-NEXAFS data shows that, in the fine and intermediate clay fractions, during the first 50 years of BF all mineral particles are associated with SOC. On the contrary, in the coarse clays, SOC displays more diversity: the chemical signature is more diverse and mineral particles not associated with SOC appear more quickly.

Minerals and clay minerals assemblages in organic-rich facies: the case study of the Sinemurian-Pliensbachian carbonate deposits of the western Lusitanian Basin (Portugal)

NASA Astrophysics Data System (ADS)

Caniço, Ana; Duarte, Luís V.; Silva, Ricardo L.; Rocha, Fernando; Graciano Mendonça Filho, João

2015-04-01

The uppermost Sinemurian-Pliensbachian series of the western part of the Lusitanian Basin is composed by hemipelagic carbonates particularly enriched in organic matter. Great part of this succession, considered to be one of the most important potential source rock intervals of Portugal, crops out in the S. Pedro de Moel and Peniche sectors, belonging to the Água de Madeiros and Vale das Fontes formations. In this study, supported by a detailed and integrated stratigraphic framework, we analyzed 98 marly samples (whole-rock mineralogy and clay minerals assemblages) from the aforementioned formations in the S. Pedro de Moel and Peniche sectors. X-ray Diffraction analysis followed the standard procedures and the semi-quantification of the different mineral phases was calculated using MacDiff 4.2.6. The goals of this work are to demonstrate the vertical variability of the mineral composition of these two units and investigate the relationship between the clay minerals assemblages and the content in organic matter (Total organic carbon: TOC). Besides the abundance of calcite and phyllosilicates, whole-rock mineralogy revealed the presence of quartz, potassium feldspar, dolomite, and pyrite (trace amounts). Other minerals like anhydrite, barite and gypsum occur sporadically. The clay minerals assemblages are dominated by illite+illite/smectite mixed-layers (minimum of 59%), always associated with kaolinite (maximum of 37%) and chlorite (maximum of 25%); sporadically smectite occurs in trace amounts. Generally, high TOC levels (i.e., black shale facies with TOC reaching up to 22 wt.% in both units, see Duarte et al., 2010), show a major increase in chlorite and kaolinite (lower values of illite+illite/smectite mixed layers). A kaolinite enrichment is also observed just above the Sinemurian-Pliensbachian boundary (base of Praia da Pedra Lisa Member of Água de Madeiros Formation; values varying between 30 and 37%). This event is associated with a second-order regressive phase, and marks the disappearance of the organic-rich facies and increase of carbonate sedimentation. This enrichment was likely favored by the development of more humid conditions at the Sinemurian-Pliensbachian transition. References Duarte, L.V., Silva, R.L., Oliveira, L.C.V., Comas-Rengifo, M.J., Silva, F. 2010. Organic-rich facies in the Sinemurian and Pliensbachian of the Lusitanian Basin, Portugal: Total Organic Carbon distribution and relation to transgressive-regressive facies cycles. Geologica Acta 8, 325-340.

Safety Evaluation of New Hemostatic Agents, Smectite Granules, and Kaolin-Coated Gauze in a Vascular Injury Wound Model in Swine

DTIC Science & Technology

2010-02-01

risk of using WS when compared with kaolin-coated gauze, Combat Gauze (CG); or regular gauze, Kerlix (KX) to treat an external wound with vascular...communication with combat medics implied limited use or avoidance of these agents in the field because of either painful side effects (thermal injury with QC...potential thrombogenicity of WS and CG when they are used to control external bleeding due to major vascular injury. For this purpose, a new wound model was

Dehydroxylated clay silicates on Mars: Riddles about the Martian regolith solved with ferrian saponites

NASA Technical Reports Server (NTRS)

Burns, Roger G.

1992-01-01

Clay silicates, resulting from the chemical weathering of volcanic glasses and basaltic rocks of Mars, are generally believed to be major constituents of the martian regolith and atmospheric dust. Because little attention has been given to the role, if any, of Mg-bearing clay silicates on the martian surface, the crystal chemistry, stability, and reactivity of Mg-Fe smectites are examined. Partially dehydroxylated ferrian saponites are suggested to be major constituents of the surface of Mars, regulating several properties of the regolith.

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

NASA Astrophysics Data System (ADS)

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

2015-06-01

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

Mineralogical, geochemical and radiological characterisation of Selmo Formation in Batman area, Turkey.

PubMed

Isik, Umit; Damla, Nevzat; Akkoca, Dicle Bal; Cevik, Uğur

2012-06-01

This work deals with the mineralogical, geochemical and radiological characterisations of Selmo Formation in Batman neighbourhood. The upper Miocene-Pliocene Selmo Formation is common in the centre of Batman and composed of carbonated sandy claystones and silty-sandy stone lenses. The common whole minerals of the samples are quartz, feldspars, calcite and dolomite. The clay minerals are smectite, illite, chlorite and mixed-layer clay (chlorite-smectite). The geochemical mean values of the samples are 51.7% SiO(2); 12.6% Al(2)O(3); 6.2% Fe(2)O(3); 3.6% MgO; 6.3% CaO; 1.1% Na(2)O; 1.7% K(2)O; 0.8% TiO(2); 0.2% P(2)O(5); 0.1% MnO; and 0.03% Cr(2)O(3). In addition, baseline maps for the concentrations of each radionuclide, the radium equivalent activity and the outdoor gamma dose rate distributions have been plotted for the study area. The mean activity concentrations of (226)Ra, (232)Th, (40)K and (137)Cs were determined to be 32, 24, 210 and 9 Bq kg(-1), respectively. The assessments of the radiological hazard indices, such as radium equivalent activity, absorbed dose rate in air, annual effective dose equivalent, excess lifetime cancer risk, external hazard index and internal hazard index, were calculated and compared with the internationally accepted reference values. This study shows that the concentrations of radioactivities in the measured samples were within the recommended safety limits and did not pose to be any significant source of radiation hazard.

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.

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

PubMed

Benzine, Jason; Shelobolina, Evgenya; Xiong, Mai Yia; Kennedy, David W; McKinley, James P; Lin, Xueju; Roden, Eric E

2013-01-01

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

In Situ 13C and 23Na Magic Angle Spinning NMR Investigation of Supercritical CO2 Incorporation in Smectite-Natural Organic Matter Composites

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

Bowers, Geoffrey M.; Hoyt, David W.; Burton, Sarah D.

2014-01-29

This paper presents an in situ NMR study of clay-natural organic polymer systems (a hectoritehumic acid [HA] composite) under CO2 storage reservoir conditions (90 bars CO2 pressure, 50°C). The 13C and 23Na NMR data show that supercritical CO2 interacts more strongly with the composite than with the base clay and does not react to form other C-containing species over several days at elevated CO2. With and without organic matter, the data suggest that CO2 enters the interlayer space of Na-hectorite equilibrated at 43% relative humidity. The presence of supercritical CO2 also leads to increased 23Na signal intensity, reduced line widthmore » at half height, increased basal width, more rapid 23Na T1 relaxation rates, and a shift to more positive resonance frequencies. Larger changes are observed for the hectorite-HA composite than for the base clay. In light of recently reported MD simulations of other polymer-Na-smectite composites, we interpret the observed changes as an increase in the rate of Na+ site hopping in the presence of supercritical CO2, the presence of potential new Na+ sorption sites when the humic acid is present, and perhaps an accompanying increase in the number of Na+ ions actively involved in site hopping. The results suggest that the presence of organic material either in clay interlayers or on external particle surfaces can significantly affect the behavior of supercritical CO2 and the mobility of metal ions in reservoir rocks.« less

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

PubMed Central

Benzine, Jason; Xiong, Mai Yia; Kennedy, David W.; McKinley, James P.; Lin, Xueju; Roden, Eric E.

2013-01-01

Microorganisms capable of reducing or oxidizing structural iron (Fe) in Fe-bearing phyllosilicate minerals were enriched and isolated from a subsurface redox transition zone at the Hanford 300 Area site in eastern Washington, USA. Both conventional and in situ “i-chip” enrichment strategies were employed. One Fe(III)-reducing Geobacter (G. bremensis strain R1, Deltaproteobacteria) and six Fe(II) phyllosilicate-oxidizing isolates from the Alphaproteobacteria (Bradyrhizobium japonicum strains 22, is5, and in8p8), Betaproteobacteria (Cupriavidus necator strain A5-1, Dechloromonas agitata strain is5), and Actinobacteria (Nocardioides sp. strain in31) were recovered. The G. bremensis isolate grew by oxidizing acetate with the oxidized form of NAu-2 smectite as the electron acceptor. The Fe(II)-oxidizers grew by oxidation of chemically reduced smectite as the energy source with nitrate as the electron acceptor. The Bradyrhizobium isolates could also carry out aerobic oxidation of biotite. This is the first report of the recovery of a Fe(II)-oxidizing Nocardioides, and to date only one other Fe(II)-oxidizing Bradyrhizobium is known. The 16S rRNA gene sequences of the isolates were similar to ones found in clone libraries from Hanford 300 sediments and groundwater, suggesting that such organisms may be present and active in situ. Whole genome sequencing of the isolates is underway, the results of which will enable comparative genomic analysis of mechanisms of extracellular phyllosilicate Fe redox metabolism, and facilitate development of techniques to detect the presence and expression of genes associated with microbial phyllosilicate Fe redox cycling in sediments. PMID:24379809

Distribution and composition of gold in porphyry gold systems: example from the Biely Vrch deposit, Slovakia

NASA Astrophysics Data System (ADS)

Koděra, Peter; Kozák, Jaroslav; Brčeková, Jana; Chovan, Martin; Lexa, Jaroslav; Jánošík, Michal; Biroň, Adrián; Uhlík, Peter; Bakos, František

2018-03-01

The Biely Vrch deposit in the Western Carpathians is assigned to the shallow, sulfide-poor porphyry gold deposit type and has an exceptionally low Cu/Au ratio. According to 3-D geochemical models, there is a limited spatial correlation between Au and Cu due to the primary introduction of gold by a salt melt and Cu by low-density vapor. Despite a rough spatial correlation of gold grades with quartz stockwork intensity, gold is hosted mostly by altered rock, exclusively in native form. Three main gold mineral assemblages were recognized here. In the deepest parts of the system, the K- and Ca-Na silicate gold assemblage is associated with minerals of high-temperature alteration (plagioclase, K-feldspar, actinolite), with gold grades and fineness depending on depth and potassium content of the host rock: K-silicate alteration hosts the lowest fineness gold ( 914), whereas Ca-Na silicate alteration has the highest ( 983). The intermediate argillic gold assemblage is the most widespread, with gold hosted mainly by chlorite, illite, smectite, and interstratified illite-chlorite-smectite minerals. The gold fineness is mostly variable (875-990) and inherited from the former gold mineral assemblages. The latest advanced argillic gold assemblage has its gold mostly in kaolinite. The extremely high fineness ( 994) results from gold remobilization by late-stage aqueous magmatic-hydrothermal fluids. Uncommon bonanza-grade appears where the earlier gold mineral assemblages were further enriched by this remobilized gold. Primary precipitation of gold occurred during ascent and cooling of salt melts at 450 to 309 °C, mostly during retrograde quartz solubility.

Late Eocene clay boron-derived paleosalinity in the Qaidam Basin and its implications for regional tectonics and climate

NASA Astrophysics Data System (ADS)

Ye, Chengcheng; Yang, Yibo; Fang, Xiaomin; Zhang, Weilin

2016-12-01

The Qaidam Basin, located on the northeastern Tibetan Plateau and containing Cenozoic sediments with a maximum thickness of 12,000 m, is an ideal place to study the phased uplift of the NE Tibetan Plateau and regional climate change. The estimation of the paleosalinity of sedimentary environments not only helps to evaluate the evolution of lakes in this region but offers insights into contemporaneous climate change. We present detailed geochemical and mineralogical investigations from the lacustrine interval of the Hongliugou section in the northern Qaidam Basin to reconstruct salinity fluctuations in the paleolake during the late Eocene era ( 42.0-35.5 Ma). The clay mineral assemblages mainly contain smectite, illite, chlorite, kaolinite and irregular illite/smectite mixed layers. Clay boron-derived paleosalinity estimates (equivalent boron content, Couch's paleosalimeter and B/Ga ratios) along with other proxies sensitive to salinity changes (e.g., Rb/K ratios and ostracod assemblages) collectively indicate an overall brackish sedimentary environment with a higher-salinity period at approximately 40.0-39.2 Ma. This higher-salinity period indicates a more arid environment and is probably related to global cooling. However, the global cooling in late Eocene cannot explain the overall stable long-term salinity pattern, implying that other factors exist. We propose that the migration of the Yiliping depression depocenter in the northern Qaidam and increased orographic rainfall induced by late Eocene tectonic activity at the northern margin of the basin might have partly offset the increase in salinity driven by global cooling.

Distinguishing palagonitized from pedogenically-altered basaltic Hawaiian tephra: Mineralogical and geochemical criteria

USGS Publications Warehouse

Schiffman, P.; Southard, R.J.; Eberl, D.D.; Bishop, J.L.

2002-01-01

Palagonitization is a common, but imperfectly defined process that greatly modifies the physical and chemical properties of glassy basaltic tephra deposited in subaquatic/subglacial environments on Earth and perhaps Mars. It also results in textures and mineralogies that are distinct from other forms of (mainly pedogenic) low temperature alteration. Specifically, the process of palagonitization (1) initially results in the formation of 'palaginitized glass', a quasi- or nano-crystalline, rind-like material that contains smectite, as well as lesser amounts of other clays (e.g. serpentine), and (2) eventually results in consolidation of tephra, mediated through the accretion of palagonitized glass and later- formed authigenic cements. Conversely, pedogenic weathering of glassy basaltic tephra is characterized by disaggregation of tephra, and formation of a wide range of pedogenic products, including layer silicates (although not primarily smectite), short-range-order aluminosilicates and oxyhydroxides, whose composition reflects the intensity of the weathering environment. These mineralogical and textural properties can be readily recognized through a variety of techniques including electron microscopy/microprobe analysis, reflectance spectroscopy, X-ray diffraction and soil chemistry. Analyses of samples collected from the summit regions of Kilauea and Mauna Kea volcanoes on the island of Hawaii are presented here in order to illustrate differences between palagonitization and pedogenic weathering of glassy basaltic tephra. In the young Hawaiian tephras studied, palagonitization has occured in response to hydrothermal activity shortly after deposition. Although some, non-hydrothermally affected tephras may eventually become palagonitized, those that have been strongly desilicated by intense pedogenic weathering will probably never become palagonitized.

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

NASA Astrophysics Data System (ADS)

Arvidson, Raymond E.

2016-09-01

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

Diffusion of Na(I), Cs(I), Sr(II) and Eu(III) in smectite rich natural clay.

PubMed

Kasar, Sharayu; Kumar, Sumit; Bajpai, R K; Tomar, B S

2016-01-01

Diffusion of Na(I), Cs(I), Sr(II) and Eu(III) in smectite rich natural clay, proposed as a backfill material in the Indian geological repository, was studied using the out-diffusion method. Radiotracers (22)Na, (137)Cs, (85)Sr and (154)Eu were used; the first three are carrier-free enabling experimental work at sub-micromolar metal ion concentration, and Eu(III) tracer (154)Eu was used at sub millimolar concentration. An out-diffusion methodology, wherein a thin planar source of radioactivity placed between two clay columns diffuses out, was used to obtain the apparent diffusion coefficient (Da) values. This methodology enabled determination of diffusion coefficient even for strongly sorbing (154)Eu. Da values for (22)Na, (137)Cs, (85)Sr and (154)Eu were 2.35 (±0.14) × 10(-11), 2.65 (±0.09) × 10(-12), 3.32 (±0.15) × 10(-11) and 1.23 (±0.15) × 10(-13) m(2) s(-1), respectively. Da values were found to be in fair agreement with literature data reported for similar mineralogical sediments. Sorption of radionuclides on the clay was also determined in the present study and differences in Da values were rationalized on the basis of sorption data. Distribution ratios (Kd) for Cs(I) and Eu(III) were higher than that for Sr(II), which in turn was higher than that for Na(I). Copyright © 2015 Elsevier Ltd. All rights reserved.

Provenance of Holocene sediment on the Chukchi-Alaskan margin based on combined diffuse spectral reflectance and quantitative X-Ray Diffraction analysis

USGS Publications Warehouse

Ortiz, J.D.; Polyak, L.; Grebmeier, J.M.; Darby, D.; Eberl, D.D.; Naidu, S.; Nof, D.

2009-01-01

Sediment clay and silt mineral assemblages provide an excellent means of assessing the provenance of fine-grained Arctic sediment especially when a unique mineral assemblage can be tied to specific source areas. The diffuse spectral reflectance (DSR) first derivative measurements and quantitative X-Ray Diffraction (qXRD) on a high-resolution sediment core from the continental slope north of Alaska constrain the sediment mineralogy. DSR results are augmented by measurements on several adjacent cores and compared to surface sediment samples from the northern Alaskan shelf and slope. Using Principal Component Analysis (PCA), we infer that the three leading DSR modes relate to mixtures of smectite + dolomite, illite + goethite, and chlorite + muscovite. This interpretation is consistent with the down core qXRD results. While the smectite + dolomite, and illite + goethite factors show increased variability down core, the chlorite + muscovite factor had highest positive loadings in the middle Holocene, between ca. 6.0 and 3.6??ka. Because the most likely source of the chlorite + muscovite suite in this vicinity lies in the North Pacific, we argue that the oscillations in chlorite + muscovite values likely reflect an increase in the inflow of Pacific water to the Arctic through the Bering Strait. The time interval of this event is associated in other parts of the globe with a non-linear response of the climate system to the decrease in insolation, which may be related to changes in water exchange between the Pacific and Arctic Ocean. ?? 2009 Elsevier B.V.

Colloids from the aqueous corrosion of uranium nuclear fuel

NASA Astrophysics Data System (ADS)

Kaminski, M. D.; Dimitrijevic, N. M.; Mertz, C. J.; Goldberg, M. M.

2005-12-01

Colloids may enhance the subsurface transport of radionuclides and potentially compromise the long-term safe operation of the proposed radioactive waste repository at Yucca Mountain. Little data is available on colloid formation for the many different waste forms expected to be buried in the repository. This work expands the sparse database on colloids formed during the corrosion of metallic uranium nuclear fuel. We characterized spherical UO 2 and nickel-rich montmorilonite smectite-clay colloids formed during the corrosion of uranium metal fuel under bathtub conditions at 90 °C. Iron and chromium oxides and calcium carbonate colloids were present but were a minor population. The estimated upper concentration of the UO 2 and clays was 4 × 10 11 and 7 × 10 11-3 × 10 12 particles/L, respectively. However, oxygen eventually oxidized the UO 2 colloids, forming long filaments of weeksite K 2(UO 2) 2Si 6O 15 · 4H 2O that settled from solution, reducing the UO 2 colloid population and leaving predominantly clay colloids. The smectite colloids were not affected by oxygen. Plutonium was not directly observed within the UO 2 colloids but partitioned completely to the colloid size fraction. The plutonium concentration in the colloidal fraction was slightly higher than the value used in the viability assessment model, and does not change in concentration with exposure to oxygen. This paper provides conclusive evidence for single-phase radioactive colloids composed of UO 2. However, its impact on repository safety is probably small since oxygen and silica availability will oxidize and effectively precipitate the UO 2 colloids from concentrated solutions.

Oceanographic controls over sediment water content: northern Bermuda rise

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

Baker, M.; Laine, E.P.

1985-01-01

Cores taken from the plateaus of Northern Bermuda Rise show that the region is underlain at depths of 1-5 m by a 1-3 m thick layer of hemipelagic lutites with anomalously high water contents. The lack of visually apparent textural and lithological changes in this extremely fine grained sediment rule out these common causes for variation in water content. The water content averages 175% within this layer and 100% immediately above and below it. This is an increase of 9.5% in porosity. The high water content sediment is confined to a period between 12 and 16 ka. Current work onmore » the mineralogy of the sediments which comprise this layer suggest two oceanographic factors that may have influenced its formation. A meltwater spike associated with deglaciation may have altered the ecological conditions above the thermocline sufficiently to promote the increased production of radiolaria, resulting in the deposition of silica enriched sediment on the sea floor. A combination of textural and perhaps chemical factors caused by the silica enrichment may have influenced the increase in water content. Intensified bottom currents at this time also may have eroded smectite rich sediments from exposures of Neogene age and deposited them on the plateaus. An increase in smectite would increase the water content due to the extremely fine grain size and the chemistry of the clay. Thus, the lateral continuity and isochroniety of this layer, combined with its mineralogical characteristics suggests that oceanographic changes can influence water content and perhaps other geotechnical properties on a regional scale.« less

Depositional environment of near-surface sediments, King George Basin, Bransfield Strait, Antarctica

NASA Astrophysics Data System (ADS)

Yoon, H. I.; Park, B. K.; Chang, S. K.; Han, M. W.; Oh, J. K.

1994-03-01

Four sediment cores were collected to determine the depositional environments of the King George Basin northeast of Bransfield Strait, Antarctica. The cored section revealed three distinct lithofacies: laminated siliceous ooze derived from an increased paleoproductivity near the receding sea-ice edges, massive muds that resulted from hemipelagic sedimentation in open water, and graded sediments that originated from nearby local seamounts by turbidity currents. Clay mineral data of the cores indicate a decreasing importance of volcanic activity through time. Active volcanism and hydrothermal activity appear to be responsible for the enrichment of smectite near the Penguin and Bridgeman Islands.

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

NASA Astrophysics Data System (ADS)

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

2007-12-01

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

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.

Oxygen and hydrogen isotope geochemistry of Cretaceous bentonites and shales from the Disturbed Belt, Montana

NASA Astrophysics Data System (ADS)

Eslinger, Eric V.; Yeh, Hsueh-Wen

1986-01-01

The mineralogy, δO 18, and δD of the <0.1 μm fraction of 22 Cretaceous bentonites and the mineralogy and δO 18 of the < 0.1 μm fraction of 14 adjacent shales collected from outcrops in the Sweetgrass Arch and Disturbed Belt, Montana, have been determined. Mixed-layer illite/smectite (I/S) is the dominant mineral in the bulk bentonite and usually the only mineral in the < 0.1 μm fraction. I/S is also the major clay mineral in the shales. The diagenetic grade in bentonite is qualitatively given by the percentage of illite layers in I/S, which varies from 2 to 25 (Sweetgrass Arch) to as high as 95 (Disturbed Belt). δO 18 of < 0.1 μm bentonite generally decreases from about +20%. to about +13%. with increasing diagenetic grade. On a plot of δD versus δO 18, data for the < 0.1 μm bentonite define a field that generally parallels, but falls on the meteoric water line side of the smectite-water line (Savin and Epstein, 1970). δO 18 of bulk bentonite is 1 to 3%. more negative than the δO 18 of the < 0.1 μm fraction, due to the presence of volcanic quartz and feldspar. δO 18 of several size fractions of clay-sized quartz separated from the bentonite varies from +11%. to +24%., and, in a given bentonite, generally increases with decreasing grain size. Among the different bentonites, the δO 18 range of the different grain sizes decreases as the percentage of illite layers in the coexisting I/S increases. The δO 18 of 0.1-0.5 μm shale quartz is generally 1 to 4%. more positive than clay-sized quartz from an adjacent bentonite, and the δO 18 of < 0.1 μm I/S concentrate of shales is generally < 1 to 4%. more negative than the < 0.1 μm I/S from an adjacent bentonite. Isotopic temperatures, interpreted to be maximum burial temperatures, range between about 160°C (shale), to about 250°C (bentonite). The isotopic data can be interpreted using the stages: 1) deposition of volcanic glassy ash containing some quartz and feldspar; 2) devitrification into mostly 100% expandable smectite with a δO 18 of about 20%. and δD of -60 to -80%.; 3) tectonic burial beneath thrust sheets in the Disturbed Belt region which induced elevated temperatures that allowed oxygen and hydrogen isotope reequilibration as the percentage of illite layers in I/S increased and diagenetic quartz formed; and 4) exhumation of the strata with preservation of O 18/O 16 and D/H attained during burial.

Weathering and hydrothermal alteration of basalts in Iceland: mineralogy from VNIR, TIR, XRD, and implications for Mars

NASA Astrophysics Data System (ADS)

Ehlmann, B. L.; Mustard, J. F.; Bish, D. L.

2009-12-01

Recent orbital investigations have revealed that aqueous alteration on early Mars took place in diverse alteration environments indicated by distinctive assemblages of minerals (Murchie et al., 2009, JGR). There is growing evidence for past diagenetic or low-temperature/pressure hydrothermal activity on Mars at neutral to alkaline pH, indicated by the presence of Fe/Mg smectites, chlorite, prehnite, serpentine, opaline silica, and zeolites such as analcime in Noachian terrains (Ehlmann et al., 2009, JGR). In recent investigations of terrestrial Mars analog sites, neutral to alkaline pH alteration of basalt, both pedogenic and hydrothermal, has been understudied in favor of sulfur-rich, acidic systems including those at the Hawaiian volcanoes and Rio Tinto, Spain. We began study of the alteration of basalt lava flows in Iceland as a geochemical analog for Noachian Mars. Because the basaltic bedrock is recently formed (<16Ma) with few localities of more highly evolved composition and has poorly formed soils and spare vegetation, the ground and surface waters are broadly similar to those which might have existed on Noachian Mars. Iceland has a variety of geothermal spring systems--low T, low S; low T, high S; and high T, high S--each of which creates distinctive mineralogic assemblages. Here we examine rocks of the Hvalfjordur peninsula, collected from basalt flows that were in some places altered at the surface by pedogenesis and in other locations were hydrothermally altered by non-sulfurous groundwater circulation (low T, low S) following the emplacement of a later hot basalt flow. Rock samples were surveyed in the field using a portable VNIR spectrometer. Altered and unaltered rocks that were typical for the locality were collected as were altered rocks whose spectra were most similar to those measured by CRISM from Mars orbit. Ten rocks were ultimately selected for detailed laboratory analyses: zeolitized basaltic rocks bearing minerals including analcime and thomsonite, basalts with silica/quartz-bearing veins, basalts bearing celadonite, and basalts partially altered to montmorillonite, Fe/Mg smectite, or mixed smectite-chlorite. Analyses included: (1) measurement of reflectance spectra of the whole rock by the ASD; (2) measurement of VNIR and TIR spectra in RELAB of particle-size separates (<25um and <125um) derived from the bulk rock and from precipitated minerals extracted from the vesicles; (3) measurement of X-ray diffraction (XRD) patterns, including quantitative XRD; and (4) electron microprobe chemical analyses. These data emulate orbital data from CRISM, OMEGA, and TES, which detect the infrared active components, linked to in-situ data on whole rock modal mineralogy such as will be measured by the ChemMin instrument on the MSL rover.

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

NASA Astrophysics Data System (ADS)

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

2009-12-01

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

Mineralogy and stratigraphy of phyllosilicate-bearing and dark mantling units in the greater Mawrth Vallis/west Arabia Terra area: Constraints on geological origin

USGS Publications Warehouse

Noe Dobrea, E.Z.; Bishop, J.L.; McKeown, N.K.; Fu, R.; Rossi, C.M.; Michalski, J.R.; Heinlein, C.; Hanus, V.; Poulet, F.; Mustard, R.J.F.; Murchie, S.; McEwen, A.S.; Swayze, G.; Bibring, J.-P.; Malaret, E.; Hash, C.

2010-01-01

Analyses of MRO/CRISM images of the greater Mawrth Vallis region of Mars affirm the presence of two primary phyllosilicate assemblages throughout a region ∼1000 × 1000 km. These two units consist of an Fe/Mg-phyllosilicate assemblage overlain by an Al-phyllosilicate and hydrated silica assemblage. The lower unit contains Fe/Mg-smectites, sometimes combined with one or more of these other Fe/Mg-phyllosilicates: serpentine, chlorite, biotite, and/or vermiculite. It is more than 100 m thick and finely layered at meter scales. The upper unit includes Al-smectite, kaolin group minerals, and hydrated silica. It is tens of meters thick and finely layered as well. A common phyllosilicate stratigraphy and morphology is observed throughout the greater region wherever erosional windows are present. This suggests that the geologic processes forming these units must have occurred on at least a regional scale. Sinuous ridges (interpreted to be inverted channels) and narrow channels cut into the upper clay-bearing unit suggesting that aqueous processes were prevalent after, and possibly during, the deposition of the layered units. We propose that layered units may have been deposited at Mawrth Vallis and then subsequently altered to form the hydrated units. The Fe/Mg-phyllosilicate assemblage is consistent with hydrothermal alteration or pedogenesis of mafic to ultramafic rocks. The Al-phyllosilicate/hydrated silica unit may have formed through alteration of felsic material or via leaching of basaltic material through pedogenic alteration or a mildly acidic environment. These phyllosilicate-bearing units are overlain by a darker, relatively unaltered, and indurated material that has probably experienced a complex geological history.

HSDP II Drill Core: Preliminary Rock Strength Results and Implications to Flank Stability, Mauna Kea Volcano

NASA Astrophysics Data System (ADS)

Thompson, N.; Watters, R. J.; Schiffman, P.

2004-12-01

Selected portions of the 3-km HSDP II core were tested to provide unconfined rock strength data from hyaloclastite alteration zones and pillow lavas. Though the drilling project was not originally intended for strength purpose, it is believed the core can provide unique rock strength insights into the flank stability of the Hawaiian Islands. The testing showed that very weak rock exists in the hyaloclastite abundant zones in the lower 2-km of the core with strength dependent on the degree of consolidation and type of alteration. Walton and Schiffman identified three zones of alteration, an upper incipient alteration zone (1080-1335m), a smectitic zone (1405-1573m) and a lower palagonitic zone from about 1573 m to the base of the core. These three zones were sampled and tested together with pillow lava horizons for comparison. Traditional cylindrical core was not available as a consequence of the entire core having been split lengthwise for archival purposes. Hence, point load strength testing was utilized which provides the unconfined compressive strength on irregular shaped samples. The lowest unconfined strengths were recorded from incipient alteration zones with a mean value of 9.5 MPa. Smectitic alteration zones yielded mean values of 16.4 MPa, with the highest measured alteration strengths from the palagonite zones with a mean value of 32.1 MPa. As anticipated, the highest strengths were from essentially unaltered lavas with a mean value of 173 MPa. Strength variations of between one to two orders of magnitude were identified in comparing the submarine hyaloclastite with the intercalated submarine lavas. The weakest zones within the hyaloclastites may provide horizons for assisting flank collapse by serving as potential thrust zones and landslide surfaces.

Measurement of illite particle thickness using a direct Fourier transform of small-angle X-ray scattering data

USGS Publications Warehouse

Shang, Chao; Rice, James A.; Eberl, Dennis D.; Lin, Jar-Shyong

2003-01-01

It has been suggested that interstratified illite-smectite (I-S) minerals are composed of aggregates of fundamental particles. Many attempts have been made to measure the thickness of such fundamental particles, but each of the methods used suffers from its own limitations and uncertainties. Small-angle X-ray scattering (SAXS) can be used to measure the thickness of particles that scatter X-rays coherently. We used SAXS to study suspensions of Na-rectorite and other illites with varying proportions of smectite. The scattering intensity (I) was recorded as a function of the scattering vector, q = (4 /) sin(/2), where  is the X-ray wavelength and  is the scattering angle. The experimental data were treated with a direct Fourier transform to obtain the pair distance distribution function (PDDF) that was then used to determine the thickness of illite particles. The Guinier and Porod extrapolations were used to obtain the scattering intensity beyond the experimental q, and the effects of such extrapolations on the PDDF were examined. The thickness of independent rectorite particles (used as a reference mineral) is 18.3 Å. The SAXS results are compared with those obtained by X-ray diffraction peak broadening methods. It was found that the power-law exponent (α) obtained by fitting the data in the region of q = 0.1-0.6 nm-1 to the power law (I = I0q-α) is a linear function of illite particle thickness. Therefore, illite particle thickness could be predicted by the linear relationship as long as the thickness is within the limit where α <4.0.

Iron-Manganese Redox Reactions in Endeavour Crater Rim Apron Rocks

NASA Technical Reports Server (NTRS)

Ming, D. W.; Mittlefehldt, D. W.; Gellert, R.; Peretyazhko, T.; Clark, B. C.; Morris, R. V.; Yen, A. S.; Arvidson, R. E.; Crumpler, L. S.; Farrand, W. H.;

The chemical evolution of Kurnub Group palcowater in the Sinai-Negev province - A mass balance approach

USGS Publications Warehouse

Rosenthal, E.; Jones, B.F.; Weinberger, G.

1998-01-01

The chemical evolution of the Kurnub Group paleowater was studied starting from rainwater in recharge areas of the Sinai and along groundwater flowpaths leading to the natural outlets of this regional aquifer. This was achieved by investigating the chemical composition of groundwater, ionic ratios, degrees of saturation with common mineral species, normative analysis of dissolved salts and by modeling of rock/water interaction and mixing processes occurring along groundwater flow paths. The initial groundwater composition used is from the Nakhel well in Sinai. It evolves from desert rainwater percolating through typical Kurnub Group lithology in Sinai. This rainwater dissolves mainly gypsum, halite and dolomite together with smaller amounts of marine aerosol and K-feldspar. At the same time it precipitates calcite, SiO2, smectite and degasses CO2. Between the area of Nakhel and the northern Negev the chemistry of Kurnub Group waters is influenced by dissolution of halite and lesser amounts of gypsum of surficial origin in recharge areas, small amounts of feldspars and of dolomite cement in sandstones eroded from the Arabo-Nubian igneous massif of Sinai and organic degradation-derived CO2. Concomitantly, there is precipitation of calcite, smectite, SiO2 and probably analcime characteristic of sediments in continental closed basins. North of the Negev, the Kurnub Group fluids are diluted and altered by mixing with Judea Group aquifer groundwaters. On the E there is mixing with residual brines from the water body ancestral to the Dead Sea, prior to discharge into the Arava valley. Rock/water interaction indicated by NETPATH and PHREEQC modeling is in agreement with lithology and facies changes previously observed in the Kurnub Group sequence.

Modification of the quality of water injected into Louisiana gulf coast sands: Effects of cation exchange

NASA Astrophysics Data System (ADS)

Hanor, Jeffrey S.

1982-06-01

Interest in artificially recharging selected shallow sands in South Louisiana with fresh water has been stimulated by the desire to retard contamination of municipal groundwater supplies by brackish water, to retard ground subsidence and decrease pumping lifts, and to develop emergency subsurface supplies of potable water for communities dependent on surface waters susceptible to contamination. Results of field experiments, laboratory work, and model calculations demonstrate that ion exchange reactions involving clays dispersed in aquifer sands can be expected to modify significantly the composition of waters injected into Gulf Coast sediments. As little as 0.1 weight percent smectite (montmorillonite) can remove, by exchange with absorbed Na, a significant fraction of the dissolved Ca and Mg present in the injected water. The hardness of the water is thus reduced, which may be a desirable modification in water quality. Exchange occurs as fast as the fluids can be pumped into or out of the aquifer, and the water-softening capacity of the aquifer can be restored by allowing sodium-rich native pore waters to sweep back over the dispersed clays. Each acre of an aquifer 50 feet thick and containing 0.1 wt % smectite could soften half a million gallons of injected Mississippi River water. Many individual Gulf Coast aquifers underlie tens of thousands of acres, and their potential softening capacity is thus enormous. Additional exchange processes involving adjacent aquitard shales presumably will operate over long-term periods. It is possible that Gulf Coast aquifers will be used at some point in the future as processing plants to treat injected water to improve its quality for a variety of municipal and industrial purposes.

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.

Analysis of mineral matrices of planetary soil analogues from the Utah Desert

NASA Astrophysics Data System (ADS)

Kotler, J. M.; Quinn, R. C.; Foing, B. H.; Martins, Z.; Ehrenfreund, P.

2011-07-01

Phyllosilicate minerals and hydrated sulphate minerals have been positively identified on the surface of Mars. Studies conducted on Earth indicate that micro-organisms influence various geochemical and mineralogical transitions for the sulphate and phyllosilicate minerals. These minerals in turn provide key nutrients to micro-organisms and influence microbial ecology. Therefore, the presence of these minerals in astrobiology studies of Earth-Mars analogue environments could help scientists better understand the types and potential abundance of micro-organisms and/or biosignatures that may be encountered on Mars. Bulk X-ray diffraction of samples collected during the EuroGeoMars 2009 campaign from the Mancos Shale, the Morrison and the Dakota formations near the Mars Desert Research Station in Utah show variable but common sedimentary mineralogy with all samples containing quantities of hydrated sulphate minerals and/or phyllosilicates. Analysis of the clay fractions indicate that the phyllosilicates are interstratified illite-smectites with all samples showing marked changes in the diffraction pattern after ethylene glycol treatment and the characteristic appearance of a solvated peak at ˜17 Å. The smectite phases were identified as montmorillonite and nontronite using a combination of the X-ray diffraction data and Fourier-Transform Infrared Spectroscopy. The most common sulphate mineral in the samples is hydrated calcium sulphate (gypsum), although one sample contained detectable amounts of strontium sulphate (celestine). Carbonates detected in the samples are variable in composition and include pure calcium carbonate (calcite), magnesium-bearing calcium carbonate (dolomite), magnesium, iron and manganese-bearing calcium carbonate (ankerite) and iron carbonate (siderite). The results of these analyses when combined with organic extractions and biological analysis should help astrobiologists and planetary geologists better understand the potential relationships between mineralogy and microbiology for planetary missions.

Hydrated silicate minerals on Mars observed by the Mars Reconnaissance Orbiter CRISM instrument

USGS Publications Warehouse

Mustard, J.F.; Murchie, S.L.; Pelkey, S.M.; Ehlmann, B.L.; Milliken, R.E.; Grant, J. A.; Bibring, J.-P.; Poulet, F.; Bishop, J.; Dobrea, E.N.; Roach, L.; Seelos, F.; Arvidson, R. E.; Wiseman, S.; Green, R.; Hash, C.; Humm, D.; Malaret, E.; McGovern, J.A.; Seelos, K.; Clancy, T.; Clark, R.; des Marais, D.; Izenberg, N.; Knudson, A.; Langevin, Y.; Martin, T.; McGuire, P.; Morris, Robert; Robinson, M.; Roush, T.; Smith, M.; Swayze, G.; Taylor, H.; Titus, T.; Wolff, M.

2008-01-01

Phyllosilicates, a class of hydrous mineral first definitively identified on Mars by the OMEGA (Observatoire pour la Mineralogie, L’Eau, les Glaces et l’Activitié) instrument1,2, preserve a record of the interaction of water with rocks on Mars. Global mapping showed that phyllosilicates are widespread but are apparently restricted to ancient terrains and a relatively narrow range of mineralogy (Fe/Mg and Al smectite clays). This was interpreted to indicate that phyllosilicate formation occurred during the Noachian (the earliest geological era of Mars), and that the conditions necessary for phyllosilicate formation (moderate to high pH and high water activity3) were specific to surface environments during the earliest era of Mars’s history4. Here we report results from the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM)4 of phyllosilicate-rich regions. We expand the diversity of phyllosilicate mineralogy with the identification of kaolinite, chlorite and illite or muscovite, and a new class of hydrated silicate (hydrated silica). We observe diverse Fe/Mg-OH phyllosilicates and find that smectites such as nontronite and saponite are the most common, but chlorites are also present in some locations. Stratigraphic relationships in the Nili Fossae region show olivine-rich materials overlying phyllosilicate-bearing units, indicating the cessation of aqueous alteration before emplacement of the olivine-bearing unit. Hundreds of detections of Fe/Mg phyllosilicate in rims, ejecta and central peaks of craters in the southern highland Noachian cratered terrain indicate excavation of altered crust from depth. We also find phyllosilicate in sedimentary deposits clearly laid by water. These results point to a rich diversity of Noachian environments conducive to habitability.

Extraction of hydrothermal alterations from ASTER SWIR data from east Zanjan, northern Iran

NASA Astrophysics Data System (ADS)

Azizi, H.; Tarverdi, M. A.; Akbarpour, A.

2010-07-01

The use of satellite images for mineral exploration has been very successful in pointing out the presence of minerals such as smectite and kaolinite which are important in the identification of hydrothermal alterations. Shortwave infrared (SWIR) bands from Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) with the wavelength of ASTER SWIR bands between 1.65 and 2.43 μm has a good potential for mapping a hydrothermal alteration minerals such as alunite, pyrophyllite, kaolinite, illite-muscovite-sericite, and carbonate. In this range, hydroxide minerals which have been produced by hydrothermal alteration exhibit good absorption compared to shorter or longer wavelengths. In this research which aims to remove atmospheric and topographic effects from ASTER SWIR data, the authors used the log-residual method (LRM) with the minimum noise fraction (MNF) transformation to create a pixel purity index (PPI) which was used to extract the most spectrally pure pixels from multispectral images. Spectral analyses of the clay mineralogy of the study area (east Zanjan, in northern Iran) were obtained by matching the unknown spectra of the purest pixels to the U.S. Geological Survey (USGS) mineral library. Three methods, spectral feature fitting (SFF), spectral angle mapping (SAM), and binary encoding (BE) were used to generate a score between 0 and 1, where a value of 1 indicates a perfect match showing the exact mineral type. In this way, it was possible to identify certain mineral classes, including chlorite, carbonate, calcite-dolomite-magnesite, kaolinite-smectite, alunite, and illite. In this research, two main propylitic and phyllic-argillic zones could be separated using their compositions of these minerals. These two alteration zones are important for porphyry copper deposits and gold mineralization in this part of Iran.

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

USGS Publications Warehouse

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

2009-01-01

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

Organic and clay mineral diagenesis in Neogene sediments of western Taiwan

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

Hsueh, C.M.

1985-01-01

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

Effect of Mineral and Microbe Interactions on Biomass Yield

NASA Astrophysics Data System (ADS)

Pena, S. A.; Block, K. A.; Katz, A.; Gottlieb, P.

2016-12-01

The ecological feedback of microbes (bacteria and viruses) in association with minerals is virtually unexplored in the context of characterizing how carbon cycles in the terrestrial ecosystem. These interactions include the ability for bacteriophage to control bacteria populations, the ability of minerals to provide a substrate for bacteria growth, and the effect of minerals on bacteriophage viability. We investigate bacteriophage aggregation with minerals in the clay size fraction (< 0.2 µm) as well as the interaction between bacteriophage and mineral biofilms. In our virus experiments, bacteriophage Φ6 was suspended with the minerals smectite, illite, kaolinite, and goethite at low divalent cation concentrations so aggregation was in the reaction limited colloidal aggregation (RLCA) regime, at neutral pH and room temperature conditions. Virus remained viable at a 1:1 virus-clay ratio for clays, and at an approximate 100:1 ratio for goethite. However, the number of plaque forming units was reduced by 99%. Electron micrographs show viable as well as partially disassembled virus, similar to the results found by Block et al. 2014. We found that inactivation of a 4 x 1011 cm-3 concentration of bacteriophage Φ6 by smectite, illite, kaolinite, and goethite, required a minimum sediment concentration of 1.5 x 1011 cm-3, 1.4 x 1011 cm-3, 2.5 x 1011 cm-3, and 1.1 x 109 cm-3, respectively. Mineral biofilms were generated by suspension of tropical soil clays with gram-positive and gram-negative microbes and characterized by x-ray diffraction and imaged by electron microscopy (SEM and TEM). Mineral biomass produced by gram negative organisms were subjected to virus infection to determine influence of minerals on community resilience. Lastly, we report biomass yield in each instance to quantify the influence of mineral composition on total biomass production.

Quaternary Sediment Accumulation in the Aleutian Trench: Implications for Dehydration Reaction Progress and Pore Pressure Development Offshore Alaska

NASA Astrophysics Data System (ADS)

Meridth, L. N.; Screaton, E.; Jaeger, J. M.; James, S. R.; Villaseñor, T. G.

2015-12-01

Sediment inputs to subduction zones impart a significant control on diagenetic reaction progress, fluid production and pore pressure development and thus affect hydrologic and tectonic behavior during subduction. Intensified glaciation following the mid-Pleistocene transition increased sediment flux to the Gulf of Alaska. Rapid sediment accumulation (>1 km/my) in the Aleutian Trench increases overburden and should accelerate dehydration of hydrous sedimentary components by elevating temperatures in the incoming sediment column. These processes have the potential to generate fluid overpressures in the mud-dominated, low permeability sediments deposited on the incoming plate, offshore SE Alaska. Mineralogical analyses on incoming sediments from Deep Sea Drilling Project Leg 18 and Integrated Ocean Drilling Program Expedition 341 show that both smectite and Opal-A are present as hydrous mineral phases. A 1-D numerical model was developed to track dehydration reaction progress and pore pressures in the incoming sediment column from the abyssal plain to the Aleutian Trench. Simulated temperatures in the incoming column increase due to the insulating effect of trench sediments. As a result, trench sedimentation causes smectite dehydration to begin and Opal-A dehydration to nearly reach completion at the deformation front. Simulated excess pore pressures in the proto-decollement zone increase from nearly hydrostatic to almost half of lithostatic due to the rapid deposition of trench sediments. The 1-D modeling results were incorporated into a 2-D model that follows the underthrust column at the deformation front into the subduction zone. Simulated results of the 2-D flow model illustrate the effects of lateral flow on pore pressure distribution following subduction.

Provenance and accommodation pathways of late Quaternary sediments in the deep-water northern Ionian Basin, southern Italy

NASA Astrophysics Data System (ADS)

Perri, Francesco; Critelli, Salvatore; Dominici, Rocco; Muto, Francesco; Tripodi, Vincenzo; Ceramicola, Silvia

2012-12-01

The northern Calabria along the southeastern coast of Italy provides a favorable setting in which to study complete transects from continental to deep-marine environments. The present northern Ionian Calabrian Basin is a wedge-top basin within the modern foreland-basin system of southern Italy. The Ionian margin of northern Calabria consists of a moderately developed fluvial systems, the Crati and Neto rivers, and diverse smaller coastal drainages draining both the Calabria continental block (i.e., Sila Massif) and the southern Apennines thrust belt (i.e., Pollino Massif). The main-channel sand of the Crati and Neto rivers is quartzofeldspathic with abundant metamorphic and plutonic lithic fragments (granodiorite, granite, gneiss, phyllite and sedimentary lithic fragments). Sedimentary lithic fragments were derived from Jurassic sedimentary successions of the Longobucco Group. The mud samples contain mostly phyllosilicates, quartz, calcite, feldspars and dolomite. Traces of gypsum are present in some samples. The I-S mixed layers, 10 Å-minerals (illite and micas), chlorite and kaolinite are the most abundant phyllosilicates, whereas smectite and chlorite/smectite mixed layers are in small amounts. The geochemical signatures of the muds reflect a provenance characterized by both felsic and mafic rocks with a significant input from carbonate rocks. Furthermore, the degree of source-area weathering was most probably of low intensity rather than moderately intense because CIA values for the studied mud samples are low. Extrapolation of the mean erosion budget from 1 to 25 Ma suggests that at least 5 to 8 km of crust have been removed from the Calabrian orogenic belt and deposited in the marine basins. The Calabrian microplate played an important role in the dynamic evolution of southern Italian fossil and modern basins, representing the key tectonic element of the entire orogenic belt.

A model for predicting embankment slope failures in clay-rich soils; A Louisiana example

NASA Astrophysics Data System (ADS)

Burns, S. F.

2015-12-01

A model for predicting embankment slope failures in clay-rich soils; A Louisiana example It is well known that smectite-rich soils significantly reduce the stability of slopes. The question is how much smectite in the soil causes slope failures. A study of over 100 sites in north and south Louisiana, USA, compared slopes that failed during a major El Nino winter (heavy rainfall) in 1982-1983 to similar slopes that did not fail. Soils in the slopes were tested for per cent clay, liquid limits, plasticity indices and semi-quantitative clay mineralogy. Slopes with the High Risk for failure (85-90% chance of failure in 8-15 years after construction) contained soils with a liquid limit > 54%, a plasticity index over 29%, and clay contents > 47%. Slopes with an Intermediate Risk (55-50% chance of failure in 8-15 years) contained soils with a liquid limit between 36-54%, plasticity index between 16-19%, and clay content between 32-47%. Slopes with a Low Risk chance of failure (< 5% chance of failure in 8-15 years after construction) contained soils with a liquid limit < 36%, a plasticity index < 16%, and a clay content < 32%. These data show that if one is constructing embankments and one wants to prevent slope failure of the 3:1 slopes, check the above soil characteristics before construction. If the soils fall into the Low Risk classification, construct the embankment normally. If the soils fall into the High Risk classification, one will need to use lime stabilization or heat treatments to prevent failures. Soils in the Intermediate Risk class will have to be evaluated on a case by case basis.

Highly selective direct determination of chlorate ions by using a newly developed potentiometric electrode based on modified smectite.

PubMed

Topcu, Cihan

2016-12-01

A novel polyvinyl chloride membrane chlorate (ClO 3 - ) selective electrode based on modified smectite was developed for the direct determination of chlorate ions and the potentiometric performance characteristics of its were examined. The best selectivity and sensitivity for chlorate ions were obtained for the electrode membrane containing ionophore/polyvinylchloride/o-nitrophenyloctylether in composition of 12/28/60 (w/w%). The proposed electrode showed a Nernstian response toward chlorate ions at pH=7 in the concentration range of 1×10 -7 -1×10 -1 M and the limit of detection was calculated as 9×10 -8 M from the constructed response plot. The linear slope of the electrode was -61±1mVdecade -1 for chlorate activity in the mentioned linear working range. The selectivity coefficients were calculated according to both the matched potential method and the separate solution method. The calculated selectivity coefficients showed that the electrode performed excellent selectivity for chlorate ions. The potentiometric response of electrode toward chlorate ions was found to be highly reproducible. The electrode potential was stable between pH=4-10 and it had a dynamic response time of <5s. The potentiometric behavior of the electrode in partial non-aqueous medium was also investigated and the obtained results (up to 5% (v/v) alcohol) were satisfactory. The proposed electrode was used during 15 weeks without any significant change in its potential response. Additionally, the electrode was very useful in water analysis studies such as dam water, river water, tap water, and swimming pool water where the direct determination of chlorate ions was required. Copyright © 2016 Elsevier B.V. All rights reserved.

Visible Wavelength Spectroscopy of Ferric Minerals: A Key Tool for Identification of Ancient Martian Aqueous Environments

NASA Technical Reports Server (NTRS)

Murchie, Scott L.; Bell, J. F., III; Morris, Richard V.

2000-01-01

The mineralogic signatures of past aqueous alteration of a basaltic Martian crust may include iron oxides and oxyhydroxides, zeolites, carbonates, phyllosilicates, and silica. The identities, relative abundances, and crystallinities of the phases formed in a particular environment depend on physicochemical conditions. At one extreme, hot spring environments may be characterized by smectite-chlorite to talc-kaolinite silicate assemblages, plus crystalline ferric oxides dominated by hematite. However, most environments, including cold springs, pedogenic layers, and ponded surface water, are expected to deposit iron oxides and oxyhydroxides, carbonates, and smectite-dominated phyllosilicates. A substantial fraction of the ferric iron is expected to occur in nanophase form, with the exact mineralogy strongly influenced by Eh-pH conditions. Detection of these phases has been an objective of a large body of terrestrial telescopic, Mars orbital, and landed spectral investigations and in situ compositional measurements. However, clear identifications of many of these phases is lacking. Neither carbonate nor silica has been unequivocally detected by any method. Although phyllosilicates may occur near the limit of detection by remote sensing, in general they appear to occur in only poorly crystalline form. In contrast, compelling evidence for ferric iron minerals has been gathered by recent telescopic investigations, the Imager for Mars Pathfinder (IMP), and the Thermal Emission Spectrometer (TES) on the Mars Global Surveyor (MGS). These data yield two crucial findings: (1) In the global, high spatial resolution TES data set, highly crystalline ferric iron (as coarse-grained 'gray' hematite) has been recognized but with only very limited spatial occurrence and (2) Low-resolution telescopic reflectance spectroscopy, very limited orbital reflectance spectroscopy, and landed multispectral imaging provide strong indications that at least two broad classes of ferric iron minerals are commonplace in non-dust covered regions.

Animated molecular dynamics simulations of hydrated caesium-smectite interlayers

PubMed Central

Sutton, Rebecca; Sposito, Garrison

2002-01-01

Computer animation of center of mass coordinates obtained from 800 ps molecular dynamics simulations of Cs-smectite hydrates (1/3 and 2/3 water monolayers) provided information concerning the structure and dynamics of the interlayer region that could not be obtained through traditional simulation analysis methods. Cs+ formed inner sphere complexes with the mineral surface, and could be seen to jump from one attracting location near a layer charge site to the next, while water molecules were observed to migrate from the hydration shell of one ion to that of another. Neighboring ions maintained a partial hydration shell by sharing water molecules, such that a single water molecule hydrated two ions simultaneously for hundreds of picoseconds. Cs-montmorillonite hydrates featured the largest extent of this sharing interaction, because interlayer ions were able to inhabit positions near surface cavities as well as at their edges, close to oxygen triads. The greater positional freedom of Cs+ within the montmorillonite interlayer, a result of structural hydroxyl orientation and low tetrahedral charge, promoted the optimization of distances between cations and water molecules required for water sharing. Preference of Cs+ for locations near oxygen triads was observed within interlayer beidellite and hectorite. Water molecules also could be seen to interact directly with the mineral surface, entering its surface cavities to approach attracting charge sites and structural hydroxyls. With increasing water content, water molecules exhibited increased frequency and duration of both cavity habitation and water sharing interactions. Competition between Cs+ and water molecules for surface sites was evident. These important cooperative and competitive features of interlayer molecular behavior were uniquely revealed by animation of an otherwise highly complex simulation output.

Clay minerals related to the circulation of geothermal fluids in boreholes at Rittershoffen (Alsace, France)

NASA Astrophysics Data System (ADS)

Vidal, Jeanne; Patrier, Patricia; Genter, Albert; Beaufort, Daniel; Dezayes, Chrystel; Glaas, Carole; Lerouge, Catherine; Sanjuan, Bernard

2018-01-01

Two geothermal wells, GRT-1 and GRT-2, were drilled into the granite at Rittershoffen (Alsace, France) in the Upper Rhine Graben to exploit geothermal resources at the sediment-basement interface. Brine circulation occurs in a permeable fracture network and leads to hydrothermal alteration of the host rocks. The goal of the study was to characterize the petrography and mineralogy of the altered rocks with respect to the permeable fracture zones in the granitic basement. As clay minerals are highly reactive to hydrothermal alteration, they can be used as indicators of present-day and paleo-circulation systems. Special attention has been paid to the textural, structural and chemical properties of these minerals. The fine-grained clay fraction (< 5 μm) was analyzed around the originally permeable fracture zones to observe the crystal structure of clay minerals using X-ray diffraction. Chemical microanalysis of the clay minerals was performed using scanning electron microscopy coupled with energy dispersive X-ray spectroscopy. The occurrences of mixed layers illite-smectite ( 10% smectite) provide a promising guide for identifying the fracture zones that control the present-day circulation of geothermal fluids in the Rittershoffen wells. However, multistage paleo-circulation systems could lead to an abundance of heterogeneous and fine-grained illitic minerals that could plug the fracture system. The permeability of fracture zones in the GRT-1 well was likely reduced because of an intense illitization, and the well was stimulated. The occurrence of chlorite in the permeable fracture zones of GRT-2 is indicative of less intense illitization, and the natural permeability is much higher in GRT-2 than in GRT-1.

Oscillation of mineral compositions in Core SG-1b, western Qaidam Basin, NE Tibetan Plateau

PubMed Central

Fang, Xiaomin; Li, Minghui; Wang, Zhengrong; Wang, Jiuyi; Li, Jiao; Liu, Xiaoming; Zan, Jinbo

2016-01-01

Uplift of the Tibetan Plateau since the Late Miocene has greatly affected the nature of sediments deposited in the Qaidam Basin. However, due to the scarcity of continuously dated sediment records, we know little about how minerals responded to this uplift. In order to understand this response, we here present results from the high-resolution mineral profile from a borehole (7.3–1.6 Ma) in the Basin, which shows systematic oscillations of various evaporite and clay minerals that can be linked to the variation of regional climate and tectonic history. In particular, x-ray diffraction (XRD) analyses show that carbonate minerals consist mainly of calcite and aragonite, with minor ankerite and dolomite. Evaporates consist of gypsum, celesite and halite. Clay minerals are principally Fe-Mg illite, mixed layers of illite/smectite and chlorite, with minor kaolinite and smectite. Following implications can be drawn from the oscillations of these minerals phases: (a) the paleolake was brackish with high salinity after 7.3 Ma, while an abrupt change in the chemical composition of paleolake water (e.g. Mg/Ca ratio, SO42− concentration, salinity) occurred at 3.3 Ma; (b) the three changes at ~6.0 Ma, 4.5–4.1 Ma and 3.3 Ma were in response to rapid erosions/uplift of the basin; (c) pore water or fluid was Fe/Mg-rich in 7.3–6.0 Ma, Mg-rich in 6.0–4.5 Ma, and K-rich in 4.1–1.6 Ma; and (d) evaporation rates were high, but weaker than today’s. PMID:27625177

Mars Exploration Rover APXS Results from Matijevic Hill

NASA Technical Reports Server (NTRS)

Cohen, B. A.; Clark, B. C.; Gellert, R.; Klingelhoefer, G.; Ming, D. W.; Mittlefehldt, D. W.; Morris, R. V.; Schrader, C. M.; Schroeder, C.; Yen, A. S.;

South Asian monsoon history over the past 60 kyr recorded by radiogenic isotopes and clay mineral assemblages in the Andaman Sea

NASA Astrophysics Data System (ADS)

Ali, Sajid; Hathorne, Ed C.; Frank, Martin; Gebregiorgis, Daniel; Stattegger, Karl; Stumpf, Roland; Kutterolf, Steffen; Johnson, Joel E.; Giosan, Liviu

2015-02-01

The Late Quaternary variability of the South Asian (or Indian) monsoon has been linked with glacial-interglacial and millennial scale climatic changes but past rainfall intensity in the river catchments draining into the Andaman Sea remains poorly constrained. Here we use radiogenic Sr, Nd, and Pb isotope compositions of the detrital clay-size fraction and clay mineral assemblages obtained from sediment core NGHP Site 17 in the Andaman Sea to reconstruct the variability of the South Asian monsoon during the past 60 kyr. Over this time interval ɛNd values changed little, generally oscillating between -7.3 and -5.3 and the Pb isotope signatures are essentially invariable, which is in contrast to a record located further northeast in the Andaman Sea. This indicates that the source of the detrital clays did not change significantly during the last glacial and deglaciation suggesting the monsoon was spatially stable. The most likely source region is the Irrawaddy river catchment including the Indo-Burman Ranges with a possible minor contribution from the Andaman Islands. High smectite/(illite + chlorite) ratios (up to 14), as well as low 87Sr/86Sr ratios (0.711) for the Holocene period indicate enhanced chemical weathering and a stronger South Asian monsoon compared to marine oxygen isotope stages 2 and 3. Short, smectite-poor intervals exhibit markedly radiogenic Sr isotope compositions and document weakening of the South Asian monsoon, which may have been linked to short-term northern Atlantic climate variability on millennial time scales. This article was corrected on 18 MAR 2015. See the end of the full text for details.

Clay mineralogical record on the upper continental slope of the northwestern South China Sea since the Last Glacial Maximum

NASA Astrophysics Data System (ADS)

CHEN, Q.; Liu, Z.; Stattegger, K.

2012-12-01

Clay mineralogy of two gravity cores (18428 and 18429) on the upper continental slope of the northwestern South China Sea was investigated in order to understand terrigenous sediment sources and to evaluate the contribution from the Red River since the Late Glacial Maximum. Planktonic foraminiferal oxygen isotope and carbonate stratigraphies suggest that Core 18428 is constrained in Holocene while Core 18429 covers the period of MIS 1-2. Clay mineral assemblages of two cores are composed mainly of smectite (18-57%) and illite (21-41%), with minor chlorite (12-21%) and kaolinite (8-26%). In despite of relatively constant values of illite crystallinity, ranging among 0.14°-0.20° Δ2θ, the time series variation in clay mineral distributions indicates a strong glacial-interglacial shift. Contents of illite, chlorite, and kaolinite (Core 18429) in the Holocene are lower than in the glacial period, and vice versa for the smectite content. The provenance analysis based on clay mineralogy suggests the Red River as a predominant sedimentary source of illite, chlorite, and kaolinite during all the depositional period of MIS 1-2. The sea level change actually controlled the variations of clay mineral assemblages on the upper slope since the Last Glacial Maximum. When the sea level was low during the last glacial period, more terrigenous sediments from the Red River could reach the continental slope in the northwestern South China Sea. However, when the sea level is closed to the present situation during the Holocene, most of Red River sediments could be trapped in the Gulf of Tonkin, instead of draining in the deep South China Sea.

Evolution of soils on quaternary reef terraces of Barbados, West Indies

USGS Publications Warehouse

Muhs, D.R.

2001-01-01

Soils on uplifted Quaternary reef terraces of Barbados, ???125,000 to ???700,000 yr old, form a climo-chronosequence and show changes in physical, chemical, and mineralogical properties with terrace age. Parent materials are dust derived from the Sahara, volcanic ash from the Lesser Antilles island arc, and detrital carbonate from the underlying reef limestone. Although some terrace soils are probably eroded, soils or their remnants are redder and more clay-rich with increasing terrace age. Profile-average Al2O3 and Fe2O3 content increases with terrace age, which partially reflects the increasing clay content, but dithionite-extractable Fe also increases with terrace age. Profile-average K2O/TiO2, Na2O/TiO2, and P2O5/TiO2 values decrease with terrace age, reflecting the depletion of primary minerals. Average SiO2/Al2O3 values also decrease with terrace age and reflect not only loss of primary minerals but also evolution of secondary clay minerals. Although they are not present in any of the parent materials, the youngest terrace soils are dominated by smectite and interstratified kaolinite-smectite, which gradually alter to relatively pure kaolinite over ???700,000 yr. Comparisons with other tropical islands, where precipitation is higher and rates of dust fall may be lower, show that Barbados soils are less weathered than soils of comparable age. It is concluded that many soil properties in tropical regions can be potentially useful relative-age indicators in Quaternary stratigraphic studies, even when soils are eroded or changes in soil morphology are not dramatic. ?? 2001 University of Washington.

Mineralogy of fine-grained alluvium from borehole U11g, expl. 1, northern Frenchman Flat area, Nevada Test Site

USGS Publications Warehouse

Jones, B.F.

1982-01-01

The mineralogy of matrix fines in alluvium from borehole Ullg, expl. 1, north of Frenchman Flat, Nevada Test Site, has been examined for evidence of past variations in water table elevation. Although greater abundance of zeolite and slightly more expanded basal spacings in smectite clays suggest effects of increased hydration of material up to 50 m above the present water table, these differences might also be related to provenance of environment of deposition. The relative uniformity of clay hydration properties in the 50 meters above the current water table suggest long-term stability near the present level. (USGS)

The nanophase iron mineral(s) in Mars soil

NASA Technical Reports Server (NTRS)

Banin, A.; Ben-Shlomo, T.; Margulies, L.; Blake, D. F.; Gehring, A. U.

1992-01-01

Iron-enriched smectites have been suggested as important mineral compounds of the Martian soil. They were shown to comply with the chemical analysis of the Martian soil, to simulate many of the findings of the Viking Labeled Release Experiments on Mars, to have spectral reflectance in the VIS-NIR strongly resembling the bright regions on Mars. The analogy with Mars soil is based, in a number of aspects, on the nature and behavior of the iron oxides and oxyhydroxides deposited on the surface of the clay particles. A summary of the properties of these iron phases and some recent findings are presented. Their potential relevance to Mars surface processes is discussed.

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.

Geothermometry, geochronology, and mass transfer associated with hydrothermal alteration of a rhyolitic hyaloclastite from Ponza Island, Italy

USGS Publications Warehouse

Altaner, S.P.; Ylagan, R.F.; Savin, S.M.; Aronson, J.L.; Belkin, H.E.; Pozzuoli, A.

2003-01-01

A rhyolitic hyaloclastite from Ponza Island, Italy, was hydrothermally altered, producing four distinct alteration zones based on X-ray diffraction mineralogy and field textures: (1) nonpervasive argillic zone; (2) propylitic zone; (3) silicic zone; and (4) sericitic zone. The unaltered hyaloclastite is volcanic breccia with clasts of vesiculated obsidian in a matrix of predominantly pumice lapilli. Incomplete alteration of the hyaloclastite resulted in the nonpervasive argillic zone, characterized by smectite and disordered opal-CT. The other three zones exhibit more complete alteration of the hyaloclastite. The propylitic zone is characterized by mixed-layer illite-smectite (I-S) with 10 to 85% I, mordenite, opal-C, and authigenic K-feldspar (akspar). The silicic zone is characterized by I-S with ???90% I, pure illite, quartz, akspar, and occasional albite. The sericitic zone consists primarily of I-S with ???66% I, pure illite, quartz, and minor akspar and pyrite. K/Ar dates of I-S indicate hydrothermal alteration occurred at 3.38 ?? 0.08 Ma. Oxygen isotope compositions of I-S systematically decrease from zones 1 to 4. In the argillic zone, smectite has ??18 O values of 21.7 to 22.0??? and I-S from the propylitic, silicic, and sericitic zones ranges from 14.5 to 16.3???, 12.5 to 14.0???, and 8.6 to 11.9???, respectively. ??18 O values for quartz from the silicic and sericitic zones range from 12.6 to 15.9???. By use of isotope fractionation equations and data from authigenic quartz-hosted primary fluid inclusions, alteration temperatures ranged from 50 to 65 ??C for the argillic zone, 85 to 125 ??C for the propylitic zone, 110 to 210 ??C for the silicic zone, and 145 to 225 ??C for the sericitic zone. Fluid inclusion data and calculated ??18 O water values indicate that hydrothermal fluids were seawater dominated. Mass-transfer calculations indicate that hydrothermal alteration proceeded in a relatively open chemical system and alteration in the sericitic zone involved the most extensive loss of chemical species, especially Si. Systematic gains in Mg occur in all alteration zones as a result of I-S clay mineral formation, and systematic losses of Na, Ca, and K occur in most zones. With the exception of Ca, calculations of mass transfer associated with hydrothermal alteration on Ponza agree with chemical fluxes observed in laboratory experiments involving hydrothermal reactions of rhyolite and seawater. The anomalous Ca loss at Ponza may be due to hydrothermal formation of anhydrite and later low-temperature dissolution. On the basis of Mg enrichments derived from circulating seawater, we estimate the following minimum water/rock ratios: 9, 3, 6, and 9 for the argillic, propylitic, silicic, and sericitic zones, respectively. Hydrothermal fluid pH for the propylitic and silicic zones was neutral to slightly basic and relatively acidic for the sericitic zone as a result of condensation of carbonic and perhaps other acids. Copyright ?? 2003 Elsevier Science Ltd.

Fe-SAPONITE and Chlorite Growth on Stainless Steel in Hydrothermal Engineered Barrier Experiments

NASA Astrophysics Data System (ADS)

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

2012-12-01

The United States recently has initiated the Used Fuel Disposition campaign to evaluate various generic geological repositories for the disposal of high-level, spent nuclear fuel within environments ranging from hard-rock, salt/clay, to deep borehole settings. Previous work describing Engineered Barrier Systems (EBS) for repositories focused on low temperature and pressure conditions. The focus of this experimental work is to characterize the stability and alteration of a bentonite-based EBS with different waste container materials in brine at higher heat loads and pressures. All experiments were run at ~150 bar and 125 to 300 C for ~1 month. Unprocessed bentonite from Colony, Wyoming was used in the experiments as the clay buffer material. The redox conditions for each system were buffered along the magnetite-iron oxygen fugacity univariant curve using Fe3O4 and Feo filings. A K-Na-Ca-Cl-based salt solution was chosen to replicate deep groundwater compositions. The experimental mixtures were 1) salt solution-clay; 2) salt solution -clay-304 stainless steel; and 3) salt solution -clay-316 stainless steel with a water/bentonite ratio of ~9. Mineralogy and aqueous geochemistry of each experiment was evaluated to monitor the reactions that took place. No smectite illitization was observed in these reactions. However, it appears that K-smectite was produced, possibly providing a precursor to illitization. It is unclear whether reaction times were sufficient for bentonite illitization at 212 and 300 C or whether conditions conducive to illite formation were obtained. The more notable clay mineral reactions occurred at the stainless steel surfaces. Authigenic chlorite and Fe-saponite grew with their basal planes near perpendicular to the steel plate, forming a 10 - 40 μm thick 'corrosion' layer. Partial dissolution of the steel plates was the likely iron source for chlorite/saponite formation; however, dissolution of the Feo/Fe3O4 may also have acted as an iron source, with the steel plates acting as a substrate for chlorite/saponite growth. Trace amounts of pyrite in the bentonite appeared to have reacted to form H2S gas and pentlandite ((Ni,Fe)8S9). Mineral growth on the waste containers was influenced by the container, buffer, and fluid compositions, in addition to pressure and temperature conditions. No significant mineralogical changes were apparent away from the steel-smectite interface. Results of this research show that the waste container may act as a substrate for mineral growth in response to corrosion. However, it is presently unknown whether chlorite and Fe-saponite will act as passivating agents or whether their presence will facilitate further corrosion of the waste containers. The role of these Fe-rich minerals on the stability of steel canisters at elevated heat loads is currently under investigation. LA-UR-12-23845

Characterization of structures of the Nankai Trough accretionary prism from integrated analyses of LWD log response, resistivity images and clay mineralogy of cuttings: Expedition 338 Site C0002

NASA Astrophysics Data System (ADS)

Jurado, Maria Jose; Schleicher, Anja

2014-05-01

The objective of our research is a detailed characterization of structures on the basis of LWD oriented images and logs,and clay mineralogy of cuttings from Hole C0002F of the Nankai Trough accretionary prism. Our results show an integrated interpretation of structures derived from borehole images, petrophysical characterization on LWD logs and cuttings mineralogy. The geometry of the structure intersected at Hole C0002F has been characterized by the interpretation of oriented borehole resistivity images acquired during IODP Expedition 338. The characterization of structural features, faults and fracture zones is based on a detailed post-cruise interpretation of bedding and fractures on borehole images and also on the analysis of Logging While Drilling (LWD) log response (gamma radioactivity, resistivity and sonic logs). The interpretation and complete characterization of structures (fractures, fracture zones, fault zones, folds) was achieved after detailed shorebased reprocessing of resistivity images, which allowed to enhance bedding and fracture's imaging for geometry and orientation interpretation. In order to characterize distinctive petrophysical properties based on LWD log response, it could be compared with compositional changes derived from cuttings analyses. Cuttings analyses were used to calibrate and to characterize log response and to verify interpretations in terms of changes in composition and texture at fractures and fault zones defined on borehole images. Cuttings were taken routinely every 5 m during Expedition 338, indicating a clay-dominated lithology of silty claystone with interbeds of weakly consolidated, fine sandstones. The main mineralogical components are clay minerals, quartz, feldspar and calcite. Selected cuttings were taken from areas of interest as defined on LWD logs and images. The clay mineralogy was investigated on the <2 micron clay-size fraction, with special focus on smectite and illite minerals. Based on X-ray diffraction analysis measured at room temperature and a relative humidity of ~30%, we compared the shape and size of illite and smectite, as well as their water content and their polytypes. The comparison of cuttings mineralogy with logging while drilling (LWD) data allowed us to characterize structural, petrophysical and mineralogical properties at fracture and fault zones. We also analyzed the relationship between deformation structures and compositional and mineralogical changes. We established a correlation between observed results on clay mineralogy and log responses in relation with the structures and trends characterized on logging data. In general, the log data provide a good correlation with the actual mineralogy and the relative abundance of clay. In particular we analyzed trends characterized by smectite water layers as indication of compaction. These trends were correlated with log response (on sonic velocity) within Unit IV. Our results show the integration of logging data and cutting sample analyses as a valuable tool for characterization of petrophysical and mineralogical changes of the structures of the Nankai accretionary prism.