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Sample records for randomly ordered smectite

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

    Science.gov (United States)

    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.

  2. Heterogeneous reactions of dioctahedral smectites in illite-smectite and kaolinite-smectite mixed-layers: applications to clay materials for engineered barriers

    International Nuclear Information System (INIS)

    Meunier, A.; Proust, D.; Beaufort, D.; Lajudie, A.; Petit, J.-C.

    1992-01-01

    The clay materials selected for use in the engineered barriers of the French nuclear waste isolation programme are mainly composed of dioctahedral smectite, either bentonite of Wyoming type or kaolinite-smectites most often consist of randomly stacked layers with low and high charges. In the case of the Wyoming-type bentonite, these two differently charged layers do not react in the same way when subjected to hydrothermal alteration. Overall, the low-charge smectite layers react to form high-charge smectite layers + quartz + kaolinite. Then, fixing K ions, the high-charge smectite layers are transformed into illite-smectite mixed-layers (I/S) when the temperature conditions increase. A symmetrical process is observed in natural or experimental hydrothermal conditions when the high-charge smectite layers of I/S minerals react with quartz and/or kaolinite to produce low-charge smectite layers. The chemical properties of the bentonite-engineered barriers clearly depend on the low charge/high charge smectite layer proportion, which is in turn controlled by the temperature-dependent reactions in the vicinity of the waste disposal. Although there are fewer published data on the kaolinite-smectite mixed-layered minerals (K/S), a similar low charge-high charge reaction appears to affect their smectite component. The experimental alteration of K/S leads to the formation of a low-charge beidellite with an increase in the cation-exchange capacity and in the expandability of the clay material. Thus, the properties of the engineered barrier seems to be improved after hydrothermal alteration. (Author)

  3. Adsorption of imidazolinone herbicides on smectite-humic acid and smectite-ferrihydrite associations.

    Science.gov (United States)

    Leone, P; Nègre, M; Gennari, M; Boero, V; Celis, R; Cornejo, J

    2002-01-16

    Adsorption of imazapyr (IMZ), imazethapyr (IMZT), and imazaquin (IMZQ) was studied on two smectite-humic acid and two smectite-ferrihydrite binary systems prepared by treating a Wyoming smectite with a humic acid extracted from soil (4 and 8% w/w of the smectite) and with just-precipitated synthetic ferrihydrite (8 and 16% w/w of the smectite). Adsorption of the three herbicides on the smectite was not measurable at pH >4.5, presumably because of negative charges on the surface of the smectite. Adsorption on the smectite-humic acid systems was also not measurable, presumably because of negative charges on the surface, despite the high affinity of the three herbicides for humic acid, the adsorption order of which was IMZ smectite-ferrihydrite systems and IMZQ smectite cannot adsorb herbicides, it modifies the adsorption capacity of ferrihydrite. The mutual interaction of active phases such as humic acid, ferrihydrite, and smectite alters the characteristics of the resulting surface and hence the adsorption process. Investigations of herbicide adsorption have been seen to produce more reliable results if conducted on polyphasic systems rather than on single soil components.

  4. Kaolinite flocculation induced by smectite addition - a transmission X-ray microscopic study.

    Science.gov (United States)

    Zbik, Marek S; Song, Yen-Fang; Frost, Ray L

    2010-09-01

    The influence of smectite addition on kaolinite suspensions in water was investigated by transmission X-ray microscopy (TXM) and Scanning Electron Microscopy (SEM). Sedimentation test screening was also conducted. Micrographs were processed by the STatistic IMage Analysing (STIMAN) program and structural parameters were calculated. From the results of the sedimentation tests important influences of small smectite additions to about 3wt.% on kaolinite suspension flocculation has been found. In order to determine the reason for this smectite impact on kaolinite suspension, macroscopic behaviour micro-structural examination using Transmission X-ray Microscope (TXM) and SEM has been undertaken. TXM & SEM micrographs of freeze-dried kaolinite-smectite suspensions with up to 20% smectite showed a high degree of orientation of the fabric made of highly oriented particles and greatest density when 3wt.% of smectite was added to the 10wt.% dense kaolinite suspension. In contrast, suspensions containing pure kaolinite do not show such platelet mutual orientation but homogenous network of randomly oriented kaolinite platelets. This suggests that in kaolinite-smectite suspensions, smectite forms highly oriented basic framework into which kaolinite platelets may bond in face to face preferential contacts strengthening structure and allowing them to show plastic behaviour which is cause of platelets orientation. Copyright 2010 Elsevier Inc. All rights reserved.

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

    Science.gov (United States)

    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.

  6. Correlation of index tests with smectite content determined with XRD in bentonite and smectite rich clays

    International Nuclear Information System (INIS)

    Kumpulainen, Sirpa; Kiviranta, Leena; Korkeakoski, Petri

    2012-01-01

    Document available in extended abstract form only. Various index tests are used by bentonite producers and users to assess the amount of swelling minerals in bentonites and smectite rich clays. Index tests are meant to provide relative fast and inexpensive way of testing the amount of swelling minerals, and their performance should not require sophisticated equipment. Such index tests are e.g. methylene blue absorption test, liquid limit and swelling index test (free swelling). In order to select appropriate index test to control the quality of buffer and backfill materials to be used in nuclear waste end disposal in Finland, results from various index tests were correlated with the smectite content determined with XRD and Rietveld refinement. Tests evaluated were: water absorption capacity (WAC) based on DIN 18132, swelling index (SI) based on ASTM D 5890-06, cation exchange capacity (CEC) based on Cu(II)-trien adsorption by Meier and Kahr (1999) and Ammann et al. (2005), liquid limit (LL) based on CEN ISO/TS 17892- 12:2004, methylene blue absorption (MB) based on SFS-EN 933-9, and specific surface area based on absorption of ethylene glycol monoethyl ether (EGME) described by Cerato and Lutenegger (2002). The number of samples tested was 6-25 (exact number of samples was dependent on the test method), and included natural Na-bentonites, natural Ca-bentonites, sodium activated Ca-bentonites and smectite rich clays from Wyoming/USA, Milos/Greece, Gujarat/India and Friedland/Germany. Smectite content in samples was determined after Kiviranta and Kumpulainen (2011) by x-ray diffraction (XRD), optical microscopy, chemical analyses, and full-pattern fitting with the Rietveld method using Siroquant software. Exchangeable cation composition was determined after Belyayeva (1967) and Jackson (1975). In order to achieve correlation of index test results with smectite content, water absorption capacity, liquid limit, and swelling index methods required additional information

  7. Smectite Formation in Acid Sulfate Environments on Mars

    Science.gov (United States)

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

    2017-01-01

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

  8. Sorption and desorption of carbamazepine from water by smectite clays.

    Science.gov (United States)

    Zhang, Weihao; Ding, Yunjie; Boyd, Stephen A; Teppen, Brian J; Li, Hui

    2010-11-01

    Carbamazepine is a prescription anticonvulsant and mood stabilizing pharmaceutical administered to humans. Carbamazepine is persistent in the environment and frequently detected in water systems. In this study, sorption and desorption of carbamazepine from water was measured for smectite clays with the surface negative charges compensated with K+, Ca2+, NH4+, tetramethylammonium (TMA), trimethylphenylammonium (TMPA) and hexadecyltrimethylammonium (HDTMA) cations. The magnitude of sorption followed the order: TMPA-smectite≥HDTMA-smectite>NH4-smectite>K-smectite>Ca-smectite⩾TMA-smectite. The greatest sorption of carbamazepine by TMPA-smectite is attributed to the interaction of conjugate aromatic moiety in carbamazepine with the phenyl ring in TMPA through π-π interaction. Partitioning process is the primary mechanism for carbamazepine uptake by HDTMA-smectite. For NH4-smectite the urea moiety in carbamazepine interacts with exchanged cation NH4+ by H-bonding hence demonstrating relatively higher adsorption. Sorption by K-, Ca- and TMA-smectites from water occurs on aluminosilicate mineral surfaces. These results implicate that carbamazepine sorption by soils occurs primarily in soil organic matter, and soil mineral fractions play a secondary role. Desorption of carbamazepine from the sorbents manifested an apparent hysteresis. Increasing irreversibility of desorption vs. sorption was observed for K-, Ca-, TMA-, TMPA- and HDTMA-clays as aqueous carbamazepine concentrations increased. Desorption hysteresis of carbamazepine from K-, Ca-, NH4-smectites was greater than that from TMPA- and HDTMA-clays, suggesting that the sequestrated carbamazepine molecules in smectite interlayers are more resistant to desorption compared to those sorbed by organic phases in smectite clays. Copyright © 2010 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

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

    2014-01-01

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

  10. Smectite alteration

    International Nuclear Information System (INIS)

    Anderson, D.M.

    1984-11-01

    This report contains the proceedings of a second workshop in Washington DC December 8-9, 1983 on the alteration of smectites intended for use as buffer materials in the long-term containment of nuclear wastes. It includes extended summaries of all presentations and a transcript of the detailed scientific discussion. The discussions centered on three main questions: What is the prerequisite for and what is the precise mechanism by which smectite clays may be altered to illite. What are likly sources of potassium with respect to the KBS project. Is it likely that the conversion of smectite to illite will be of importance in the 10 5 to the 10 6 year time frame. The workshop was convened to review considerations and conclusions in connection to these questions and also to broaden the discussion to consider the use of smectite clays as buffer materials for similar applications in different geographical and geological settings. SKBF/KBS technical report 83-03 contains the proceedings from the first workshop on these matters that was held at the State University of New York, Buffalo May 26-27, 1982. (Author)

  11. 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.

    Science.gov (United States)

    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.

  12. Electrical properties of smectites; Smectite nendo kobutsu no denkiteki bussei

    Energy Technology Data Exchange (ETDEWEB)

    Takakura, S; Nishizawa, O; Aoki, M [Geological Survey of Japan, Tsukuba (Japan); Kozake, K [University of Tsukuba, Tsukuba (Japan)

    1997-05-27

    With an objective to evaluate effects of clayish minerals in the electric and electromagnetic exploration methods, resistivities were measured on samples which have adjusted contents of clayish minerals. Samples were prepared for an experiment by mixing 300 g of glass beads having a diameter of about 1 mm, 200 g of aqueous solutions, and 3 to 90 g of smectites. The aqueous solutions used KCL, NaCL and CaCL2 at concentrations of 0.1 to 0.001 mol/L. The result of the experiment may be summarized as follows: among the three kinds of smectites, KN-1 has the greatest effect to reduce the resistivity; the resistivity decreases when the smectite amount is increased except when the concentration of the solution is high; this phenomenon is thought to be caused by increase in the region of an electrically doubled layer which has higher ion concentration; change in the resistivity increases when the solution concentration is low, and decreases when the concentration is high; and in the case of the solution concentration being 0.1 mol/L, the resistivity increases with increase in the smectite content. 5 refs., 7 figs., 1 tab.

  13. Smectite alteration by anaerobic iron corrosion

    International Nuclear Information System (INIS)

    Sanders, D.; Kaufhold, S.; Hassel, A.W.; Dohrmann, R.

    2010-01-01

    Document available in extended abstract form only. The interaction of smectites with corroding steel/iron represents a crucial topic in the estimation of the long term confinement properties of clay barriers for the encasement of steel/iron containers. Especially in case of engineered clay barriers a possible deterioration of favourable smectite properties as response to corrosion could reduce the barrier capacity. The extent of this reduction is unknown, yet. The essential properties of bentonite clays in this context are on the one hand the relatively high swelling pressure together with low hydraulic conductivity, which results from the well known expandability of smectite interlayers in aqueous environments. On the other hand smectites are cation exchangers being able to long term encase radioactive cations in a way that negative charges of silicate layers are compensated by easily exchangeable hydrated cations. Both properties are directly related to the crystal and chemical composition of smectites. The nature of the corrosion of steel canisters in clay barriers will - after a first short aerobic phase - predominantly be anaerobic resulting in the formation of Fe(II) and two equivalents of hydroxide ions. In a set of exposition experiments anaerobic corroding iron in bentonite gels was studied in order to determine alteration of the smectite fraction. During the exposition a green coloration of the bentonite neighbouring to corroding iron was observed. Upon contact to oxygen in a humid state the bentonite turned reddish indicating the oxidation of Fe(II) to Fe(III). This observation is in accordance with reported results indicating the formation of an iron rich smectite. Chemical analysis of the 'green bentonite' reveals an increase of iron fraction e.g. from 3.4% mass to 9.3% mass . The adsorbed iron is predominantly Fe(II) which was proven by chromato-metric titration. The estimated ratio between silicon to increased iron content is Si: Fe ≅ 2

  14. Experimental study of smectite interaction with metal iron at low temperature: 1. Smectite destabilization.

    OpenAIRE

    Lantenois , Sébastien; Lanson , Bruno; Muller , Fabrice; Bauer , Andreas; Jullien , Michel; Plançon , Alain

    2005-01-01

    Interaction between metal Fe and a variety of natural and synthetic smectite samples with contrasting crystal chemistry was studied by scanning electron microscopy and X-ray diffraction from experiments conducted at 80°C. These experiments demonstrate an important reactivity contrast as a function of smectite crystal chemistry. An XRD method involving the use of an internal standard allowed quantification of the relative proportion of smectite destabilized as a function of initial pH conditio...

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

    Science.gov (United States)

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

    2008-01-01

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

  16. Smectite for acute infectious diarrhoea in children.

    Science.gov (United States)

    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

  17. Influence of smectite hydration and swelling on atrazine sorption behavior.

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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

  19. In-situ interferometric measurements of compacted smectite under hyper-alkaline condition - 59124

    International Nuclear Information System (INIS)

    Satoh, Hisao; Kurosawa, Susumu; Ishii, Tomoko; Owada, Hitoshi

    2012-01-01

    Document available in abstract form only. Full text of publication follows: Alteration of bentonite buffer at the repository for radioactive waste is an unavoidable phenomenon. However, precise kinetic data is useful for evaluation of the endurance for long-term safety. Alkaline attack to bentonite by cement-leachates may enhance alteration of smectite into the other phase such as zeolite. Until recently, there are a number of detailed dissolution studies (e.g., Cama et al., 2000; Yokoyama et al., 2005; Rozalen et al., 2008) for suspended smectite, using high precision measurements by ICPMS and AFM analyses. In contrast, dissolution study of compacted smectite is very limited (e.g., Nakayama et al., 2003). In order to verify the previous data, the dissolution rate of compacted smectite with realistic density needs to be confirmed experimentally. We have, for the first time, applied in-situ vertical scanning interferometry (VSI) along with the auto-compaction cell for measuring dissolution rates of smectite compacted at 0.04-20.0 MPa and 70 deg. C in 0.3 M NaOH (pH 12.1). At less-compaction (0.04 MPa), Kunipia-P smectite initially showed a relatively fast dissolution of ∼2E-11 mol/m 2 /s which is comparable to the rate for suspended smectite under same pH-T condition. At high-compaction ( 2 /s, but at higher compaction (>5 MPa), smectite dissolution was enhanced again to ∼5E-13 mol/ m 2 /s

  20. Influence of smectites on resistivity of rocks and soils; Smectite nendo kobutsu ga ganseki dojo no hi teiko ni oyobosu eikyo

    Energy Technology Data Exchange (ETDEWEB)

    Takakura, S; Nishizawa, O; Aoki, M [Geological Survey of Japan, Tsukuba (Japan); Kozake, K [University of Tsukuba, Ibaraki (Japan)

    1996-10-01

    This paper illustrates the measurement results of resistivity for specimens including smectite clay minerals artificially synthesized, and also discusses the influence of smectites on resistivity. Three kinds of bentonites, i.e., KN-1, Kawasaki ore, and Kawasaki Sanhaku, were used for preparing smectites. The KN-1 is Na type smectite, the Kawasaki ore is Ca type smectite, and the Kawasaki Sanhaku is acid clay. It is well known that smectites lower the resistivity of rocks. However, the experimental results suggested that the degree of decreasing the resistivity depends on the kind of smectites. The effect of decreasing the resistivity by the KN-1 was much superior to the other smectites. For the KN-1, a thick electrical double layer was formed by Na ions in the interlayers, which resulted in the larger effect of decreasing the resistivity. Swelling capacity and cation exchange capacity (CEC) of the KN-1 were large, which agreed with the above mentioned consideration. Reversely, it was considered that smectites having larger effect of decreasing the resistivity exhibited larger swelling capacity and CEC. 4 refs., 3 figs.

  1. Smectite alteration

    International Nuclear Information System (INIS)

    Anderson, D.M.

    1983-02-01

    The colloquium was convened to compose a summary of the most recent data and the best scientific appraisal of present knowledge on the process of smectite conversion to illite. A brief account of a consensus view on the probable stability of smectite clays when employed as the buffer material in the Swedish nuclear fuel storage system. It is concluded that if the quantitiy of nuclear waste to be put in each bore hole is carefully limited, temperatures surrounding the cannister will not rise to an acceptable level and the clay buffer material can be relied upon to be effective throughout the life of the repository. (G.B.)

  2. Studies on certain physical properties of modified smectite nanocatalysts

    International Nuclear Information System (INIS)

    Wu, Ming Ching; Kuo, Shu Lung; Lin, Jao Chuan; Ma, Chih Ming; Hong, Gui Bing; Chang, Chang Tang

    2011-01-01

    Most volatile organic compounds (VOCs) are toxic to humans in some manner. Generally, transitional metal catalysts have better conversion rates for controlling VOCs. However, catalyst activity will decay at high temperature, though the oxidizing catalyst is cheap. This study used smectite as the carrier to exchange with Ag + , Zn 2+ and Ti 4+ to modify the surface and form smectite catalysts. In addition, the transmission electron microscopy (TEM), FT-IR spectrum, and DSC-TGA instrument were applied to characterize their physical properties. After the FT-IR analysis of the modified smectite catalyst (smectite-Ag, smectite-Zn and smectite-Ti), both smectite and smectite catalyst had significant and complicated wave crests between the fingerprint area with the wave numbers of 415-600 cm -1 and 750-1170 cm -1 , that indicated the existence of a strong bond between impure silicates (Si-O) and silicates (O-Si-O). TEM observation proved that sintering at 350 deg. C results in the distribution of catalyst ions on clay carrier with a nanoscale. As thermal analysis reveals, the smectite reached endothermic peaks at the temperatures of 920 deg. C and 1057 deg. C, respectively, and shows the decomposition in a non-crystal form. Besides, the disappearance of the endothermic peak of smectite-Ag occurs at 920.5 deg. C and the exothermic peak occurs at 950 deg. C. The results indicating crystals formed of smectite-Ag are more comprehensive and stable than the other smectite or modified smectite catalysts at high temperature.

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

    Science.gov (United States)

    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.

  4. On the smectite-to-illite reaction

    International Nuclear Information System (INIS)

    Oscarson, D.W.; Hume, H.B.

    1993-08-01

    The smectite component of the buffer material in a nuclear fuel waste disposal vault could slowly transform over long periods of time to an inter-stratified illite/smectite (I/S) material. This has important implications for the long-term effectiveness of the buffer material. The smectite-to-illite reaction was examined by treating Wyoming bentonite at 150, 200 and 250 degrees C for periods ranging from 90 to 194 days in five synthetic solutions having widely varying compositions. The solution-to-clay ratio was 0.025 m 3 /kg. Progress of the smectite alteration reaction was determined by measuring the expandability of the reaction products by X-ray diffractometry after the exchange complex of the clay was saturated with K and solvated with ethylene glycol. In all systems, the expandability of the I/S run products generally decreased (increase in the amount of I/S formed) with increasing temperature and time. The cation-exchange capacity of the clay was not, however, markedly affected by the hydrothermal treatments. The results indicate the presence of K in solution is not necessary for the development of high-charge layers in smectite (an increase in layer charge is the first step in the formation of illite from smectite). The expandability of the I/S was greater in the solutions with comparatively high concentrations of Ca. This supports the observation that the presence of Ca, rather than Na, on the exchange complex of smectite inhibits the formation of high-charge layers. The data do not allow us to predict the rate at which smectite will transform to I/S in a disposal vault environment. But the reaction will undoubtedly be very slow given that the temperature in a disposal vault will be <100 C and the concentration of K in groundwaters deep in granite rock very low compared with that of Ca and Na. (author). 54 refs., 4 tabs., 3 figs

  5. Prophylaxis of irradiation-induced Diarrhea with smectite. Results of a placebo-controlled investigation

    International Nuclear Information System (INIS)

    Hombrink, J.; Froehlich, D.; Glatzel, M.; Krauss, A.; Thiel, H.J.; Meier, J.; Hamann, D.; Muecke, R.; Glaser, F.H.; Koest, S.

    2000-01-01

    Between April 1994 and May 1995, a total of 176 patients obtaining radiotherapy of the pelvis or the abdomen were evaluated in a double-blind, randomized placebo-controlled investigation regarding the prophylactic effect of smectite (=Colina trademark ) against radiotherapy-induced diarrhea. During the whole period of radiotherapy 85 patients obtained 2x6 g smectite daily and 91 patients received 2x6 g placebo. The primary end point of the analysis was the time to the first appearance of diarrhea (≥3 pappy stools). Results: All 176 patients were evaluated according to an intent-to-treat analysis. There was no significant difference between the prophylactic effects of smectite and placebo. For an explorative post-hoc analysis the total study group was split up into 2 subgroups, one with an irradiated small bowel volume ≤837.5 ml, the other with a small bowel volume >837.5 ml (median); the analysis indicated that the first subgroup showed a benefit for the smectite-treated patients in contrast to the placebo treatment (32 vs. 18 calendar days to the first appearance of diarrhea). This benefit was statistically not significant. Conclusion: Prophylactic application of smectite during irradiation of the pelvis and the abdomen can delay the development of radiotherapy-induced diarrhea, a statistical significance could not be verified neither in the total study group nor in the post-hoc subgroup analysis. (orig.) [de

  6. Effect of radiation-induced amorphization on smectite dissolution.

    Science.gov (United States)

    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.

  7. Instrumental characterization of the smectite clay–gentamicin hybrids

    Indian Academy of Sciences (India)

    This paper focusses on the intercalation of clay mineral with gentamicin (an aminoglycoside antibiotic). The smectite clay–gentamicin hybrids were prepared by a solution intercalation at 60°C and the process was carried out on unmodified smectite clay and on smectite after Na+ ionic activation. The resulting ...

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

    Science.gov (United States)

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

    2014-01-01

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

  9. USAGE OF DIOCTAHEDRAL SMECTITE IN CHILDREN WITH ATOPIC DERMATITIS

    Directory of Open Access Journals (Sweden)

    A.S. Botkina

    2008-01-01

    Full Text Available The results of enter sorbent — dioctahedral Smectite (Neosmektin — usage as part of complex therapy of children with atopic dermatitis (ATD. It is shown that the administration of Smectite favored better efficacy of baseline treatment of ATD, more express and quick regression of skin manifestations of the disease, decrease in number of children with eosinophilia. High efficacy of ATD treatment with Smectite indicates the pathogenetic justification of efferent therapy of the disease. Observation results witness the good tolerability of Smectite: side effects related to the treatment were only observed in 14 percent of children.Key words: children, atopic dermatits, smectite, treatment.

  10. Fired products of Cr-smectite clays in nitrogen

    Directory of Open Access Journals (Sweden)

    C. Volzone

    2004-12-01

    Full Text Available The products of Cr-smectite clays heated to 1350 ° C in nitrogen were evaluated by X-ray diffraction and chemical analysis. Cr-smectite clays were prepared at room temperature by contact between smectite clays and Cr species contained in OH-Cr solutions. The Cr species were prepared using chromium nitrate solution by addition of NaOH solution with OH/Cr = 2. Products of firing in nitrogen at the high temperature were different (magnesia chromite, donathite, iron chromium oxide and picrochromite depending on the type of isomorphous substitution of the smectite structure and the amount of retained chromium.

  11. Wound healing effect of bioactive ion released from Mg-smectite.

    Science.gov (United States)

    Sasaki, Yu; Sathi, Gulsan Ara; Yamamoto, Osamu

    2017-08-01

    Bioactive ions like Mg 2+ and Si 4+ have been known as promotion factors of tissue regeneration. In the present work, Mg-smectite, consisting of Mg 2+ and Si 4+ ions, was synthesized by a solution process, and evaluated for the efficiency of the powder on wound healing in rats. White precipitates were obtained by mixing a magnesium chloride hexahydrate solution and a sodium silicate hexahydrate solution at room temperature. The precipitates mixed with a NaOH aqueous solution were subjected to hydrothermal reaction, and finally crystalline Mg-smectite powder was obtained. The crystal and molecular structure of Mg-smectite was identified by X-ray diffractometry (XRD) and Fourier-transform infrared spectroscopy (FT-IR). The synthesized material was determined to be crystalline Mg-smectite. The amount of Mg 2+ and Si 4+ ions released from Mg-smectite in physiological saline was analyzed by inductively coupled plasma mass spectroscopy (ICP-MS). The total amount of Si 4+ ion released from Mg-smectite was greater than that of Mg 2+ ion. To evaluate the wound healing effect of Mg-smectite, Mg-smectite powder was applied to a full-thickness surgical wound reaching the subcutaneous tissue in the rat's abdomen. At 1 and 2weeks, skin tissue was collected and subjected to histological analysis. The results for skin regeneration showed no significant difference in wound size between the control and Mg-smectite group. However, it was found that the neovascularization, collagen deposition, and maturation were notedly accelerated by applying Mg-smectite powder in comparison with the control. Mg-smectite can then be hypothesized to stimulate the regeneration of skin tissue by releasing Mg 2+ and Si 4+ ions. These results suggested that Mg-smectite could offer great potential as a wound dressing material. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Role of interlayer hydration in lincomycin sorption by smectite clays.

    Science.gov (United States)

    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- 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.

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

    Science.gov (United States)

    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 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.

  14. Illitization of Potassium, Cesium, and Ammonium Exchanged Smectite

    Science.gov (United States)

    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 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

  15. Kinetic Study of Denatonium Sorption to Smectite Clay Minerals.

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  17. Interaction between tetracycline and smectite in aqueous solution.

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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 smectite increased (p smectite. LAB and smectite also increased (p smectite affected (p 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.

  19. Fired products of Cr-smectite clays in nitrogen

    OpenAIRE

    C. Volzone; A. M. Cesio

    2004-01-01

    The products of Cr-smectite clays heated to 1350 ° C in nitrogen were evaluated by X-ray diffraction and chemical analysis. Cr-smectite clays were prepared at room temperature by contact between smectite clays and Cr species contained in OH-Cr solutions. The Cr species were prepared using chromium nitrate solution by addition of NaOH solution with OH/Cr = 2. Products of firing in nitrogen at the high temperature were different (magnesia chromite, donathite, iron chromium oxide and picrochromi...

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

    Science.gov (United States)

    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.

  1. Influence of Iltization on the Ion-sorbing Capacity of Smectitic Clay

    International Nuclear Information System (INIS)

    Lee, Jae Owan; Cho, Won Jin

    2008-01-01

    A high-level waste(HLW) repository uses smectitic clay as a buffer material to inhibit the penetration of groundwater and to retard the release of radionuclides from the radioactive wastes to the surrounding environment. However, when the smectitic clay is exposed to an elevated temperature due to radioactive decay heat and geochemical conditions for a long time, its physicochemical and mineralogical properties may be degradated and thus lose its barrier functions. It has been known in literature that the degradation of these properties of the smectitic clay occurs by a illitization in which the smectite transforms into illite. Therefore, an understanding of the illitization is essential to evaluate the long-term barrier performance of smectitic clay for the buffer of a HLW repository. This paper will carry out hydrothermal reaction tests with domestic smectitic clay which will be favorably considered for the buffer material of a Korean HLW repository, and also investigate the influence of illization on the ion-sorbing capacity of the smectitic clay

  2. Effect of crystallochemistry of starting materials on the rate of smectite to illite reaction

    International Nuclear Information System (INIS)

    Sato, Tsutomu; Isobe, Hiroshi; Ohnuki, Toshihiko; Murakami, Takashi

    1995-01-01

    A series of hydrothermal experiments was performed to determine the effect of layer charge of starting materials on the smectite to illite reaction rate that might be applied to nuclear-waste repository design. The experiments were conducted on K-saturated fractions of Wyoming smectite (SWy-1) and Tsukinuno smectite (SKu-F) in a closed system at temperatures of 95, 150, 200, 250, 300 C for run durations of up to 477 days with a 1:20 mass ratio of solid to deionized water. The mean layer charge and tetrahedral charge of SKu-F are larger than those of SWy-1. The proportion of smectite layers in illite/smectite interstratified minerals rapidly decreases, and then slowly decreases with increase in reaction time; a plot of ln (100/% smectite) vs. time produces two distinct straight lines in all experiments. These lines are suggestive of two first-order kinetic processes with different rates for this reaction; the first process has a greater rate than the second one. An Arrhenius plot of the reaction rates for each process produces a folding and straight lines for the first and second processes, respectively, suggesting that there are at least two parallel processes in the first process, and a dominant process is different between high- and low-temperature reactions. The activation energies of the first and second processes determined from the plots are the same for the two starting materials, meaning that the reaction mechanisms for the two starting materials are the same. However, the rate of the first process is different between the two starting materials, although that of the second process is similar. The difference in the rate of the first process results possibly from the difference in the amount of layer charge between the two starting smectites

  3. The smectite to chlorite transition in the Chipilapa geothermal system, El Salvador

    Energy Technology Data Exchange (ETDEWEB)

    Robinson, D. [Univ. of Bristol (United Kingdom). Dept. of Earth Sciences; Santana de Zamora, A. [Comision Ejecutiva Hidroelectrica del Rio Lempa (El Salvador)

    1999-04-01

    Clay mineralogical, X-ray diffraction and electron microprobe studies have been carried out on separated <2 {micro}m fractions from cutting and core material from three wells in the Chipilapa geothermal system in El Salvador. The data indicate that the smectite to chlorite transition is prevalent, but a secondary smectite to illite transition is also present. At depths approximately <750 m, smectite with very minor chlorite mixed-layers (approximately <15%) is dominant, and has a composition midway between a di- and tri-smectite. At {approximately}750 m there is a very clear distinction and sharp transition into discrete chlorite with very minor smectite mixed-layers (approximately <10%). Corrensite is recorded only as a rare and minor phase. Smectite occurs in abundance at temperatures up to {approximately}200 C, and the transition from a smectite-dominant to chlorite-dominant assemblage takes place over a narrow temperature range ({approximately}150 to 200 C). The stability range of smectite is very similar to that recorded in other geothermal systems, whereas the smectite to chlorite transition differs greatly from that recorded in other systems. The transition does not involve continuous chlorite/smectite mixed-layering but a marked step: It is the sharpest and most discontinuous stepped sequence of this mineralogical transition recorded.

  4. Siderophore-promoted dissolution of smectite by fluorescent Pseudomonas.

    Science.gov (United States)

    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.

  5. Ethylene glycol intercalation in smectites. molecular dynamics simulation studies

    International Nuclear Information System (INIS)

    Szczerba, Marek; Klapyta, Zenon; Kalinichev, Andrey

    2012-01-01

    Document available in extended abstract form only. Intercalation of ethylene glycol in smectites (glycolation) is widely used to discriminate smectites and vermiculites from other clays and among themselves. During this process, ethylene glycol molecules enter into the interlayer spaces of the swelling clays, leading to the formation of two-layer structure (∼17 A) in the case of smectites, or one-layer structure (∼14 A) in the case of vermiculites. In spite of the relatively broad literature on the understanding/characterization of ethylene glycol/water-clays complexes, the simplified structure of this complex presented by Reynolds (1965) is still used in the contemporary X-ray diffraction computer programs, which simulate structures of smectite and illite-smectite. The monolayer structure is only approximated using the assumption of the interlayer cation and ethylene glycol molecules lying in the middle of interlayer spaces. This study was therefore undertaken to investigate the structure of ethylene glycol/water-clays complex in more detail using molecular dynamics simulation. The structural models of smectites were built on the basis of pyrophyllite crystal structure (Lee and Guggenheim, 1981), with substitution of particular atoms. In most of simulations, the structural model assumed the following composition, considered as the most common in the mixed layer illite-smectites: EXCH 0.4 (Si 3.96 Al 0.04 )(Al 1.46 Fe 0.17 Mg 0.37 )O 10 (OH) 2 Atoms of the smectites were described with CLAYFF force field (Cygan et al., 2004), while atoms of water and ethylene glycol with flexible SPC and OPLS force fields, respectively. Ewald summation was used to calculate long range Coulombic interactions and the cutoff was set at 8.5 A. Results of the simulations show that in the two-layer glycolate the content of water is relatively small: up to 0.8 H 2 O per half of the smectite unit cell. Clear thermodynamic preference of mono- or two-layer structure of the complex is

  6. Rheological properties of sodium smectite clay

    International Nuclear Information System (INIS)

    Boergesson, L.; Hoekmark, H.; Karnland, O.

    1988-12-01

    The rheological properties of Na-smectite Mx-80 have been investigated by various laboratory tests. The investigations include determination of the hydraulic conductivity, the undrained stress-strain-strength properties, the creep properties, the compression and swelling properties in drained and undrained conditions and the undrained thermomechanical properties. Measurements have been made at different densities, clay/sand mixtures and pore water compositions. The influence of temperature, rate of strain and testing technique has also been considered. The investigation has led to a supply of basic data for the material models which will be used at performance calculations. The results have also increased the general understanding of the function of smectitic clay as buffer material. The microstructural behaviour has been considered at the validation of the different test results and the validity of the effective stress theory has been discussed. Comparisons with the properties of Ca-smectite have also been made. (orig.)

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

    Science.gov (United States)

    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.

  8. Sorption characteristics of radioactive cesium and strontium on smectite

    International Nuclear Information System (INIS)

    Ohnuki, Toshihiko; Kozai, Naofumi

    1994-01-01

    Sorption of 137 Cs and 85 Sr on smectite has been studied by combining sorption and desorption experiments. In the desorption experiments, the 137 Cs and 85 Sr were desorbed from the smectite by 0.1 N different desorption reagents solution of Li + , Na + , K + , Rb + , Cs + , Mg 2+ , Ca 2+ and Ba 2+ . The effects of Cs and Sr concentrations on sorption were examined by desorption experiments using 1 N KCl as a desorption reagent over a Cs and Sr concentrations range from 10 -8 to 1 N (saturated). All of Sr sorbed was desorbed with a 1 N KCl solution over Sr concentrations range of 10 -8 and 1 M. Approximately 50% of the 137 Cs sorbed at a concentration of 10 -8 M was desorbed with a 1 N KCl solution, and the fraction desorbed increased with increasing a Cs concentration. These results show that all Sr was reversibly sorbed on smectite, and a fraction of Cs was irreversibly sorbed on smectite. Thus, smectite has reversible sorption sites for Sr and both reversible and irreversible sorption sites for Cs. The fractions of Sr desorbed were related to the products of an ionic radius and charge of a desorption reagent, and those of Cs were related to the hydration energy. These results suggest that sorbed Sr and Cs reversibly on smectite form hydrated and dehydrated ions, respectively. (orig.)

  9. Removal of lead and phosphate ions from aqueous solutions by organo-smectite.

    Science.gov (United States)

    Bajda, Tomasz; Szala, Barbara; Solecka, Urszula

    2015-01-01

    Smectite has been modified using hexadecyltrimethyl ammonium bromide in an amount of double cationic exchange capacity. This alteration makes it possible to use organo-smectite as a sorbent to remove anionic forms. The experiment consisted of the interchangeable sorption of phosphate(V) and lead(II) by organo-smectite. Research was carried out with varying pH (2-5) and various concentrations (0.1-5 mmol/L). Organo-smectite with previously adsorbed lead ions removed more phosphate than the untreated organo-smectite. Experimental data show that lead is more likely to absorb on the organo-smectite than on the organo-smectite with previously adsorbed phosphate ions. It follows that the most effective use of the organo-smectite is through the sorption of first - Pb cations and then PO4 anions. With an increasing concentration of Pb(II) or P(V), the sorption efficiency increases. The maximum sorption efficiency of lead and phosphate ions is observed at pH 5. This enables the removal of harmful lead and phosphorus compounds from waste water and immobilizes them on the sorbent's surface. The alternating reactions of lead and phosphorus ions result in the crystallization of brompyromorphite Pb5(PO4)3Br.

  10. 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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

  12. Reducing bioavailability and phytotoxicity of 2,4-dinitrotoluene by sorption on K-smectite clay.

    Science.gov (United States)

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

    2007-02-01

    Smectite clays demonstrate high affinities for nitroaromatics that strongly depend on the exchangeable cation. The K-smectites have high affinities for nitroaromatics, but Ca-smectites do not. Here we evaluate the ability of K-smectite to attenuate the bioavailability and hence toxicity of 2,4-dinitrotoluene (2,4-DNT) to the aquatic plant duckweed. In the absence of K-smectite, 2,4-DNT was highly toxic to duckweed. Small amounts of K-smectite reduced toxicity substantially, presumably by reducing 2,4-DNT bioavailability via sorption.

  13. Synthetic mullite fabrication from smectite clays

    International Nuclear Information System (INIS)

    Lima, L.N. de; Kiminami, R.H.G.A.

    1988-01-01

    The technological importance of mullite is mostly due to its refractory properties. Mullite in native form is very rare, and therefore it may be necessary to produced it by synthetic means. Brazil has a large reserve of smectite clays. In this work the process to produce synthetic mullite from these clays by treatment with aluminum sulphate was studied. X-ray analyses has shown the presence of mullite crystals in treated smectite clays of several colours, sinterized at 1100 0 C. By sintering at 1300 0 C, pure mullite was obtained in some colours. (author) [pt

  14. Transmission X-ray microscopy (TXM) reveals the nanostructure of a smectite gel.

    Science.gov (United States)

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

    2008-08-19

    The unusual behavior of smectites, the ability to change volume when wetted (swelling) or dried (shrinking), makes soil rich in smectites very unstable and dangerous for the building industry because of the movement of building foundations and poor slope stability. These macroscopic properties are dominated by the structural arrangement of the smectites' finest fraction. Here, we show in three dimensions how the swelling phenomenon in smectite, caused by a combination of hydratation and electrostatic forces, may expand the dry smectite volume not 10-fold, as previously thought, but to more than 1000-fold. A new technique, transmission X-ray microscopy, makes it possible to investigate the internal structure and 3-D tomographic reconstruction of clay aggregates. This reveals, for the first time, the smectite gel arrangement in the voluminous cellular tactoid structure within a natural aqueous environment.

  15. A simple way to constrain the stoichiometry of secondary smectites upon aqueous glass alteration

    International Nuclear Information System (INIS)

    Thien, Bruno M.J.

    2014-01-01

    Highlights: • Si/Al of different glasses were compared to Si/Al of associated secondary smectites. • Si/Al of secondary smectite is nearly equal to Si/Al of parent glass. • This is a simple way which can help to constrain smectite composition. • Accurate smectite composition cannot be measured in many cases. - Abstract: The comparison of the stoichiometry of several nuclear waste glasses and basaltic glasses with their associated secondary smectites evidenced that Si/Al ratios of secondary smectites are nearly equal to the Si/Al ratios of parent glasses. This information may be very useful in constraining secondary smectites structure and stoichiometry in cases where other identification methods are difficult to apply

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

    Science.gov (United States)

    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

  17. A study of specific sorption of neptunium(V) on smectite in low pH solution

    International Nuclear Information System (INIS)

    Kozai, Naofumi; Ohnuki, Toshihiko; Matsumoto, Junko; Banba, Tsunetaka; Ito, Yoshimoto

    1996-01-01

    The 'specific sorption' of neptunium(V) on smectite, in other words, a strong sorption undesorbable by 1 M KCl, is studied with a combination of batch type sorption and desorption experiments over a pH range of 2 to 5. Six types of homoionic smectite (Li-, Na-, K-, Cs-, Mg-, and Ca-smectite) are used in this study. Distribution coefficients (K d ) of neptunium for smectite vary over a wide pH range; the maximum K d value of ∝300 cm 3 x g -1 at around pH 2 for Li- and Na-smectite and the minimum value of ∝2 cm 3 x g -1 for Cs-smectite. The specific sorption of neptunium depends on pH and on the affinity of the exchangeable cation for smectite; the lower the pH of solution or the affinity, the larger the specific sorption. The neptunium-smectite association varies with the elapse of contact time. Within the first day of the neptunium-smectite contact the neptunium sorbed on na-smectite at low pH is desorbable by 1 M KCl solution, and on the passage of time most of the neuptunium sorbed becomes undesorbable by KCl (the specific sorption). Hydronium ion in solution is sorbed on smectite at low pH and dissociates the exchangeable cation from smectite into solution, and the specific sorption of neuptunium increases with increasing the exchangeable cation that is dissociated from smectite. (orig.)

  18. Ordered random variables theory and applications

    CERN Document Server

    Shahbaz, Muhammad Qaiser; Hanif Shahbaz, Saman; Al-Zahrani, Bander M

    2016-01-01

    Ordered Random Variables have attracted several authors. The basic building block of Ordered Random Variables is Order Statistics which has several applications in extreme value theory and ordered estimation. The general model for ordered random variables, known as Generalized Order Statistics has been introduced relatively recently by Kamps (1995).

  19. Redistribution of strontium and cesium during alteration of smectite to illite

    International Nuclear Information System (INIS)

    Ohnuki, Toshihiko; Murakami, Takashi; Sato, Tsutomu; Isobe, Hiroshi

    1994-01-01

    The redistribution of strontium and cesium during the alteration of smectite to illite has been studied under hydrothermal conditions at 200 C using solutions of 1x10 -4 M Sr and Cs. Two different sorption conditions were applied for the hydrothermal experiments. One was the condition in which strontium and cesium were sorbed by smectite before the hydrothermal experiments (dynamic condition). The other was the condition in which strontium and cesium were sorbed by the alteration products, illite/smectite (I/S) interstratified minerals after the hydrothermal experiments (static condition). The sorption characteristics of strontium and cesium by smectite, I/S interstratified minerals were examined by a sequential extraction method. Most of the strontium was desorbed from smectite and the I/S interstratified minerals with a 1 M KCl solution under both the dynamic and static conditions. Less than 1% of cesium was desorbed from the I/S interstratified minerals with any solution of a 1 M KCl, a 1 M HCl and a 6 M HCl under the dynamic condition, while most of cesium was desorbed with either solution of a 1 M KCl and 1 M HCl from smectite and from the I/S interstratified minerals under the static condition. These suggest that cesium sorbed by smectite changes its sorption characteristic during the alteration process, but strontium does not. Possible sites for more strongly bounded cesium to the I/S interstratified minerals may be at the 'ditrigonal cavity' of adjacent tetrahedral layers. (orig.)

  20. Geological evidence of smectite longevity

    International Nuclear Information System (INIS)

    Pusch, R.; Karnland, O.

    1988-12-01

    Search is going on for geological evidence of natural smectite clay materials that have been exposed to conditions that are similar to those radioactive in repositories. Cases in which heating to 90 degree C or more for long periods has taken place, are of particular interest. The report describes two bentonite layers, one of Miocenic age located at central Sardinia (Busachi), and the other of Ordovician age, forming a basal stratum of southern Gotland, (Hamra), Sweden. They both serve as excellent examples of the survival potential of montmorillonite-rich clays. The more than 10 m thick Sardinian bentonite bed was very significantly heated when the magma moved in and covered it. The upper meter was heated to more than 200 degree C for several days, while at more than 4 m depth, the temperature did note exceed 80 degree C. The test show that the smectite content was not reduced to less than 60 percent in any part of the layer sequence, while slight cementation was caused by precipitation of heat-released silica in the uppermost layer. The 0.3 m thick bed on Gotland is presently located at 515 m depth. Various investigations indicate that it has been exposed to an effective pressure of 300 MPa and a temperature of 110 degree C for several million years due to burial under almost 3 km of Devonian sediments. The content of smectite is around 25 percent of the bulk material, and 30-40 percent of the clay fraction. Illite appears to have been neoformed in small voids of the smectite matrix and the identified apparent I/S material is suggested to consist of mixed-layer minerals with hydrous mica and Ca or Na locked in instead of K, which would be the conventional interpretation. The earlier developed alteration model appears to be valid and it is extended in the present report on the basis of the findings. (28 illustrations, 9 tables)

  1. Influence of smectite crystal chemistry on the organization of interlayer water and cations

    International Nuclear Information System (INIS)

    Dazas, Baptiste

    2014-01-01

    Swelling clay minerals such as smectites are ubiquitous at the Earth surface and possess major hydration ability and contaminant uptake/retention capacity. As a consequence smectites exert a pivotal influence on elemental transfers in surficial environments. These properties are especially relevant also when smectites are used as sealant in engineered or geological barriers for waste disposal facilities. As interlayer H_2O molecules account for more than 80% of smectite water in under-saturated conditions, characterization of H_2O organization and dynamics in smectites interlayers is essential to determining the geometrical and dynamical properties of clay barriers for waste disposal and to predicting the mobility of contaminant whose principal vector is water. Within this general framework, the present works describe, in a first time, the structuration of interlayer water/cations in saturated conditions. Then, in a second time, review the influence of structural parameters such as the amount and location of layer charge deficit and the chemical composition (and more especially the presence of structural fluorine/hydroxyl) on smectite hydration properties. A set of samples covering the whole compositional range of swelling phyllosilicates has thus been synthesized and characterized chemically and structurally. Special attention was paid to determining the amount (water vapor sorption isotherms) and the distribution (X-ray diffraction) of interlayer water. Molecular modeling allowed unraveling the origin of the contrasting behaviors observed experimentally and to determine the influence of the different crystal-chemical parameters on smectite hydration. This step is essential for the prediction of smectite reactivity in the environment from a limited number of crystal-chemical parameters. Molecular modeling allowed unraveling the origin of the contrasting behaviors observed experimentally and to determine the influence of the different crystal-chemical parameters on

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

    Science.gov (United States)

    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 Smectite powder is beneficial to the protection of the intestinal mucosa in scalded rats, and can effectively prevent postburn intestinal bacterial translocation in rats.

  3. Smectite dehydration and stability: Applications to radioactive waste isolation at Yucca Mountain, Nevada

    International Nuclear Information System (INIS)

    Bish, D.L.

    1988-03-01

    Montmorillonite-beidellite smectites are present in amounts up to 50% in the rocks directly underlying the potential high-level radioactive waste repository horizon at Yucca Mountain, Nevada. The thermal reactions of concern include reversible collapse/expansion of the smectite layers due to loss/gain of interlayer water;irreversible collapse due to loss of interlayer water and migration of interlayer cations into the 2:1 silicate layers;irreversible reduction of the osmotic swelling ability through reaction in a steam atmosphere;and inhomogeneous transformation of the smectite into an interstratified illite/smectite. Reversible collapse should be of minor importance because any thermally driven collapse will be reversed when water is introduced and temperatures go down. The amounts of smectite in the potential repository horizon itself are probably insufficient to give rise to rock strength problems due to reversible collapse. The irreversible reduction of somotic selling capacity in a steam environment may be significant in the rocks near the repository horizon. This effect on naturally occurring Na-rich smectites would probably increase permeabilitie shut would also provide for increased cation exchange by the smectite. 60 refs., 9 figs

  4. Mechanisms for adsorption of organic bases on hydrated smectite surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Laird, D.A.; Fleming, P.D.

    1999-08-01

    The environmental fate of anthropogenic organic bases introduced to soils and sediments, either deliberately as pesticides or inadvertently as contaminants, depends, to a large extent, on reactions between those compounds and the surfaces of soil mineral and organic constituents. Mechanisms by which organic bases are adsorbed on hydrated smectite surfaces were investigated. Three Ca-saturated reference smectites (Otay, SPV, and Panther Creek) were dispersed in distilled water containing 5 {micro}mol of pyridine or 3-butylpyridine. The pH was adjusted to between 7.5 and 3 using 0.01 M HCl. After a 2-h equilibration, the amounts of pyridine or 3-butylpyridine adsorbed on the clay and the amount of Ca desorbed from the clay were determined. Negligible amounts of pyridine were adsorbed by the Ca-smectites in the neutral systems (pH > 7); however, most of the added pyridine was adsorbed on the smectites in the acidified systems (pH < 5). Equivalent amounts of Ca{sup 2+} were desorbed from the clays, indicating that pyridine was adsorbed as a protonated species by cation exchange. By contrast, 40 to 90% of added 3-butylpyridine was adsorbed on the smectites at neutral pHs, whereas only small amounts of Ca{sup 2+} were desorbed. The results suggest that 3-butylpyridine is initially retained by hydrophobic bonding between the alkyl side chain of the molecule and hydrophobic nanosites located between the charge sites on smectite surfaces. Surface acidity catalyzed protonation 1 to 1.5 pH units above the pK{sub a} of the bases.

  5. Sorption behavior of cobalt on manganese dioxide, smectite and their mixture

    International Nuclear Information System (INIS)

    Ohnuki, T.; Kozai, N.

    1995-01-01

    The sorption behavior of cobalt on manganese dioxide, the clay mineral smectite and mixtures of the two was studied by batch type sorption/desorption experiments at neutral pH. Sorption behavior was examined by sequential extraction, in which the sorbents were contacted first with a 1 M CH 3 COONH 4 solution and then with a hydroxylamine solution (NH 2 OH of 1 M with 25 weight % CH 3 COOH). More than 70% of the sorbed cobalt was desorbed from smectite with a 1 M CH 3 COONH 4 solution: about 15% of the cobalt remained on the smectite after treatment with the hydroxylamine solution. Less than 1% of the remaining cobalt was desorbed from manganese dioxide with a 1 M CH 3 COONH 4 solution; with the hydroxylamine solution, all was desorbed. In mixtures of MnO 2 and smectite that were formulated to sorb equal amounts of cobalt regardless of the MnO 2 /smectite ratio in the mixture, less than 5% of the sorbed cobalt was desorbed by treatment with 1 M CH 3 COONH 4 . The fraction of the cobalt desorbed by treatment with the hydroxylamine solution increased with increased MnO 2 in the mixtures. The fraction of the cobalt sorbed on MnO 2 in the mixture was estimated from the desorption experiments. The results showed that higher fractions were sorbed onto MnO 2 than were estimated by the weighted averages of distribution coefficients for MnO 2 and smectite. Therefore, in minerals of the mixture, manganese dioxide is a more important component than smectite for the sorption of cobalt. (orig.)

  6. The conversion of smectite to illite in hydrothermal systems

    International Nuclear Information System (INIS)

    Johnston, R.M.

    1983-06-01

    In natural diagenetic shale systems, smectite converts to illite and mixed-layer illite-smectite in less than a million years at temperatures between 75 degrees C and 200 degrees C. This has raised questions as to the stability of smectite-based bentonite buffers under nuclear waste disposal vault conditions. Experimental and geological evidence indicate that the reaction is dependent on the availability of K + , and that the rate of reaction in K + -poor systems (such as the disposal vault) may be much lower than that observed in shale. The presence of Na + , Ca 2+ and Mg 2+ in the system slows the reaction and may halt it altogether at lower temperatures. Two different reaction mechanisms have been proposed; the evidence for, and implication of, each are discussed

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

    Science.gov (United States)

    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.

  8. Quantum-chemical modeling of smectite clays

    Science.gov (United States)

    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.

  9. Sensitivity of Clay Suspension Rheological Properties to pH, Temperature, Salinity, and Smectite-Quartz Ratio

    Science.gov (United States)

    Kameda, Jun; Morisaki, Tomonori

    2017-10-01

    Understanding the rheological properties of clay suspensions is critical to assessing the behavior of sediment gravity flows such as debris flow or turbidity current. We conducted rheological measurements of composite smectite-quartz suspensions at a temperature of 7°C and a salt concentration of 0.6 M. This is representative of smectite-bearing sediments under conditions on the seafloor. The flow curves obtained were fitted by the Bingham fluid model, from which we determined the Bingham yield stress and dynamic viscosity of each suspension. At a constant smectite-quartz mixing ratio, the yield stress and the dynamic viscosity tend to increase as the solid/water ratio of the suspension is increased. In the case of a constant solid/water ratio, these values increase with increasing smectite content in the smectite-quartz mixture. Additional experiments exploring differing physicochemical conditions (pH 1.0-9.0; temperature 2-30°C; and electrolyte (NaCl) concentration 0.2-0.6 M) revealed that the influence of temperature is negligible, while pH moderately affects the rheology of the suspension. More significantly, the electrolyte concentration greatly affects the flow behavior. These variations can be explained by direct and/or indirect (double-layer) interactions between smectite-smectite particles as well as between smectite-quartz particles in the suspension. Although smectite is known as a frictionally weak material, our experimental results suggest that its occurrence can reduce the likelihood that slope failure initiates. Furthermore, smectite can effectively suppress the spreading distance once the slope has failed.

  10. Transformation of adsorbed aflatoxin B1 on smectite at elevated temperatures

    Science.gov (United States)

    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 ...

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

    Science.gov (United States)

    2007-01-01

    American Mineralogist, Volume 92. pages 1401-1410, 2007 Microbial effects in promoting the smectite to illite reaction: Role of organic matter...rich smectite (non- tronile, NAu-2). The illitization of these intercalated smectites as induced by microbial reduction of structural Fe" was...transmission electron microscopy did not detect any discrete illite, although illite/ smectite mixed layer or high charge smectite phases were observed. In

  12. Experimental study and modelling of selenite sorption onto illite and smectite clays.

    Science.gov (United States)

    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.

  13. Changes in the Expandability, Layer charge, and CEC of Smectitic Clay due to a Illitization

    International Nuclear Information System (INIS)

    Lee, Jae Owan; Cho, Won Jin

    2007-01-01

    In a high-level waste(HLW) repository, the major fucntions of the smectitic clay for use as a buffer material are to inhibit the penetration of groundwater and to retard the release of radionuclides from the radioactive wastes to the surrounding environment. However, when the smectite clay is exposed to an elevated temperature due to radioactive decay heat and geochemical conditions for a long time, its physicochemical and mineralogical properties may be degradated and thus lose its barrier functions. It has been known in literature that the degradation of these properties of the smectitic clay occurs by a illitization in which the smectite transforms into illite. Therefore, an understanding of the illitization is essential to evaluate the long-term barrier performance of smectitic clay for the buffer of a HLW repository. This paper will carry out hydrothermal reaction tests with domestic smectitic clay which will be favorably considered for the buffer material of a Korean HLW repository, and investigate changes in the expandibility, layer charge and cation exchange capacity(CEC) of the smectitic clay due to a illitization

  14. Chemical and physical stability of smectites and illite in electrolyte solutions: experimental study at 150 C

    International Nuclear Information System (INIS)

    Boutiche, M.

    1995-01-01

    Chemical interactions between electrolytic solutions commonly used i drilling muds and clays have been studies under P-T conditions similar to those of drillings (150 deg C) in order to determine the eventual consequences on the stability of clay rich formations. The experimental work has been carried out using several solutions (water, NaOH (pH 8, 10, 12), KCI (0,1, 1 2 mol./l), sea water, and K 2 CO 3 ) and clay minerals with low to high amounts of swelling layers (smectite (Na, Na-Ca, Ca), mixed layered illite-smectite minerals). Run products are studied by X-ray diffraction and electronic microprobe. Smectite layers show series of mineralogical changes (cation exchange in the interlayer site, formation of non-swelling layers, hydrolysis), which, however, do not yield to the formation of new minerals, except in the case of the interaction with K 2 CO 3 at 150 deg C (zeolite crystallisation). Cation exchange in the interlayer depends on the nature of the cation, cation concentration in the solution, exchange constants, and liquid/solid ratio. In dilute solutions ( 1 mol./l), because they favour the collapse of swelling layers, and dispersion. Solutions of K 2 CO 3 at 150 deg C are at the origin of the transformation of smectite to zeolites, and high pH - highly saline solutions are rather aggressive, and would probably not stabilize the argilites. (author)

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

    Science.gov (United States)

    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.

  16. Stability of deep-sited smectite minerals in crystalline rock-chemical aspects

    International Nuclear Information System (INIS)

    Pusch, R.

    1983-03-01

    A recent survey of possible conditions and mechanisms of smectite alteration, with special respect to the Swedish concept of radioactive waste disposal, has shown that the charge change by replacement of tetrahedral Si by Al is the key mechanism of the only practically important alteration, namely that of smectite/illite conversion. If K is available in sufficient quantities it will be fixed and permanent conversion to the unwanted illite-type minerals is a fact; if not, the smectite will be beidellitelike with practically unchanged physico/mechanical properties. Heating to more than about 100degreeC is thought to be the cause of the charge change. One other process may be critical and that is cementation of various substances. A possible cementation mechanism, i.e. that of quartz precipitation, is very probably associated with the smectite/illite conversion. Practical examples of smectite alteration and survival under reasonably well documented geological conditions with respect to temperature and pressure are available, one being that of the Kinnekulle bentonites, another one, although less well known, being the smectitic clay beds in the Hoeganaes depression. Rather comprehensive core sampling was made at both sites and elemental and mineral analyses were conducted as well as microstructural studies. They support the hypothesis that practically important charge change through Si/Al replacement requires a temperature of more than 100degreeC, and that such replacement does not yield permanent lattice collapse unless K is available in sufficient quantities. The Hoeganaes case also serves as an example of drastic loss in plasticity and swelling potential by cementation of other precipitates than quartz, namely iron compounds. (author)

  17. Smectite Formation from Basaltic Glass Under Acidic Conditions on Mars

    Science.gov (United States)

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

    2015-01-01

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

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

    Science.gov (United States)

    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.

  19. Investigation of chloritization of smectite. Document prepared by other institute, based on the trust contact

    International Nuclear Information System (INIS)

    Oba, Takanobu

    2003-03-01

    The stability of smectite under the bulk composition of high iron content is as follows: (1) and (2). (1) In early burial diagenesis, the chemical variations of chlorite and dioctahedral smectite in Tertiary formations of Niigata prefecture. (2) The experiment of the stability of smectite in iron - rich bulk composition under oxygen fugacity. In the present study, the results are as follows: (1) Samples were taken from the cores and cuttings of exploratory test well of Oguni. The trioctahedral smectite in tertiary formation decreases with a depth. Below 3800m, Si content of chlorite increases with a depth. In the study, corrensite at 2700m depth has higher Si content, as compared to chlorite at 3800m. Mg/(Mg+Fe) ratios of chlorite/smectite interstratified mineral increase with increasing Si content regardless of the depth. (2) Chlorite/smectite interstratified mineral forms at 250degC on the compositions of the starting material of Mont:Mt=5:5. Chlorite did not crystallize by using of the starting material of Sap:Mt 5:5 at 250degC. At 400degC, montomorillonite did not decompose on the starting material composition with low iron content. The iron density is very important for the stability of smectite. (author)

  20. Studies on the acid activation of Brazilian smectitic clays

    Directory of Open Access Journals (Sweden)

    Valenzuela Díaz Francisco R.

    2001-01-01

    Full Text Available Fuller's earth and acid activated smectitic clays are largely used as bleaching earth for the industrial processing of vegetable, animal and mineral oils and waxes. The paper comments about the nomenclature used for these materials, the nature of the acid activation of smectitic clays (bentonites, activation laboratory procedures and presents a review of the acid activation of bentonites from 20 deposits from several regions of Brazil. The activated clays were tested and show good decolorizing power for soybean, castor, cottonseed, corn and sunflower oils.

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

    Science.gov (United States)

    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.

  2. The effect of pH on the stability of smectite

    International Nuclear Information System (INIS)

    Johnston, R.M.; Miller, H.G.

    1984-11-01

    The hydrothermal stability of smectite at temperatures less than 275 degrees C was investigated experimentally over a range of pH values. In the near-neutral pH region, the smectite to illite conversion predominated; in the mildly acid region, there was extensive formation of aluminum hydroxy interlayers in the clay; and in the alkaline region, framework silicates (feldspar and zeolites) were produced. The geological evidence for these reactions is also reviewed

  3. Smectite-zeolite envelope surrounding the Tsukiyoshi uranium deposit, central Japan. A natural analogue study

    International Nuclear Information System (INIS)

    Utada, Minoru

    2003-01-01

    The Tsukiyoshi uranium deposit in Gifu Prefecture is the largest one in Japan. It is embedded in lower part of the Mizunami Group of Miocene age. Relating to the existence of this uranium deposit, the constituent minerals in sediments were studied by XRD and SEM, using many drilling cores. The most abundant authigenic mineral is smectite. The amount of smectite increases generally from upper to lower horizons, and a highly smectitized zone is situated around the uranium deposit. Smectitization predominated in mafic glassy grains of sediments, which was probably formed in early burial diagenesis. Zeolites including clinoptilolite-heulandite, mordenite, analcime, chabazite and philipsite are secondly abundant authigenic minerals. They seem to have been formed at early to late diagenetic stages. Opaline silica is rather rare. Carbonate minerals, including calcite, dolomite, siderite and rhodocrosite are common. They may be formed by diagenesis as well. Gypsum and pyrite occur in upper horizons and lower horizons, respectively. In particular, a highly smectitized zone including pyrite probably played an important role for retarding the migration of uranium and as a result keeping the uranium deposit for past one million years. This smectite-zeolite envelope surrounding the Tsukiyoshi uranium deposit is regarded as a natural analogue of the buffer materials surrounding the high-level radioactive waste repository. (author)

  4. Development of swelling strain in smectite clays through exposure to carbon dioxide

    NARCIS (Netherlands)

    de Jong, S.M.; Spiers, C.J.; Busch, A.

    2014-01-01

    Smectites are common constituents of claystones, mudstones and shales and are often present in the caprocks and faults that seal potential CO2 storage reservoirs at depths up to 2 or even 3 km. Whilst the marked swelling behaviour of smectites caused by hydration through interlayer sorption of water

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

    Science.gov (United States)

    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.

  6. Production of polyol carbonates and their intercalation into Smectite clays

    OpenAIRE

    Shaheen, Uzma

    2017-01-01

    In hyper-saline conditions, clays in geosynthetic clay liners contract and fail to form a hydraulic barrier due to removal of water from the interlayer spaces of smectite, which is the swelling mineral component of bentonites used in geosynthetic clay liners. Five-membered cyclic carbonates such as propylene carbonate have been reported to form stable intercalated complexes with hydrated Na-smectite, which maintain swollen states at 1M). Glycerol carbonate was selected as an alternative c...

  7. Quantitative evaluation of silicates present in samples of Brazilian smectite by magic angle spinning/Silicon-29 NMR

    International Nuclear Information System (INIS)

    Guarino, A.W.S.; San Gil, R.A.S.; Menezes, S.M.C.; Dieguez, L.C.

    1997-01-01

    This work presents the several attempts performed in order to determinate the chemical composition of silicates in Brazilian smectite by nuclear magnetic resonance. Due to specific characteristics of the compounds, common methods are not reliable and give to wrong conclusions. The methodology is presented. Results are presented

  8. Thermodynamic data of water on smectite surface and those applications to swelling pressure of compacted bentonite

    International Nuclear Information System (INIS)

    Sato, H.

    2009-01-01

    Swelling pressure was discussed focusing on the thermodynamic properties of water on smectite (montmorillonite) which is the major clay mineral constituent of the bentonite buffer. The thermodynamic data of the water on the smectite surface were obtained as a function of water content and temperature in a range of dry density 0.6-0.9 Mg/m 3 . Purified Na-smectite of which all interlayer cations were exchanged with Na+ ions, was used. The activity (a H 2 O ) and the relative partial molar Gibbs free energy (ΔG H 2 O ) of the water were obtained at 25 C. Both a H 2 O and ΔG H 2 O decreased with a decrease of water content, and similar results were obtained to data reported for montmorillonite (Kunipia-F bentonite). Since the specific surface area of smectite is about 800 m 2 /g, water up to approximately 2 water layers from smectite surface is thermodynamically evaluated to be bound. Swelling pressure versus smectite partial density was calculated based on ΔG H 2 O and compared to data experimentally obtained for various kinds of bentonites. The calculated results were in good agreement with the measured data over the range of smectite partial density between 1.0 and 2.0 Mg/m 3 . (author)

  9. Structural characterization of hexadecyltrimethylammonium-smectite composites and their potentiometric electrode applications

    Energy Technology Data Exchange (ETDEWEB)

    Cubuk, Osman [Department of Chemistry, Faculty of Arts and Sciences, Erzincan University, 24100 Erzincan (Turkey); Caglar, Bulent, E-mail: bcaglar55@gmail.com [Department of Chemistry, Faculty of Arts and Sciences, Erzincan University, 24100 Erzincan (Turkey); Topcu, Cihan; Coldur, Fatih; Sarp, Gokhan [Department of Chemistry, Faculty of Arts and Sciences, Erzincan University, 24100 Erzincan (Turkey); Tabak, Ahmet [Department of Chemistry, Faculty of Arts and Sciences, Recep Tayyip Erdoğan University, 53100 Rize (Turkey); Sahin, Erdal [Department of Chemistry, Faculty of Arts and Sciences, Erzincan University, 24100 Erzincan (Turkey)

    2015-05-30

    Graphical abstract: - Highlights: • Surfactant cations intercalated with different molecular arrangements into smectite layers. • The electrophoretic mobility values indicate that excess surfactant loadings also create positive charges on the organosmectites surfaces. • A novel potentiometric SCN{sup −} selective electrode was fabricated based on modified smectite. - Abstract: Organosmectites were prepared by the intercalation of hexadecyltrimethylammonium cations at various ratios into interlayer of Unye smectite. Structural, thermal, morphological and textural properties of the synthesized organosmectites were characterized. Afterwards, a novel potentiometric PVC-membrane thiocyanate selective electrode was prepared based on the obtained hexadecyltrimethylammonium modified smectites as electroactive material. The basal spacing values of organosmectites were observed in the range of 15.61 and 35.50 Å. Powder X-ray diffraction data show that the surfactant cations penetrated into the smectite layers with different molecular arrangements. Modification of smectite with hexadecyltrimethylammonium led to appreciable decreases in the intensities of the FTIR bands at 3402 and 1635 cm{sup −1} and the new characteristic vibrational bands at 2927, 2850, 1472 and 722 cm{sup −1} originating from the surfactant molecules appeared. The thermal analysis data showed that the decomposition of surfactant species occurred in the temperature range of 170–720 °C and the amount of dehydrated water gradually decreased with the increase in surfactant amount. The intercalation of surfactant species within the gallery spacing led gradually to smaller surface areas. In addition, the electrophoretic mobility values indicate that excess surfactant loadings also generate positive charges on the organosmectite surfaces. The most convenient membrane composition resulting in the best potentiometric performance was investigated. The optimum membrane composition was determined to

  10. Intercalated theophylline-smectite hybrid for pH-mediated delivery.

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  13. Thermodynamic properties of a smectite and an illite: comparison between solubility experiments and calorimetric results

    International Nuclear Information System (INIS)

    Gailhanou, H.; Gaboreau, S.; Gaucher, E.C.; Blanc, P.; Rogez, J.; Olives, J.; Amouric, M.; Van Miltenburg, J.C.; Michau, N.; Giffaut, E.

    2010-01-01

    Document available in extended abstract form only. In the context of nuclear waste repositories in argillaceous formations, it is necessary to assess the geochemical behaviour of natural and engineered clay barriers, namely by the stability of clay minerals over long periods of time. However, thermodynamic data of clay minerals, which are required for geochemical modelling, are still poorly known. The present study aims to improve our comprehension of clay mineral stability. The thermodynamic properties of smectite MX-80 and illite IMt-2 (Silver Hill, Montana) have already been determined using calorimetric methods between 0 K and 520 K, under both dried and hydrated states in the case of smectite. In parallel, solubility experiments were carried out in order to determine the solubility products of the clay minerals. Such experiments require some particular precautions as published by May et al. (1986) and Aja and Rosenberg (1992). According to these authors, it is namely important to reach the equilibrium from both under and over saturation and to characterize from a mineralogical point of view the end products. Taking advantage of previous calorimetric measurements, we propose to compare the solubility products obtained here from dissolution experiments with respect to calorimetry results, in order to assess the equilibrium achievement for the solubility experiments. The study is integrated in the Thermochimie project, which aims to provide a consistent thermodynamic database (Thermochimie) for modelling purposes. This work dealing with a smectite and an illite is being completed by the study of a set of typical clays, selected to be well-representative of the clay group. Enthalpies of formation of the minerals were determined by isothermal dissolution calorimetry at 25 deg. C, using a HF-HNO 3 solution. They were obtained by measuring the enthalpies of dissolution of (i) the sample (clay mineral + impurities) and (ii) the oxide or hydroxide constituent mixture

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

    Science.gov (United States)

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

    2004-01-01

    A new method has been developed for quantifying smectite abundance by sorbing polyvinylpyrrolidone (PVP) on smectite particles dispersed in aqueous solution. The sorption density of PVP-55K on a wide range of smectites, illites and kaolinites is ~0.99 mg/m2, which corresponds to ~0.72 g of PVP-55K per gram of montmorillonite. Polyvinylpyrrolidone sorption on smectites is independent of layer charge and solution pH. PVP sorption on SiO2, Fe2O3 and ZnO normalized to the BET surface area is similar to the sorption densities on smectites. γ-Al2O3, amorphous Al(OH)3 and gibbsite have no PVP sorption over a wide range of pH, and sorption of PVP by organics is minimal. The insensitivity of PVP sorption densities to mineral layer charge, solution pH and mineral surface charge indicates that PVP sorption is not localized at charged sites, but is controlled by more broadly distributed sorption mechanisms such as Van der Waals’ interactions and/or hydrogen bonding. Smectites have very large surface areas when dispersed as single unit-cell-thick particles (~725 m2/g) and usually dominate the total surface areas of natural samples in which smectites are present. In this case, smectite abundance is directly proportional to PVP sorption. In some cases, however, the accurate quantification of smectite abundance by PVP sorption may require minor corrections for PVP uptake by other phases, principally illite and kaolinite. Quantitative XRD can be combined with PVP uptake measurements to uniquely determine the smectite concentration in such samples.

  15. Activation energies of diffusion for I and Cs in interlayer of smectite

    International Nuclear Information System (INIS)

    Sato, H.

    2009-01-01

    The apparent diffusivities (Da) and activation energies (ΔEa) for I - and Cs + ions in compacted Na-smectite with an interlayer space of only 2 water layers were measured at a dry density of 1.79 Mg/m 3 . In-diffusion experiments were carried out under the conditions that interlayer space, orientation of smectite stacks and dry density were controlled. Basal spacing was checked by X-ray diffractometry (XRD). All diffraction peaks to d(001) indicated basal spacing, of which interlayer space was equal to 2 water layers. The ΔEa of I - ions was at similar level as that for the ionic diffusivity of I - ions in free water (Do) at a dry density of 1.0 Mg/m 3 , but was 35.24 kJ/mol at a dry density of 1.79 Mg/m 3 . The ΔEa for Cs + ions was 46.27 kJ/mol which was higher than that for I? ions, at a dry density of 1.79 Mg/m 3 . Such high ΔEa for I - ions in the interlayer of smectite could be explained by the lowering in the activity (a H 2 O ) of interlayer water. Since Cs + ions sorb onto smectite by ion exchange, such high ΔEa for Cs + ions could be explained by the combined effects of the Cs+/Na+ ion exchange enthalpy (ΔH o ) in smectite and the lowering in the a H 2 O of interlayer water. (author)

  16. Structural stability of the smectite-doped lanthanum under high pressures and high temperatures

    International Nuclear Information System (INIS)

    Stefani, Vicente Fiorini

    2012-01-01

    Smectites are phyllosilicates that have a tetrahedron: octahedron structure ratio of 2:1, with high cation exchange capacity (CEC) in the interlayers. For these and other features, smectites have been used in many parts of the world as secondary barriers with the goal of containing a possible leak of radioactive elements in final disposal facilities for radioactive waste through cation exchange. Our aim in this work is to reach the cation exchange in calcium montmorillonite (smectite dioctahedral) by lanthanum to simulate trivalent radionuclides and to study the stability of this structure under high pressure and high temperature. To achieve high pressure it was used two different technique: DAC (Diamond Anvil Cell), achieving pressures up to 12GPa at room temperature and hydraulic press with a toroidal chamber profile to achieve pressures up to 7,7GPa and temperatures up to 900 degree C. The heating is achieved simultaneously by an electric system coupled in the hydraulic press. The outcomes show that the smectite structure doped with lanthanum remains stable under 12GPa at room temperature and 2.5GPa at 200 degree C. However, above 300 degree C at 2.5GPa the structure becomes a new phase of muscovite-like, rich of La, where it loses its interlayer water and turns out to be irreversible. Furthermore, it is important to point out that the higher temperature the better ordered is the structure and it is still stable under 7.7GPa and 900 degree C. Moreover, after all experiments the structure continues being dioctahedral. The new phase of muscovite-like, rich of La, in contact with a calcium solution remains partially unchanged, whereas the other part returns to the original structure (montmorillonite-Ca). The following analyses were performed: X-ray diffraction (XRD) for evaluating the spatial structure; Fourier transform infrared spectroscopy (FTIR) for getting information about the vibrational modes; scanning electron microscopy with dispersive Xray spectroscopy

  17. Chemical processes causing cementation in heat-affected smectite - the Kinnekulle bentonite

    Energy Technology Data Exchange (ETDEWEB)

    Pusch, R. [Geodevelopment AB, Lund (Sweden); Takase, Hiroyasu; Benbow, S. [Quantisci Ltd., Oxfordshire (United Kingdom)

    1998-12-01

    Numerical calculation of silica migration and precipitation that can cause cementation of smectite buffer clay has been made using the Grindrod/Takase chemical model. It is used here to investigate whether the silicification of the bentonite and surrounding sediments at Kinnekulle, southwestern Sweden, can be explained by the heat pulse caused by the diabase intrusion that took place in Permian time. Compilation of data concerning silica cementation and associated microstructural and rheological changes showed that significant silica precipitation should have occurred in the Kinnekulle case and this is also documented. Thus, precipitation of quartz has taken place to an extent that can be explained by the chemical model, which also showed conversion of smectite to illite by neoformation of the latter mineral but only for the 3000 years long heating period. Introduction of a criterion for non-reversible illitization is hence a necessary improvement of the model for explaining the actual presence of neoformed illite, which may in fact be wholly or partly responsible for the cementation. (The report is made up of two articles: `Cementation processes in smectite clay associated with conversion of smectite to illite as exemplified by the Kinnekulle bentonites` and `Nonisothermal modelling of geochemical evolution in the Kinnekulle bentonite layer. Mathematical modelling and simulation`) 33 refs, 40 figs.

  18. Chemical processes causing cementation in heat-affected smectite - the Kinnekulle bentonite

    International Nuclear Information System (INIS)

    Pusch, R.; Takase, Hiroyasu; Benbow, S.

    1998-12-01

    Numerical calculation of silica migration and precipitation that can cause cementation of smectite buffer clay has been made using the Grindrod/Takase chemical model. It is used here to investigate whether the silicification of the bentonite and surrounding sediments at Kinnekulle, southwestern Sweden, can be explained by the heat pulse caused by the diabase intrusion that took place in Permian time. Compilation of data concerning silica cementation and associated microstructural and rheological changes showed that significant silica precipitation should have occurred in the Kinnekulle case and this is also documented. Thus, precipitation of quartz has taken place to an extent that can be explained by the chemical model, which also showed conversion of smectite to illite by neoformation of the latter mineral but only for the 3000 years long heating period. Introduction of a criterion for non-reversible illitization is hence a necessary improvement of the model for explaining the actual presence of neoformed illite, which may in fact be wholly or partly responsible for the cementation. (The report is made up of two articles: 'Cementation processes in smectite clay associated with conversion of smectite to illite as exemplified by the Kinnekulle bentonites' and 'Nonisothermal modelling of geochemical evolution in the Kinnekulle bentonite layer. Mathematical modelling and simulation')

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Jia, Hanzhong, E-mail: jiahz@ms.xjb.ac.cn [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); Li, Li [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); Chen, Hongxia; Zhao, Yue [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); School of Geology and Mining Engineering, Xinjiang University, Urumqi 830046 (China); Li, Xiyou [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); Wang, Chuanyi, E-mail: cywang@ms.xjb.ac.cn [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China)

    2015-04-28

    Graphical abstract: Roles of exchangeable cations in PAHs photodegradation on clay surafces under visible light. - Highlights: • Photolysis rate are strongly dependent on the type of cations on clay surface. • The strength of “cation–π” interactions governs the photodegradation rate of PAHs. • Several exchangeable cations could cause a shift in the absorption spectrum of PAHs. • Exchangeable cations influence the type and amount of reactive intermediates. - Abstract: 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{sup 3+} > Al{sup 3+} > Cu{sup 2+} >> Ca{sup 2+} > K{sup +} > Na{sup +}, 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{sup +}-smectite and K{sup +}-smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe{sup 3+}, Al{sup 3+}, and Cu{sup 2+} are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O{sub 2}{sup −}· , 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.

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

    International Nuclear Information System (INIS)

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

    2015-01-01

    Graphical abstract: Roles of exchangeable cations in PAHs photodegradation on clay surafces under visible light. - Highlights: • Photolysis rate are strongly dependent on the type of cations on clay surface. • The strength of “cation–π” interactions governs the photodegradation rate of PAHs. • Several exchangeable cations could cause a shift in the absorption spectrum of PAHs. • Exchangeable cations influence the type and amount of reactive intermediates. - Abstract: 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 O 2 − · , 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

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

    Science.gov (United States)

    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.

  3. Sorption of uranium and cesium by Hanford basalts and associated secondary smectite

    International Nuclear Information System (INIS)

    Ames, L.L.; McGarrah, J.E.; Walker, B.A.; Salter, P.F.

    1982-01-01

    Three characterized basalts and an associated secondary smectite were used in comparative uranium and cesium sorption studies. Experiments utilizing two synthetic characteristic basalt groundwaters at 23 and 60 0 C allowed comparison of increased temperature and carbonate concentration effects on Cs and U sorption. The sorption data were fitted to the Dubinin-Radushkevich (D-R) isotherm, and loading maxima and energetics derived. An increase in temperature caused a decrease in Cs sorption maxima on all solids from all groundwaters studied and an increase in U sorption maxima, especially from the higher-carbonate-content groundwater. Sorption energies were characteristic of ion exchange for both Cs and U sorption processes. Basalt U sorption maxima were relatively insignificant, but smectite U sorption maxima surpassed Cs sorption maxima in both groundwaters at 60 0 C. The uranyl carbonate complexes thus may be relatively temperature-sensitive. Upon removal of excess Fe-oxides from the secondary smectite, U sorption decreased and the D-R isotherm reverted to a normal Freundlich sorption isotherm. Removal of excess Fe-oxides from the basalts and secondary smectite would probably result in Freundlich sorption isotherms for both Cs and U. (Auth.)

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

    Science.gov (United States)

    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.

  5. Composition, oxygen isotope geochemistry, and origin of smectite in the metalliferous sediments of the Bauer Deep, southeast Pacific

    Energy Technology Data Exchange (ETDEWEB)

    Cole, T G [Imperial Coll. of Science and Technology, London (UK). Geology Dept.

    1985-01-01

    The sediments of the Bauer Deep, an open ocean basin situated on the northwest Nazca Plate in the southeast Pacific, constitute a regional metalliferous deposit dominated by authigenic smectite. Two 2-metre long cores from the Bauer Deep were examined to investigate the nature and origin of the smectite. Infra-red and Mossbauer spectroscopy, and wet chemical analysis (LiBO/sub 2/ fusion) of isolated smectite, indicate the mineral is a Mg-rich, Al-rich nontronite. Oxygen isotopic compositions for isolated smectite are uniform and translate to a non-hydrothermal temperature of formation of about 3 deg C. SEM observations show an abundance of well-preserved biogenic opal in surface and near surface sediment but postburial dissolution and transformation of this phase to smectite is evident at depth. Smectite formation is the result of interaction between iron oxyhydroxide, ponded in the Bauer Deep following a hydrothermal origin at the adjacent East Pacific Rise, and biogenic opal. A reaction mechanism is proposed. Regional factors control smectite formation. In particular, formation is inhibited in areas of CaCO/sub 3/ accumulation (topographic elevations) but favoured in areas of oxyhydroxide and opal ponding (topographic depressions.)

  6. Composition, oxygen isotope geochemistry, and origin of smectite in the metalliferous sediments of the Bauer Deep, southeast Pacific

    International Nuclear Information System (INIS)

    Cole, T.G.

    1985-01-01

    The sediments of the Bauer Deep, an open ocean basin situated on the northwest Nazca Plate in the southeast Pacific, constitute a regional metalliferous deposit dominated by authigenic smectite. Two 2-metre long cores from the Bauer Deep were examined to investigate the nature and origin of the smectite. Infra-red and Mossbauer spectroscopy, and wet chemical analysis (LiBO 2 fusion) of isolated smectite, indicate the mineral is a Mg-rich, Al-rich nontronite. Oxygen isotopic compositions for isolated smectite are uniform and translate to a non-hydrothermal temperature of formation of about 3 deg C. SEM observations show an abundance of well-preserved biogenic opal in surface and near surface sediment but postburial dissolution and transformation of this phase to smectite is evident at depth. Smectite formation is the result of interaction between iron oxyhydroxide, ponded in the Bauer Deep following a hydrothermal origin at the adjacent East Pacific Rise, and biogenic opal. A reaction mechanism is proposed. Regional factors control smectite formation. In particular, formation is inhibited in areas of CaCO 3 accumulation (topographic elevations) but favoured in areas of oxyhydroxide and opal ponding (topographic depressions.) (author)

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

    Science.gov (United States)

    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.

  8. Evolution of models for conversion of smectite to non-expandable minerals

    International Nuclear Information System (INIS)

    Pusch, R.

    1993-12-01

    Hydrothermal alteration of smectite has long been regarded as conversion to illite and chlorite as concluded from investigations of Gulf sediments. As manifested by statements given earlier at various international scientific meetings and in the literature, smectite-to-illite conversion (S→I) has been assumed to be a solid-state reaction with layer-by-layer alteration via mixed layer I/S to illite. In the last 10 years this opinion has successively changed and in recent years the concept of dissolution of smectite and accessory minerals and precipitation of illite and possibly I/S has been favored by many investigators. The present report reports laboratory and field investigations on bentonite and also calculations based on geochemical codes, which all support the dissolution/precipitation process. Applying Pytte's model for calculating the rate of conversion to illite, one finds good agreement with a number of experiments and field data, and this model is therefore recommended for practical use

  9. Instrumental characterization of the smectite clay–gentamicin hybrids

    Indian Academy of Sciences (India)

    use of conventional drugs may lead to fluctuations whereby drug concentrations in ... ence of smectite, as well as determination of the capacity of gentamicin to fill ... the pharmaceutical and cosmetic industries manufactured by. R.T. Vanderbilt ...

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

    Science.gov (United States)

    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.

  11. Formation of Fe- and Mg-Rich Smectite under Hyperalkaline Conditions at Narra in Palawan, the Philippines

    OpenAIRE

    Shimbashi, Misato; Sato, Tsutomu; Yamakawa, Minoru; Fujii, Naoki; Otake, Tsubasa

    2018-01-01

    The formation of Fe- and Mg-rich smectite and zeolite under alkaline conditions, as secondary minerals after the alkaline alteration of bentonite in repositories for radioactive waste, is of major concern. It is crucial for safety assessments to know whether smectite is formed as a secondary mineral after the alkaline alteration of bentonite. In the present paper, Fe- and Mg-rich smectite, which interacted with the hyperalkaline groundwater at Narra in Palawan, Philippines, was used. Mineralo...

  12. Radiation-stability of smectite.

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  17. Sorption Behavior of Strontium-85 Onto Colloids of Silica and Smectite

    International Nuclear Information System (INIS)

    Lu, N.; Triay, I.R.; Mason, C.F.V.; Longmire, P.A.

    1998-01-01

    Strontium-90 is one of the sizable radioactive contaminants found in DP Canyon at Los Alamos, New Mexico. Radioactive surveys found the 90 Sr is present in surface and groundwater in DP Canyon and Los Alamos Canyon. Colloids may influence the transport of this radionuclide in surface water and groundwater environments in both canyons. In this study, we investigated the sorption/desorption behavior of Sr on colloids of smectite and silica. Laboratory batch sorption experiments were conducted using 85 Sr as a surrogate to 90 Sr. Groundwater, collected from DP Canyon and from Well J-13 at Yucca Mountain, Nevada, and deionized water were used in this study. Our results show that 92% to 100% of 85 Sr was rapidly adsorbed onto smectite colloids in all three waters. The concentrations of Ca 2+ significantly influence the adsorption of 85 Sr onto silica colloids. Desorption of 85 Sr from smectite colloids is much slower than the sorption process. Desorption of 85 Sr from silica colloids was rapid in DP groundwater and slow using J-13 groundwater and deionized water

  18. Evaluation of the organization of the homoionic smectite layers (Na(+) or Ca(2+)) in diluted dispersions using granulometry, microscopy and rheometry.

    Science.gov (United States)

    Paumier, S; Pantet, A; Monnet, P

    2008-09-01

    Smectites are swelling clay materials with pronounced colloidal properties that are widely used in industry. These properties originate in the electrokinetic properties of the smectite layers and their linkage capacities. Thin layers may be dispersed or aggregated according to many parameters, such as concentration, particle size and morphology, exchangeable cation nature and chemical environment (pH, ionic strength). The literature usually provides general rules, like the sodium dispersion contains a lot of small units whereas the calcium dispersion contains a few large units. A volume of water molecules bound to the clay surface is considered as the immobile water phase that behaves like the solid phase obstructing the flow. The water immobilized around layers and trapped inside aggregates cannot participate to the flow. In this study, we evaluated the volume occupied by calcium and sodium units inside the dispersion containing the immobile water phase. First, the smectite was cautiously extracted from a raw bentonite and its physicochemical properties were determined. A large quantity of extracted and saturated smectite (Na-smectite and Ca-smectite) was obtained. Second, the unit size and a shape factor for each sample were evaluated using granulometry and scanning transmission electron microscopy on wet samples (Wet STEM) and some flow curves. Na-smectite dispersions contain 0.13 microm(2) surface units with a shape factor of 50. Ca-smectite dispersions contain 0.32 microm(2) surface units with a shape factor of 3.3. Finally, rheometry allowed us to evaluate the unit occupancy using an adaptation of the Krieger-Dougherty law. We used shape factors and evaluated the concentration from which the entire immobile volume was connected (6.4% for Na-smectite and 11.9% for Ca-smectite). This study explains the evolution of flow properties with increasing concentrations by the evolution of layer interactions at the microscopic scale for homoionic smectite particles in

  19. Chromium rich smectites from Jordan: a sink for hazardous elements of a high pH plume

    International Nuclear Information System (INIS)

    Khoury, H.N.

    2010-01-01

    Document available in extended abstract form only. A green earthy chromium rich di-octahedral smectite is widely distributed in Jordan. The green clay mineral is associated with marbles and travertines in central Jordan and in Suweileh area near Amman. A wide range of chromium substitution in the octahedral layer of smectites is indicated in samples from the different localities. The chromium rich smectites followed the precipitation of calcite and preceded the precipitation of opaline silica from highly alkaline paleo-groundwater. SEM photo indicating the sequence of precipitation is shown. These waters were evolved as a result of retrograde alteration and hydration reactions in the metamorphic zone. The secondary mineral precipitation followed the thermal metamorphic event of the bituminous marls. The travertine in central Jordan indicates a long-term analogue of carbonation and remobilization of silica in cementitious barriers for radioactive waste repositories. The presence of Cr-rich smectites and relatively high levels of U in the associated opaline silica may suggest the use of central Jordan outcrops as analogues with the repository disturbed zone. Smectites and silica phases are expected to be a sink for alteration products in the late stage evolution of a high pH plume. (authors)

  20. Macrostructure of smectite-water systems. Influence of anionic poly-electrolytes on the organisation of montmorillonite suspensions

    International Nuclear Information System (INIS)

    Morvan, Mikel

    1993-01-01

    In its first part, this research thesis reports a bibliographical study which aimed at highlighting the main aspects of smectite swelling, discusses the organisation of smectite suspension, and briefly presents the knowledge on clay-polymer mixtures. Then, the author describes the method he used to characterise clay suspensions (relaxation, MNR, osmometric techniques, small-angle X-ray diffraction), and theoretical elements required to interpret results. He addresses more particularly the organisation of smectite-water systems with either a natural smectite (montmorillonite) or a synthetic one (laponite) which have different geometries. The last part addresses the interactions between a montmorillonite suspension and sodium polyacrylates. The author, based on the use of small-angle X-ray diffraction and the measurement of the polyelectrolyte osmotic pressure, proposes a new interpretation of the action mechanism of an anionic polyelectrolyte of low molecular mass within a montmorillonite suspension

  1. Thermochemically induced transformations in Al-smectites: A Spanish natural analogue of the bentonite barrier behaviour in a radwaste disposal

    International Nuclear Information System (INIS)

    Perez del Villar, L.; Delgado, A.; Reyes, E.; Pelayo, M.; Fernandez-Soler, J.M.; Cozar, J.S.; Tsige, M.; Quejido, A.J.

    2005-01-01

    The thermal effect induced by the Morron de Mateo volcanic dome (Cabo de Gata volcanic region, Spain) on the adjacent bentonitised tuffaceous beds has been studied as a natural analogue of the thermal behaviour of the bentonite-engineered barrier of a geological radwaste repository. These bentonites consist mainly of Fe-rich smectites and were formed in equilibrium with seawater at temperatures between 75 and 95 o C, according to the δ 18 O and δD values. In contrast, bentonites from other localities in the region consist mainly of Al-smectites, formed in equilibrium with meteoric water below 25 deg. C. This investigation is focussed on the detection of the chemical differences between smectites from proximal and distal zones to the dome, as well as to test whether the temperatures calculated based on the O and H isotopic values correspond to their formation or transformation. The initial hypothesis was that the chosen smectites could be formed under marine conditions, being later transformed and isotopically re-equilibrated as a result of the intrusion. To check this hypothesis, a detailed mineralogical, chemical, geochemical and isotopic study has been performed on the smectitised tuffaceous materials and the overlaying biocalcarenites outcropping near and far from the dome. The results show that distal smectites are dioctahedral Al-smectites, similar to those from other deposits in the region, while proximal smectites are Fe- and Mg-rich smectites, showing two evolutionary trends on a Fe-Mg-Al ternary diagram. Similar features are observed when their structural formulae are plotted on the muscovite-celadonite-pyrophylite diagram. Thus, they plot in the smectite domain with interlayer charge less than 1, which is mainly due to octahedral substitution for distal smectites, while for proximal ones it is caused by both octahedral and tetrahedral substitutions. In this ternary diagram, the domains of both proximal and distal smectites are partially overlapped. The

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

    Science.gov (United States)

    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.

  3. Studies of adsorption of pillarized and organofunctionalized smectite clay for Th"4"+ removal

    International Nuclear Information System (INIS)

    Guerra, D.J.L.; Menonca, E.S.; Silva, R.A.R.; Lara, W.

    2012-01-01

    A natural smectite clay sample was taken from the Amazon region, Amazonas State, Brazil. Zirconium polyoxycations were inserted into the smectite structure in a pillaring process. The pillarized smectite was organofunctionalized with the compound 3-mercaptopropyltrimethoxysilane. The natural and modified clay samples were used for the adsorption of tetravalent thorium cation from aqueous solution in a batch process. The adsorption process was fitted to equilibrium and kinetic models. The effects of stirring time, adsorbent dosage and pH on the adsorption capacity demonstrated that 90 min is sufficient to reach equilibrium at room temperature at pH 6.0. From the cation/basic center interactions for each smectite at the solid-liquid interface, the equilibrium constant and exothermic thermal effects were calculated with calorimetric methodology. By considering the net interactive number of moles for thorium cation and the equilibrium constant, the enthalpy, (-7.2 ± 0.11 to -7.0 ± 0.11 kJ mol"-"1) and negative Gibbs free energy, (-22.4 ± 0.1 to -23.1 ± 0.1 kJ mol"-"1) were calculated. These values enabled determination of the positive entropy, (51.2 ± 0.1 to 54.1 ± 0.1 JK"-"1mol"-"1). All liquid/solid interface adsorptions were spontaneous in nature and enthalpically driven.

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

    Science.gov (United States)

    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.

  5. Textural and structural modifications of one smectite treated with different 0.1 M Zr solutions, with and without thermal treatment

    International Nuclear Information System (INIS)

    Volzone, Cristina; Hipedinger, Nora E.

    1997-01-01

    Smectite treated with with hydrolyzed Zr-solutions and posterior thermal treatment provide a product generally known as pillared inter layered clays (PILC), with interest as adsorbents, gas separation and catalysis. The smectite was dispersed in distilled water for one day at room temperature. The hydroxy-zirconium solutions were prepared from 0.1 M Zr O Cl 2 .8 H 2 O and hydrolyzed at different conditions: a) at room temperature 15 days; b) at 60 deg C one day; C) refluxed 2 hours and d) refluxed 12 hours. These solutions were slowly added to the dispersed smectite with stirring. After one day of contact at room temperature the solid was separated and washed several times. The amount of Zr added was 2.5 mmol per gram of smectite. The different Zr-smectites, at room temperature and 350 deg C, were characterized by: XRD, DTA, TGA and adsorption-desorption of N 2 . Textural and structural changes were observed in Zr-smectites depending on the prepared Zr solutions. (author)

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

    Science.gov (United States)

    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.

  7. Estimation of illitization rate of smectite from the thermal history of Murakami deposit, Japan

    International Nuclear Information System (INIS)

    Kamei, G.; Arai, T.; Yusa, Y.; Sasaki, N.; Sakuramoto, Y.

    1990-01-01

    The research on illitization of smectite in the natural environment affords information on the long-term durability of bentonite which is the candidate for buffer material for high-level radioactive waste disposal facilities. Murakami bentonite deposit in central Japan, where the bentonite and rhyolitic intrusive rock were distributed, was surveyed and the lateral variation of smectite to illite in the aureole of the rhyolite was studied. The radiometric ages of some minerals from the intrusive rock and the clay deposit were determined. Comparison of the mineral ages with closure temperature estimated for the various isotopic systems allowed the thermal history of the area. The age of the intrusion was 7.1 ± 0.5 Ma, and the cooling rate of the intrusive rock was estimated to be approximately 45C/Ma. Sedimentation ages of the clay bed were mostly within the range from 18 to 14 Ma. However, the fission-track age of zircon in the clay containing illite/smectite mixed layers was 6.4 ± 0.4 Ma, which was close to that of the intrusion. The latter value could be explained as the result of annealing of fission-tracks in zircon. The presence of annealing phenomena and the estimated cooling rate concluded that illitization had occurred in the period of 3.4 Ma at least under the temperature range from above 240 ± 50 to 105C. Illite-smectite mixed layers occurred from smectite in the process. The proportion of illite was about 40%. Approximately, 29 kcal/mol as a value of activation energy was calculated to the illitization

  8. Enrichment and activation of smectite-poor clay

    Energy Technology Data Exchange (ETDEWEB)

    Sarcevica, Inese; Kostjukovs, Juris; Actint, Andris, E-mail: inese.sarcevicha@gmail.com [Department of Chemistry, University of Latvia, Kr. Valdemara street 48, Riga (Latvia)

    2011-06-23

    A new method of smectite clay enrichment has been developed. The method is based on dispersing clay in a phosphate solution and sequential coagulation. The product of enrichment is characterized with X-ray powder diffraction, wavelength dispersive X-ray fluorescence spectrometry, differential thermal analysis and thermogravimetry. Sorption of methylene blue and hexadecylpyridinium bromide on raw and purified clays was studied.

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

    Energy Technology Data Exchange (ETDEWEB)

    Guerra, Denis L., E-mail: denis@cpd.ufmt.br [Universidade Federal de Mato Grosso, DRM-UFMT, Mato Grosso, Brasil 78060 900 (Brazil); Silva, Weber L.L. [Universidade Federal de Mato Grosso, DRM-UFMT, Mato Grosso, Brasil 78060 900 (Brazil); Oliveira, Helen C.P. [Universidade Estadual do Norte Fluminense, UENF, Rio de Janeiro, Brasil 28013 602 (Brazil); Viana, Rubia R. [Universidade Federal de Mato Grosso, DRM-UFMT, Mato Grosso, Brasil 78060 900 (Brazil); Airoldi, Claudio [Chemistry Institute, State University of Campinas, P.O. Box 6154, 13084-971 Campinas, Sao Paulo (Brazil)

    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{sup -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.

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

    International Nuclear Information System (INIS)

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

    2011-01-01

    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.

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

    Science.gov (United States)

    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 (V0.3 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.

  12. Experimental Study and modelling of the Sorption of Selenite and Europium Onto Smectite and Illite Clays

    Energy Technology Data Exchange (ETDEWEB)

    Missana, T.; Alonso, U.; Garcia-Gutierrez, M.

    2009-10-12

    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 and independent of ionic strength. Selenite sorption was also analysed in the illite/smectite system with the clays mixed in two different proportions. 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 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. 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 models predictions were consistent with the experimental adsorption data. (Author) 42 refs.

  13. Experimental Study and modelling of the Sorption of Selenite and Europium Onto Smectite and Illite Clays

    International Nuclear Information System (INIS)

    Missana, T.; Alonso, U.; Garcia-Gutierrez, M.

    2009-01-01

    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 and independent of ionic strength. Selenite sorption was also analysed in the illite/smectite system with the clays mixed in two different proportions. 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 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. 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 models predictions were consistent with the experimental adsorption data. (Author) 42 refs

  14. Influence of microorganisms on swelling behavior of smectites

    International Nuclear Information System (INIS)

    Viefhaus, Hanna; Schanz, Tom

    2012-01-01

    stimulated microbial growth. This is all with respect to the fact that electrolyte concentration has to be unaltered in comparison to the liquid that was used for the reference samples without microbial accumulation. Therefore C 6 H 12 O 6 was added to tap water, with a concentration of 20 g/l, as it acted as the desired energy and carbon source for the microbial growth. Reference samples were treated with tap water as well. The changes measured in COD (chemical oxygen demand), which acted as an indicator for microbial growth, and the microscopic analysis of the samples in ESEM (environmental scanning electron microscope) were utilized to monitor the accumulation during and following the test. In the first series of tests 1-D volume change was measured and in the second series of tests it was added by weight measurement. This was in order to differentiate water adsorption from other volume changing effects, such as gas generation by metabolism processes, which seemed to appear during the first series of tests. Water content was plotted against time for each sample of Calcigel and MX80 mixtures. Both mixtures began to swell with the rapid occurring hydration of the cations and the charged surfaces, within the first 24 hours. This was followed by time intensive osmotic swelling in the case of MX80 smectite occupied with Na + . While hydration depends on the initial condition 'dry' or 'wet', osmotic swelling leads to water adsorption regardless of these conditions. Rapid occurring hydration of the charge carriers remains relatively unaffected by the presence of microorganisms. In comparison osmotic swelling exhibits considerable differences in water adsorption and volume change when samples have been accumulated with microorganisms. Therefore the influence reacts in different fashions, with negligible hydration increase and a significant decrease in osmotic swelling behavior of microbial accumulated samples. Also biological cells appear as charge carriers, and for this purpose

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

    Science.gov (United States)

    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

  16. Analysis of the structural stability of the smectite submitted to high pressures and temperatures

    International Nuclear Information System (INIS)

    Alabarse, Frederico Gil

    2009-10-01

    The thermal stability of bentonite is of particular interest for containment barrier in nuclear waste disposal facilities. However, very little is known about the stability of smectite (principal component of bentonite) under high-pressure and high-temperature conditions (HPHT). The objective of this work was to investigate the stability of the smectite structure under HP-HT conditions. The HP-HT experiments were performed on toroidal chambers (TC) with pressure up 7.7 GPa and temperatures of 1000 deg C. The samples were characterized by X-ray diffraction after the HP-HT processing. Furthermore, one sample from the original material was analyzed using Fourier transformed infra-red (FTIR) in situ measurements on a diamond anvil cell (DAC) in experiments up to 12 GPa. The original sample of bentonite, calcium dioctahedral montmorillonite with small fraction of quartz, was characterized by FTIR, XRD, X-ray fluorescence (XRF), scanning electron microscopy (SEM), surface area, thermogravimetric analysis (TGA) and differential thermal analysis (DTA). In the experiment performed using the DAC up to 12 GPa, the FTIR in situ measurements analysis showed that the smectite structure is stable with a reversible deformation in the Si-O bond and that the smectite did not loose water. Experiments performed in TC at 7.7 GPa of pressure and 250 deg C of temperature, during 3.5 h showed, after analysis by XRD and FTIR, that the smectite structure is stable and did not loose water. Experiments performed in TC at 7.7 GPa of pressure and 1000 deg C of temperature, during 3.5 h showed, after analysis by XRD and SEM, the transformation of bentonite to the mineral assemblage: Coesite, Quartz, Kyanite and Pyrope. (author)

  17. Impact factors on the structuration and the rheological behavior of the clay-water system for smectite dispersions; Facteurs determinant l'organisation et la rheologie du systeme argile-eau pour des suspensions de smectites

    Energy Technology Data Exchange (ETDEWEB)

    Paumier, S

    2007-11-15

    Smectite are swelling clays widely used in industry. Their mechanical properties are unequal according to their mineralogical and physico-chemical characteristics. The aim of this study is to improve the knowledge of the interlayer cation impact on the structure built by the smectite-water system according to the concentration. Homo-ionic (Na{sup +} et Ca{sup 2+}) and bi-ionic systems are observed. This study cross checks mineralogical methods, physicochemical analysis and broad range of rheometric tests. At low concentration (less than 60 g/l) the calcium dispersions are shear thinning and few viscous due to the layer association in huge deformable flocks. The sodium smectite layers are dispersed; the dispersions are highly viscous. The lowest viscosity is detected for mix of 20 % of sodium smectite and 80 % of calcium smectite. At higher concentration (60 to 100 g/l), the yield stress and viscoelastic properties are studied by creep-recovery tests, oscillatory tests and imposed shear step. At the liquid state, the flow is first heterogeneous with a shear banding effect then homogeneous. The results make it possible to define the concentration area characteristic of each mechanical behavior (viscosity, shear thinning and yield stress) according to the saturation cation. The thixotropic properties are characterized with de-structuring-restructuring tests. Two kinetics are determined. Finally we realize a data base with 12 natural and industrial bentonite. The rheograms would be efficient to differentiate the natural calcium bentonite (Newtonian law), natural sodium bentonite (Herschel-Bulkley law) and activated calcium bentonite (Bingham law). (author)

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

    Science.gov (United States)

    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.

  19. Comparative study of strontium adsorption on dioctahedral and trioctahedral smectites

    International Nuclear Information System (INIS)

    Galambos, M.; Rosskopfova, O.; Krajnak, A.; Rajec, P.; Osacky, M.; Comenius University, Bratislava

    2012-01-01

    Slovak bentonites characterized by good rheological, mineralogical and chemical stability are considered as suitable sealing barriers for construction of Slovak deep geological repository for high-level radioactive waste and spent nuclear fuel. There is several Slovak bentonite deposits, bentonites of which have appropriate adsorption properties meeting the geotechnical requirements for this type of barriers. Study of adsorption properties of bentonites (mainly smectites) is an essential step for developing the migration model long-lived corrosion and activation products, and fission products of uranium. Nuclear wastes contain the most important nuclear fission products, β-emitter 90 Sr with long half-life, biological half-life and high mobility. The present paper investigates and compares the strontium adsorption properties of bentonites of different mineral composition consisted mainly of dioctahedral and trioctahedral smectites. (author)

  20. Alteration of isolating properties of dense smectite clay in repository environment as exemplified by seven pre-quaternary clays

    International Nuclear Information System (INIS)

    Pusch, R.; Boergesson, L.; Erlstroem, M.

    1987-12-01

    Seven pre-quaternary clays with a smectite content ranging between zero and about 25% were taken as possible reaction products resulting from chemical alteration of dense sodium bentonite. They were characterized with respect to the mineral composition and microstructural constitution and tested with reference to their hydraulic conductivity, swelling ability and creep properties. It was found that since they were all less permeable than a typical large granitic rock mass they would serve as flow barriers in a repository. Thus, even rather extreme chemical attack is not expected to eliminate the most important barrier function of Na bentonite in repository environment. However, slight mechanical disturbance of a heterogeneously altered smectite clay buffer or seal, may be critical. Thus, the investigated, less smectitic clays experienced a rather dramatic increase in hydraulic conductivity on expansion and remolding. This is explained by the inability of a microstructurally discontinuous smectite component - particularly in the Ca-form - to swell and fill voids. The minimum content of Na smectite to preserve the self-healing capacity is estimated at 15-25%. Slight or moderate cementation was indicated by two of the clays by the creep tests. At a smectite content of 15-25% it is probable that self-healing will take place after a mechanically induced breakage of the cementing bonds. The tests gave a good basis for future development of rational, routine tests as well as for a relevant characterization of buffer material candidates. (orig.)

  1. Anisotropy in diffusion and activation energies of I- and CS+ ions in compacted smectite

    International Nuclear Information System (INIS)

    Haruo Sato

    2005-01-01

    The anisotropies and the effect of salinity in the apparent diffusivities (D a ) and activation energies (ΔE a ) of I - and Cs + in compacted Na-smectite were studied. The diffusion experiments in the parallel and perpendicular directions to the orientated direction of smectite particles were performed as a function of smectite's dry density (0.9-1.4 Mg/m 3 ), salinity ([NaCl]=0.01, 0.51 M) and temperature (295-333 K). The Da-values for both ions tended to be higher in the parallel direction than in the perpendicular direction to the orientated direction of smectite particles. The Da-values of I - in the parallel direction decreased with increasing salinity only at low-dry density, but those of Cs + increased with increasing salinity in all conditions. Considering electrostatic effect from the surface of smectite aggregates and the change in tortuosity on dry density, salinity and diffusion direction, I - is interpreted to mainly diffuse in interstitial pores. While, Cs + can diffuse in both interlayer and interstitial pores, and the Da-values of Cs + are presumed to have elevated by the decrease in retardation by competition with Na + . The ΔE a -values of I - , similar levels (ΔE a =15.1-16.1 kJ/mol) to that of the ionic diffusivity in free water (Do) for I - (ΔE a =17.36 kJ/mol) at low-dry density, increased with increasing dry density. On the contrary, the ΔE a -values of Cs + , clearly higher (ΔE a =23.7-25.7 kJ/mol) than that of the Do for Cs + (ΔE a =16.47 kJ/mol) even at low-dry density, increased with increasing dry density. Such high ΔE a -values for Cs + can be explained by considering the ion exchange enthalpy between Cs + and Na + in smectite (ΔH 0 = -11.1 kJ/mol) at low-dry density, and are considered to be due to the effects of the decrease in the activity of porewater and ΔH 0 at high-dry density. (authors)

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    Korichi, Smain; Bensmaili, Aicha

    2009-09-30

    )-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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

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

    NARCIS (Netherlands)

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

    2015-01-01

    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

  10. Impact factors on the structuration and the rheological behavior of the clay-water system for smectite dispersions

    International Nuclear Information System (INIS)

    Paumier, S.

    2007-11-01

    Smectite are swelling clays widely used in industry. Their mechanical properties are unequal according to their mineralogical and physico-chemical characteristics. The aim of this study is to improve the knowledge of the interlayer cation impact on the structure built by the smectite-water system according to the concentration. Homo-ionic (Na + et Ca 2+ ) and bi-ionic systems are observed. This study cross checks mineralogical methods, physicochemical analysis and broad range of rheometric tests. At low concentration (less than 60 g/l) the calcium dispersions are shear thinning and few viscous due to the layer association in huge deformable flocks. The sodium smectite layers are dispersed; the dispersions are highly viscous. The lowest viscosity is detected for mix of 20 % of sodium smectite and 80 % of calcium smectite. At higher concentration (60 to 100 g/l), the yield stress and viscoelastic properties are studied by creep-recovery tests, oscillatory tests and imposed shear step. At the liquid state, the flow is first heterogeneous with a shear banding effect then homogeneous. The results make it possible to define the concentration area characteristic of each mechanical behavior (viscosity, shear thinning and yield stress) according to the saturation cation. The thixotropic properties are characterized with de-structuring-restructuring tests. Two kinetics are determined. Finally we realize a data base with 12 natural and industrial bentonite. The rheograms would be efficient to differentiate the natural calcium bentonite (Newtonian law), natural sodium bentonite (Herschel-Bulkley law) and activated calcium bentonite (Bingham law). (author)

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

    Science.gov (United States)

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

    2012-01-01

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

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

    Science.gov (United States)

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

    2016-12-15

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

  13. Quantitative measure of randomness and order for complete genomes

    Science.gov (United States)

    Kong, Sing-Guan; Fan, Wen-Lang; Chen, Hong-Da; Wigger, Jan; Torda, Andrew E.; Lee, H. C.

    2009-06-01

    We propose an order index, ϕ , which gives a quantitative measure of randomness and order of complete genomic sequences. It maps genomes to a number from 0 (random and of infinite length) to 1 (fully ordered) and applies regardless of sequence length. The 786 complete genomic sequences in GenBank were found to have ϕ values in a very narrow range, ϕg=0.031-0.015+0.028 . We show this implies that genomes are halfway toward being completely random, or, at the “edge of chaos.” We further show that artificial “genomes” converted from literary classics have ϕ ’s that almost exactly coincide with ϕg , but sequences of low information content do not. We infer that ϕg represents a high information-capacity “fixed point” in sequence space, and that genomes are driven to it by the dynamics of a robust growth and evolution process. We show that a growth process characterized by random segmental duplication can robustly drive genomes to the fixed point.

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

    Science.gov (United States)

    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.

  15. Ground-state properties of ordered, partially ordered, and random Cu-Au and Ni-Pt alloys

    DEFF Research Database (Denmark)

    Ruban, Andrei; Abrikosov, I. A.; Skriver, Hans Lomholt

    1995-01-01

    We have studied the ground-state properties of ordered, partially ordered, and random Cu-Au and Ni-Pt alloys at the stoichiometric 1/4, 1/2, and 3/4 compositions in the framework of the multisublattice single-site (SS) coherent potential approximation (CPA). Charge-transfer effects in the random ...... for the ordered alloys are in good agreement with experimental data. For all the alloys the calculated ordering energy and the equilibrium lattices parameters are found to be almost exact quadratic functions of the long-range-order parameter....... and the partially ordered alloys are included in the screened impurity model. The prefactor in the Madelung energy is determined by the requirement that the total energy obtained in direct SS CPA calculations should equal the total energy given by the Connolly-Williams expansion based on Green’s function...

  16. Particle clogging in porous media. Filtration of a smectite solution

    Energy Technology Data Exchange (ETDEWEB)

    Richards, Tobias (Chalmers University of Technology, Goeteborg (Sweden))

    2010-01-15

    The goal of this project is to find out if it is possible for bentonite clay to self heal during leaching with deionized water. The investigation has focused on the formation of a filter cake made of accessory material from MX 80 and the separation of solid material when a smectite solution (1%) is pushed through the cake using a pressure difference of 5 bar. It was also in the scope of this project to design and build the necessary equipment for these experiments. In the literature review it was not found any example that the phenomenon of clogging has been used as a self-healing method previously. It was rather separated also between the clogging of a filter cake (deep bed filtration or cake filtration) and the filtration of colloidal particles. Probably because the latter are in such low concentrations in natural systems and the focus have mainly been in the transport properties of colloids within a filter cake or deep bed filter. An experimental equipment was designed and built. It consists of seven filtration cells that could operate in parallel. All of them are connected to the same source of pressure to ensure equal conditions. A system was also prepared to prevent air from dissolving in the solution because it could create an unwanted expansion in the filter cake due to lower solubility at lower pressure. The experiment showed good separation of smectite particles from the solution when it passed through the filter cake. In all tested cases, the separation was almost complete after long enough time, indicating that the cake has small enough pores to act as a geometrical hinder for the small particles. Comparison between the materials prepared at Chalmers University of Technology and at Clay Technology showed a very good agreement indicating similar properties of the produced smectite

  17. Particle clogging in porous media. Filtration of a smectite solution

    International Nuclear Information System (INIS)

    Richards, Tobias

    2010-01-01

    The goal of this project is to find out if it is possible for bentonite clay to self heal during leaching with deionized water. The investigation has focused on the formation of a filter cake made of accessory material from MX 80 and the separation of solid material when a smectite solution (1%) is pushed through the cake using a pressure difference of 5 bar. It was also in the scope of this project to design and build the necessary equipment for these experiments. In the literature review it was not found any example that the phenomenon of clogging has been used as a self-healing method previously. It was rather separated also between the clogging of a filter cake (deep bed filtration or cake filtration) and the filtration of colloidal particles. Probably because the latter are in such low concentrations in natural systems and the focus have mainly been in the transport properties of colloids within a filter cake or deep bed filter. An experimental equipment was designed and built. It consists of seven filtration cells that could operate in parallel. All of them are connected to the same source of pressure to ensure equal conditions. A system was also prepared to prevent air from dissolving in the solution because it could create an unwanted expansion in the filter cake due to lower solubility at lower pressure. The experiment showed good separation of smectite particles from the solution when it passed through the filter cake. In all tested cases, the separation was almost complete after long enough time, indicating that the cake has small enough pores to act as a geometrical hinder for the small particles. Comparison between the materials prepared at Chalmers University of Technology and at Clay Technology showed a very good agreement indicating similar properties of the produced smectite

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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 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

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

    Science.gov (United States)

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

    2012-03-01

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

  1. Hydraulic/mechanical modeling of smectitic materials for HMC analytical evaluation of the long term performance of TRU geological repository - 59090

    International Nuclear Information System (INIS)

    Kobayashi, Ichizo; Owada, Hitoshi; Ishii, Tomoko

    2012-01-01

    Aiming at evaluation of the long term performance of transuranic (TRU) geological repositories, the hydraulic/ mechanical/chemical (HMC) analysis method has been studied. In this phase of research (four years) the hydraulic/mechanical modeling of smectitic materials for HMC analyses has been studied. In this paper, new experimental methods for investigation of the hydraulic/mechanical behavior of smectitic materials were developed. For hydraulic modeling, the measurement method of the specific surface area of compacted smectitic materials was developed using X-ray diffraction (XRD). The results of the method were applied to the Kozeny-Carman law. Since the specific surface area represents the microstructure of smectitic materials such as the degree of swelling, it was found that the Kozeny-Carman law using measured specific surface area of compacted smectitic materials was useful in evaluating the hydraulic performance of smectitic materials. Moreover, since the Kozeny-Carman law can take the alteration of content of pore water into consideration by not only a coefficient of viscosity but also by changes in specific surface area, the Kozeny-Carman law will be more suitable to chemical and mechanical couple analyses than the ordinary Darcy's law. For the mechanical modeling, the procedure of one dimensional exhausting compression test was developed. The tests gave the dry density and compression stress relation in the state of full-saturation of smectitic materials with varying water content. The relations between the dry density and compression stress in the state of fully saturation were termed fully saturation lines. The group of iso-grams of degree of saturation and water content were also given with this test. It was found that the fully-saturation line is consistent with swelling deformation-pressure relation in the equilibrium state. The results indicated that the swelling deformation-pressure relation does not depend on the saturation manner, such as the

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Guimarães, Vanessa [Instituto de Ciências da Terra – Porto, DGAOT, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre 687, 4169-007 Porto (Portugal); Geobiotec. Departamento de Geociências da Universidade de Aveiro, Campo Universitário de Santiago, 3810-193 Aveiro (Portugal); Rodríguez-Castellón, Enrique; Algarra, Manuel [Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Málaga. Campus de Teatino s/n, 29071 Málaga (Spain); Rocha, Fernando [Geobiotec. Departamento de Geociências da Universidade de Aveiro, Campo Universitário de Santiago, 3810-193 Aveiro (Portugal); Bobos, Iuliu, E-mail: ibobos@fc.up.pt [Instituto de Ciências da Terra – Porto, DGAOT, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre 687, 4169-007 Porto (Portugal)

    2016-11-05

    Highlights: • The UO{sub 2}{sup 2+} sorption at pH 4 and 6 on heterogeneous smectite structure. • The cation exchange process is affected by layer charge distribution. • Surface complexation and cation exchange modelling. • New binding energy components identified by X-ray photoelectron spectroscopy. - Abstract: The UO{sub 2}{sup 2+} adsorption on smectite (samples BA1, PS2 and PS3) with a heterogeneous structure was investigated at pH 4 (I = 0.02 M) and pH 6 (I = 0.2 M) 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 4.8 nm (sample PS2), to 5.1 nm (sample PS3) and, to 7.4 nm (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 UO{sub 2}{sup 2+} sorption on smectite. The amount of UO{sub 2}{sup 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 ± 0.3 eV, assigned to hydrated UO{sub 2}{sup 2+} adsorbed by cation exchange and by inner-sphere complexation on the external sites at pH 4, were identified after the U4f{sub 7/2} peak deconvolution by X-photoelectron spectroscopy. Also, two new binding energy components at 380.3 ± 0.3 and 381.8 ± 0.3 eV assigned to ≡AlOUO{sub 2}{sup +} and ≡SiOUO{sub 2}{sup +} surface species were observed at pH 6.

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

    International Nuclear Information System (INIS)

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

    2016-01-01

    Highlights: • The UO_2"2"+ sorption at pH 4 and 6 on heterogeneous smectite structure. • The cation exchange process is affected by layer charge distribution. • Surface complexation and cation exchange modelling. • New binding energy components identified by X-ray photoelectron spectroscopy. - Abstract: The UO_2"2"+ adsorption on smectite (samples BA1, PS2 and PS3) with a heterogeneous structure was investigated at pH 4 (I = 0.02 M) and pH 6 (I = 0.2 M) 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 4.8 nm (sample PS2), to 5.1 nm (sample PS3) and, to 7.4 nm (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 UO_2"2"+ sorption on smectite. The amount of UO_2"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 ± 0.3 eV, assigned to hydrated UO_2"2"+ adsorbed by cation exchange and by inner-sphere complexation on the external sites at pH 4, were identified after the U4f_7_/_2 peak deconvolution by X-photoelectron spectroscopy. Also, two new binding energy components at 380.3 ± 0.3 and 381.8 ± 0.3 eV assigned to ≡AlOUO_2"+ and ≡SiOUO_2"+ surface species were observed at pH 6.

  7. On mean square displacement behaviors of anomalous diffusions with variable and random orders

    International Nuclear Information System (INIS)

    Sun Hongguang; Chen Wen; Sheng Hu; Chen Yangquan

    2010-01-01

    Mean square displacement (MSD) is used to characterize anomalous diffusion. Recently, models of anomalous diffusion with variable-order and random-order were proposed, but no MSD analysis has been given so far. The purpose of this Letter is to offer a concise derivation of MSD functions for the variable-order model and the random-order model. Numerical results are presented to illustrate the analytical results. In addition, we show how to establish a variable-random-order model for a given MSD function which has clear application potentials.

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

    Science.gov (United States)

    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.

  9. Cloud Macroscopic Organization: Order Emerging from Randomness

    Science.gov (United States)

    Yuan, Tianle

    2011-01-01

    Clouds play a central role in many aspects of the climate system and their forms and shapes are remarkably diverse. Appropriate representation of clouds in climate models is a major challenge because cloud processes span at least eight orders of magnitude in spatial scales. Here we show that there exists order in cloud size distribution of low-level clouds, and that it follows a power-law distribution with exponent gamma close to 2. gamma is insensitive to yearly variations in environmental conditions, but has regional variations and land-ocean contrasts. More importantly, we demonstrate this self-organizing behavior of clouds emerges naturally from a complex network model with simple, physical organizing principles: random clumping and merging. We also demonstrate symmetry between clear and cloudy skies in terms of macroscopic organization because of similar fundamental underlying organizing principles. The order in the apparently complex cloud-clear field thus has its root in random local interactions. Studying cloud organization with complex network models is an attractive new approach that has wide applications in climate science. We also propose a concept of cloud statistic mechanics approach. This approach is fully complementary to deterministic models, and the two approaches provide a powerful framework to meet the challenge of representing clouds in our climate models when working in tandem.

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

    Science.gov (United States)

    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.

  11. Controlled Synthesis of Carbon-Encapsulated Copper Nanostructures by Using Smectite Clays as Nanotemplates

    NARCIS (Netherlands)

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

    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

  12. Mean residence time of soil organic matter associated with kaolinite and smectite

    NARCIS (Netherlands)

    Wattel-Koekkoek, E.J.W.; Buurman, P.; Plicht, van der J.; Wattel, J.T.; Breemen, van N.

    2003-01-01

    To gain insight into the effect of clay mineralogy on the turnover of organic matter, we analysed the C-14 activity of soil organic matter associated with clay in soils dominated by kaolinite and smectite in natural savanna systems in seven countries. Assuming that carbon inputs and outputs are in

  13. Mean residence time of soil organic matter associated with kaolinite and smectite

    NARCIS (Netherlands)

    Wattel-Koekkoek, E.J.W.; Buurman, P.; Plicht, J. van der; Wattel, E.; Breemen, N. van

    To gain insight into the effect of clay mineralogy on the turnover of organic matter, we analysed the C-14 activity of soil organic matter associated with clay in soils dominated by kaolinite and smectite in natural savanna systems in seven countries. Assuming that carbon inputs and outputs are in

  14. An AES chip with DPA resistance using hardware-based random order execution

    International Nuclear Information System (INIS)

    Yu Bo; Li Xiangyu; Chen Cong; Sun Yihe; Wu Liji; Zhang Xiangmin

    2012-01-01

    This paper presents an AES (advanced encryption standard) chip that combats differential power analysis (DPA) side-channel attack through hardware-based random order execution. Both decryption and encryption procedures of an AES are implemented on the chip. A fine-grained dataflow architecture is proposed, which dynamically exploits intrinsic byte-level independence in the algorithm. A novel circuit called an HMF (Hold-Match-Fetch) unit is proposed for random control, which randomly sets execution orders for concurrent operations. The AES chip was manufactured in SMIC 0.18 μm technology. The average energy for encrypting one group of plain texts (128 bits secrete keys) is 19 nJ. The core area is 0.43 mm 2 . A sophisticated experimental setup was built to test the DPA resistance. Measurement-based experimental results show that one byte of a secret key cannot be disclosed from our chip under random mode after 64000 power traces were used in the DPA attack. Compared with the corresponding fixed order execution, the hardware based random order execution is improved by at least 21 times the DPA resistance. (semiconductor integrated circuits)

  15. An AES chip with DPA resistance using hardware-based random order execution

    Science.gov (United States)

    Bo, Yu; Xiangyu, Li; Cong, Chen; Yihe, Sun; Liji, Wu; Xiangmin, Zhang

    2012-06-01

    This paper presents an AES (advanced encryption standard) chip that combats differential power analysis (DPA) side-channel attack through hardware-based random order execution. Both decryption and encryption procedures of an AES are implemented on the chip. A fine-grained dataflow architecture is proposed, which dynamically exploits intrinsic byte-level independence in the algorithm. A novel circuit called an HMF (Hold-Match-Fetch) unit is proposed for random control, which randomly sets execution orders for concurrent operations. The AES chip was manufactured in SMIC 0.18 μm technology. The average energy for encrypting one group of plain texts (128 bits secrete keys) is 19 nJ. The core area is 0.43 mm2. A sophisticated experimental setup was built to test the DPA resistance. Measurement-based experimental results show that one byte of a secret key cannot be disclosed from our chip under random mode after 64000 power traces were used in the DPA attack. Compared with the corresponding fixed order execution, the hardware based random order execution is improved by at least 21 times the DPA resistance.

  16. Modular Transformations, Order-Chaos Transitions and Pseudo-Random Number Generation

    Science.gov (United States)

    Bonelli, Antonio; Ruffo, Stefano

    Successive pairs of pseudo-random numbers generated by standard linear congruential transformations display ordered patterns of parallel lines. We study the "ordered" and "chaotic" distribution of such pairs by solving the eigenvalue problem for two-dimensional modular transformations over integers. We conjecture that the optimal uniformity for pair distribution is obtained when the slope of linear modular eigenspaces takes the value n opt =maxint (p/√ {p-1}), where p is a prime number. We then propose a new generator of pairs of independent pseudo-random numbers, which realizes an optimal uniform distribution (in the "statistical" sense) of points on the unit square (0, 1] × (0, 1]. The method can be easily generalized to the generation of k-tuples of random numbers (with k>2).

  17. Effects of randomness on chaos and order of coupled logistic maps

    International Nuclear Information System (INIS)

    Savi, Marcelo A.

    2007-01-01

    Natural systems are essentially nonlinear being neither completely ordered nor completely random. These nonlinearities are responsible for a great variety of possibilities that includes chaos. On this basis, the effect of randomness on chaos and order of nonlinear dynamical systems is an important feature to be understood. This Letter considers randomness as fluctuations and uncertainties due to noise and investigates its influence in the nonlinear dynamical behavior of coupled logistic maps. The noise effect is included by adding random variations either to parameters or to state variables. Besides, the coupling uncertainty is investigated by assuming tinny values for the connection parameters, representing the idea that all Nature is, in some sense, weakly connected. Results from numerical simulations show situations where noise alters the system nonlinear dynamics

  18. Synthetic Smectite Colloids: Characterization of Nanoparticles after Co-Precipitation in the Presence of Lanthanides and Tetravalent Elements (Zr, Th

    Directory of Open Access Journals (Sweden)

    Muriel Bouby

    2015-09-01

    Full Text Available The magnesian smectite hectorite is a corrosion product frequently detected in nuclear waste glass alteration experiments. The structural incorporation of a single trivalent lanthanide was previously demonstrated. Hectorite was presently synthesized, for the first time, in the presence of several lanthanides (La, Eu, Yb following a multi-step synthesis protocol. The smallest-sized particles (nanoparticles, NPs were isolated by centrifugation and analyzed by asymmetrical flow field-flow fractionation (AsFlFFF coupled to ICP-MS, in order to obtain information on the elemental composition and distribution as a function of the size. Nanoparticles can be separated from the bulk smectite phase. The particles are able to accommodate even the larger-sized lanthanides such as La, however, with lower efficiency. We, therefore, assume that the incorporation proceeds by substitution for octahedral Mg accompanied by a concomitant lattice strain that increases with the size of the lanthanides. The presence of a mixture does not seem to affect the incorporation extent of any specific element. Furthermore, syntheses were performed where in addition the tetravalent zirconium or thorium elements were admixed, as this oxidation state may prevail for many actinide ions in a nuclear waste repository. The results show that they can be incorporated as well.

  19. GMM - a general microstructural model for qualitative and quantitative studies of smectite clays

    International Nuclear Information System (INIS)

    Pusch, R.; Karnland, O.; Hoekmark, H.

    1990-12-01

    A few years ago an attempt was made to accommodate a number of basic ideas on the fabric and interparticle forces that are assumed to be valid in montmorillonite clay in an integrated microstructural model and this resulted in an SKB report on 'Outlines of models of water and gas flow through smectite clay buffers'. This model gave reasonable agreement between predicted hydraulic conductivity values and actually recorded ones for room temperature and porewater that is poor in electrolytes. The present report describes an improved model that also accounts for effects generated by salt porewater and heating, and that provides a basis for both quantitative determination of transport capacities in a more general way, and also for analysis and prediction of rheological behaviour in bulk. It has been understood very early by investigators in this scientific field that full understanding of the physical state of porewater is asked for in order to make it possible to develop models for clay particle interaction. In particular, a deep insight in the nature of the interlamellar water and of the hydration mechanisms leading to an equilibrium state between the two types of water, and of forcefields in matured smectite clay, requires very qualified multi-discipline research and attempts have been made by the senior author to initiate and coordinate such work in the last 30 years. Despite this effort it has not been possible to get an unanimous understanding of these things but a number of major features have become more clear through the work that we have been able to carry out in the current SKB research work. Thus, NMR studies and precision measurements of the density of porewater as well as comprehensive electron microscopy and rheological testing in combination with application of stochastical mechanics, have led to the hypothetical microstructural model - the GMM - presented in this report. (au)

  20. Order-based representation in random networks of cortical neurons.

    Directory of Open Access Journals (Sweden)

    Goded Shahaf

    2008-11-01

    Full Text Available The wide range of time scales involved in neural excitability and synaptic transmission might lead to ongoing change in the temporal structure of responses to recurring stimulus presentations on a trial-to-trial basis. This is probably the most severe biophysical constraint on putative time-based primitives of stimulus representation in neuronal networks. Here we show that in spontaneously developing large-scale random networks of cortical neurons in vitro the order in which neurons are recruited following each stimulus is a naturally emerging representation primitive that is invariant to significant temporal changes in spike times. With a relatively small number of randomly sampled neurons, the information about stimulus position is fully retrievable from the recruitment order. The effective connectivity that makes order-based representation invariant to time warping is characterized by the existence of stations through which activity is required to pass in order to propagate further into the network. This study uncovers a simple invariant in a noisy biological network in vitro; its applicability under in vivo constraints remains to be seen.

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

    Science.gov (United States)

    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.

  2. Study of adsorption of zinc in clay smectite type Bofe in system of finite bath

    International Nuclear Information System (INIS)

    Souza, R.S.; Mota, J.D.; Lima, W.S.; Rodrigues, M.G.F.

    2012-01-01

    Clays are demonstrably excellent adsorbents, both for their physical and chemical characteristics and the wide coverage and low cost. Among the various groups of clay minerals, the smectite are noted for having large surface areas. The initial objective of this study was to characterize the clay Bofe through the techniques of X-Ray Diffraction (XRD), X-Ray Spectrometry by Energy Dispersive (EDX) and nitrogen adsorption (BET). To evaluate the adsorption of metal ions zinc (synthetic sewage), we used a system in finite bath, following a factorial design 2 2 , taking as input variables: pH and initial concentrations of zinc (Zn2 +) and output variables: percentage removal and removal capacity. The characterization results showed that Bofe clay belongs to the family of smectite and therefore has great potential for adsorption. (author)

  3. Thallium (Tl) sorption onto illite and smectite: Implications for Tl mobility in the environment

    Science.gov (United States)

    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

  4. Lipase immobilization on smectite nanoclays : Characterization and application to the epoxidation of alpha-pinene

    NARCIS (Netherlands)

    Tzialla, Aikaterini A.; Pavlidis, Ioannis V.; Felicissimo, Marcella P.; Rudolf, Petra; Gournis, Dimitrios; Stamatis, Haralambos

    The immobilization of lipase B from Candida antarctica on smectite group nanoclays (Laponite, SWy-2 and Kunipia), as well as on their organically modified derivatives, was investigated. A combination of techniques, namely X-ray diffraction, thermal analysis, X-ray photoelectron and FT-IR

  5. Heterogeneities in illite/smectite mixed/layers clays: some comments and recollections

    International Nuclear Information System (INIS)

    Johns, W.D.

    1995-01-01

    A review of some studies of heterogeneities, structure and surface in illite/smectite mixed-layer clays of Vienna Basin using X-ray diffraction, high resolution-transmission electron microscopy, infra-red spectroscopy, laser microprobe mass analysis, Auger electron spectroscopy, secondary ion mass spectroscopy, x-ray photoelectron spectroscopy, and ultraviolet photoelectron spectroscopy is given. The models of hexyl ammonium ion configuration complexed between silica sheets is discussed. 1 tab., 10 figs., 6 refs

  6. Occurrence of Fe-Mg-rich smectites and corrensite in the Morron de Mateo bentonite deposit (Cabo de Gata region, Spain): A natural analogue of the bentonite barrier in a radwaste repository

    Energy Technology Data Exchange (ETDEWEB)

    Pelayo, M., E-mail: m.pelayo@ciemat.es [Departamento de Medio Ambiente, CIEMAT, Avda. Complutense 22, 28040 Madrid (Spain); Garcia-Romero, E. [Departamento de Cristalografia y Mineralogia, Facultad C.C. Geologicas, UCM, 28040 Madrid (Spain); Labajo, M.A.; Perez del Villar, L. [Departamento de Medio Ambiente, CIEMAT, Avda. Complutense 22, 28040 Madrid (Spain)

    2011-07-15

    Highlights: > A hydrothermal process transformed Fe-Mg smectites into corrensite. > This transformation was favoured by the intrusion of the Morron de Mateo dome. > The intrusion caused a temperature increased and a supply of Fe-Mg rich solutions. > The system can be a good natural analogue of bentonite barrier in a radwaste disposal. > Experimental studies of stability of bentonite are in agreement with the results. - Abstract: The Morron de Mateo bentonite deposit is being studied as a natural analogue of the thermal and geochemical effects on a bentonite barrier in a deep geological repository of high level radioactive wastes. This bentonite deposit and its host rocks were intruded by a rhyodacitic volcanic dome that induced a hydrothermal metasomatic process affecting the biocalcarenite beds close to the dome. In this work, the mineralogical and chemical features of the clay minerals of the hydrothermally altered pyroclastic (white tuffs) and epiclastic rocks (mass flow), located in the NE sector of the Morron de Mateo deposit are described. White tuffs have a high content of phyllosilicates, mainly composed of dioctahedral smectites, while mass flow have a higher proportion of inherited minerals, the neoformed phyllosilicates are dioctahedral smectites and an interlayer chlorite/smectite mineral of corrensite type. The chemical composition of smectites reflects the different nature of the parent rocks, in such a way that smectites from white tuffs have a quite homogeneous chemical composition and their structural formulae correspond to montmorillonite type, while smectites from mass flow show more chemical variability, higher Fe and Mg contents and a mean structural formulae corresponding to Fe-Mg-rich beidellite and/or to an intermediate smectite member between beidellite and saponite. In addition, chemical composition and textural features of corrensite-like clay minerals in relation to Fe-Mg-rich smectites in the samples have also been studied, suggesting

  7. Occurrence of Fe-Mg-rich smectites and corrensite in the Morron de Mateo bentonite deposit (Cabo de Gata region, Spain): A natural analogue of the bentonite barrier in a radwaste repository

    International Nuclear Information System (INIS)

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

    2011-01-01

    Highlights: → A hydrothermal process transformed Fe-Mg smectites into corrensite. → This transformation was favoured by the intrusion of the Morron de Mateo dome. → The intrusion caused a temperature increased and a supply of Fe-Mg rich solutions. → The system can be a good natural analogue of bentonite barrier in a radwaste disposal. → Experimental studies of stability of bentonite are in agreement with the results. - Abstract: The Morron de Mateo bentonite deposit is being studied as a natural analogue of the thermal and geochemical effects on a bentonite barrier in a deep geological repository of high level radioactive wastes. This bentonite deposit and its host rocks were intruded by a rhyodacitic volcanic dome that induced a hydrothermal metasomatic process affecting the biocalcarenite beds close to the dome. In this work, the mineralogical and chemical features of the clay minerals of the hydrothermally altered pyroclastic (white tuffs) and epiclastic rocks (mass flow), located in the NE sector of the Morron de Mateo deposit are described. White tuffs have a high content of phyllosilicates, mainly composed of dioctahedral smectites, while mass flow have a higher proportion of inherited minerals, the neoformed phyllosilicates are dioctahedral smectites and an interlayer chlorite/smectite mineral of corrensite type. The chemical composition of smectites reflects the different nature of the parent rocks, in such a way that smectites from white tuffs have a quite homogeneous chemical composition and their structural formulae correspond to montmorillonite type, while smectites from mass flow show more chemical variability, higher Fe and Mg contents and a mean structural formulae corresponding to Fe-Mg-rich beidellite and/or to an intermediate smectite member between beidellite and saponite. In addition, chemical composition and textural features of corrensite-like clay minerals in relation to Fe-Mg-rich smectites in the samples have also been studied

  8. The diagenesis-metamorphism limit in pelitic rocks: an X-ray diffraction and decomposition study of illite and interstratified illite/smectite minerals

    International Nuclear Information System (INIS)

    Gharrabi, M.

    1995-01-01

    The definition of the limit between diagenesis and metamorphism has long been debated. Various approaches have been used to describe this limit including mineral reaction such as the appearance of pyrophyllite, illite crystallinity and rock textures (i.e. the development of schistosity). The aim of this study is to characterize the illite clays transformation during this transition. Study of the (001) and (003) XRD peaks of illite and illite-rich interstratified illite/smectite (I/S) by decomposition of XRD spectra allows to define the transformation that affect these minerals in the transition from extensive diagenesis to low grade metamorphism. We studied Paleozoic pelites from the Illinois Basin (USA), Cornwall (UK), Brittany (France) and the Anti-Atlas mountains and the Eastern-Haou/Basin (Morocco) that have undergone this transition. Illite clays pass through three evolutionary stages during the transition from diagenesis to metamorphism: advanced diagenesis where the population of illite particles is composed of the following phases: interstratified illite/smectite (I/S), small illite crystallites (PCI) and large illite crystallites (WCI). The composition of I/S particles that contain approximately 95 % illite layers changes very little at low temperatures even over long periods of time. The most important change during this stage is the reduction in the amount of this phase. These I/S particles (<5% smectite layers) dissolve and furnish the chemical constituents necessary for the growth of PCI and WCI before they are transformed into 100 % illite. Particles of PCI also contain smectite interlayers in their structure. These smectite interlayers may be considered as a characteristic of diagenetic conditions. The second stage, corresponding to anchizone metamorphism is characterized by the disappearance of I/S. The disappearance is caused by higher thermal regime. In the last stage corresponding to epizone metamorphism there exists only one population of illite

  9. Physical capture and release of drug molecules, water and cations by a smectite clay

    DEFF Research Database (Denmark)

    Carvalho dos Santos, Éverton

    -fluorohectorite (LiFh, Li1.2(Mg4.8Li1.2)Si8O20F4), a synthetic clay mineral from the smectite family, have been experimentally analyzed. By means of X-rays powder diffraction (XRD), using both an in-house instrument and synchrotron radiation, UV-Vis spectroscopy, Thermogravimetric Analysis coupled to an Infrared......-analysis and inelastic neutron scattering data we established that the drug presence into the interlayer space of Fh is weakening the water-clay interactions. Furthermore, CIPRO’s release from Fh in synthetic gastric acid juice (SGA) as a function of time and temperature was also carefully followed. Our studies showed...... and toxicological tests, we demonstrated that the effectiveness and toxicity of pure CIPRO is unaffected in the clay-drug complex. To conclude, the high drug adsorption capacity as well as the slow and gradual release from CIPRO when intercalated in Fh adds this synthetic smectite to the list of promising drug...

  10. Dissolution kinetics of smectite in geological repository system of TRU waste

    International Nuclear Information System (INIS)

    Sato, Tsutomu

    2005-02-01

    Extensive use of cement for encapsulation, mine timbering, and grouting purposes is envisaged in geological repositories of TRU waste. Degradation of cement materials in the repositories can produce a high pH pore fluid initially ranging from pH 13.0 to 13.5. The high pH pore fluids can migrate and react chemically with the host rock and bentonites which were employed to enhance repository's integrity. These chemical reactions can effect the capacity of the rocks and bentonites in retarding the migration of radionuclides. Smectite, main component of bentonite, can lose some of their desirable properties at the early stages of bentonite-cement fluid interaction. This has been a key research issue in performance assessment of TRU waste disposal. In this study, firstly, the factors affected on dissolution rate of smectite and equations describing dissolution rate were reviewed. Secondly, the effect of dissolved silica on the dissolution behavior of Na-montmorillonite was investigated. Bulk sample flow-through dissolution experiments at alkaline condition (pH 13.3) with different dissolved silica concentrations at different temperatures were performed. Titration experiments were also carried out at similar conditions. Atomic Force Microscopy (AFM) ex situ observations (i.e. on samples from flow-through experiments) was also performed to obtain the dissolution rate. Current results from bulk sample surface titration experiments indicate that dissolved silica has no pronounced effect on the surface titration behavior of Na-montmorillonite at any temperature. However, the trends for the surface titration behavior represent the averaged behavior of all particle sizes (i.e. including colloids) such that within an order of magnitude change cannot be quantified appreciably. Bulk flow-through dissolution experiments coupled with ex situ AFM observations indicate that there is also no effect of dissolved silica with comparatively low concentration of the reacting solution on

  11. Smectite clays as solid supports for immobilization of beta-glucosidase : Synthesis, characterization, and biochemical properties

    NARCIS (Netherlands)

    Serefoglou, Evangelia; Litina, Kiriaki; Gournis, Dimitrios; Kalogeris, Emmanuel; Tzialla, Aikaterini A.; Pavlidis, Ioannis V.; Stamatis, Haralambos; Maccallini, Enrico; Lubomska, Monika; Rudolf, Petra

    2008-01-01

    Nanomaterials as solid supports can improve the efficiency of immobilized enzymes by reducing diffusional limitation as well as by increasing the surface area per mass unit and therefore improving enzyme loading. In this work, beta-glucosidase from almonds was immobilized on two smectite nanoclays.

  12. Robust Fuzzy Control for Fractional-Order Uncertain Hydroturbine Regulating System with Random Disturbances

    Directory of Open Access Journals (Sweden)

    Fengjiao Wu

    2016-01-01

    Full Text Available The robust fuzzy control for fractional-order hydroturbine regulating system is studied in this paper. First, the more practical fractional-order hydroturbine regulating system with uncertain parameters and random disturbances is presented. Then, on the basis of interval matrix theory and fractional-order stability theorem, a fuzzy control method is proposed for fractional-order hydroturbine regulating system, and the stability condition is expressed as a group of linear matrix inequalities. Furthermore, the proposed method has good robustness which can process external random disturbances and uncertain parameters. Finally, the validity and superiority are proved by the numerical simulations.

  13. Dissolution kinetics of purified and synthetic smectites at 25°C and PH∼9

    International Nuclear Information System (INIS)

    Marty, Nicolas C.M.; Tournassat, Christophe; Gaucher, Eric C.; Chino, Daisuke; Sato, Tsutomu; Villieras, Frederic; Giffaut, Eric; Cama, Jordi; Soler, J.M.

    2010-01-01

    Document available in extended abstract form only. Mineral rate laws that account for the kinetics of dissolution/precipitation of clays and other minerals are used in reactive transport codes to simulate and evaluate the evolution of geochemical conditions in the near-field of high level radioactive waste (HLW) in deep geological repositories. Smectite is the main component in the compacted bentonite used in the Multi-barrier system to lower permeability. As a consequence, molecular diffusion becomes the main mechanism of mass transport, and dissolution and precipitation reactions take place in close-to-equilibrium conditions. Nonetheless, in the reactive transport codes, databases utilized mainly incorporate rate laws derived at far-from- equilibrium conditions, which are not representative of near-field and far-field conditions of concrete-clay or iron-clay interfaces. Hence, there is an important need to derive kinetic rate laws that allow extrapolation of mineral dissolution/precipitation as a function of the solution saturation state (i.e., Gibbs free energy, ΔG r ). Once the effect of the environmental variables, such as pH, T and ΔG r , etc. exert on smectite dissolution is discerned, evaluation of the evolution of geochemical conditions in the HLW repository is carried out using reactive transport codes that couple the rate laws with transport equations. Several studies related dissolution of natural smectites with pH, and just a few dealt with the rate dependency on Gibbs free energy. The present study aims at estimating dissolution rates of montmorillonite in conditions as close as possible to those expected in the Callovo-Oxfordian formation, i.e. pH∼7.2 and 25 deg. C. Dissolution kinetics of two montmorillonites (natural Na-montmorillonite purified from MX80 and synthetic smectite) were investigated by means of flow-through experiments and solution-chemistry data obtained. The calculated rates were based on release of Si, Al and Mg and normalized

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

    Science.gov (United States)

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

    2012-01-01

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

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

    Science.gov (United States)

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

    2012-01-01

    The biogeochemistry of phyllosilicate–Fe redox cycling was studied in a Phalaris arundinacea (reed canary grass) dominated redoximorphic soil from Shovelers Sink, a small glacial depression near Madison, WI. The clay size fraction of Shovelers Sink soil accounts for 16% of the dry weight of the soil, yet contributes 74% of total Fe. The dominant mineral in the clay size fraction is mixed layer illite–smectite, and in contrast to many other soils and sediments, Fe(III) oxides are present in low abundance. We examined the Fe biogeochemistry of Shovelers Sink soils, estimated the abundance of Fe redox cycling microorganisms, and isolated in pure culture representative phyllosilicate–Fe oxidizing and reducing organisms. The abundance of phyllosilicate–Fe reducing and oxidizing organisms was low compared to culturable aerobic heterotrophs. Both direct isolation and dilution-to-extinction approaches using structural Fe(II) in Bancroft biotite as a Fe(II) source, and 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

  16. Magnetic and superconducting order in some random pseudobinary compounds

    International Nuclear Information System (INIS)

    Dongen, J.C.M. van.

    1982-01-01

    This thesis presents the results of a study on the magnetic and superconducting ordering phenomena in some random pseudobinary compounds. In the investigations ternary systems are utilised in which two of the elements form a binary intermetallic compound, e.g. PdH, GdCu and YCo 2 . A third element is then randomly substituted into one of the sublattices without changing the basic intermetallic compound structure. In chapter II a study is presented on the Kondo effect and spin-glass freezing of the magnetic impurities Cr, Mn, and Fe in superconducting palladium hydride. Chapter III contains a study on crystal structure transformations and magnetic ordering phenomena in GdCusub(1-x)Gasub(x) and related pseudobinary compounds. In Chapter IV experiments on the magnetic properties and the electrical resistivity of the transition metal Laves phase compounds Y(Cosub(1-x)Fesub(x)) 2 , Y(Irsub(1-x)Fesub(x)) 2 and Hf(Cosub(1-x)Fesub(x)) 2 are described. (Auth.)

  17. Purification and characterization of smectite clay taken from Gafsa, Tunisia: Progressive elimination of carbonates

    International Nuclear Information System (INIS)

    Mhamdi, M; Gasmi, N; Elaloui, E; Kbir-Ariguib, N; Trabelsi-Ayadi, M

    2010-01-01

    This work shows the results of various analysis on a representative clay sample from southern west of Tunisia, particularly from Oued Tfal near the town of Gafsa. The raw smectite contains some carbonate, quartz, chlorite, and anorthite. During the attack of the carbonate clay with a solution of hydrochloric acid, a change of the chemical composition and physical properties was observed. This change is dependent on several factors: the initial concentration of the acid, the nature of the clay, the ratio acid / clay...). Although treatment to 0.5 M represents a total removal of carbonates, there are probably altered layers of the clay fraction. The result shows that for a treatment with acid solutions of concentrations below 0.5 M there is gradual removal of carbonate without protonation of the clay layers. The characterization of the clay fraction shows that the sodium clay purified (OTNa) consists of a sodium montmorillonite smectite. The cation exchange capacity and the specific surface of OTNa measured using the method of methylene blue are equal to 82 meq/100g and 667 m 2 / g respectively.

  18. Retention behavior of actinides and long lived fission products on Smectite rich clays

    International Nuclear Information System (INIS)

    Tomar, B.S.

    2014-01-01

    In the present work, sorption of Am(llI), Cs(I) and Sr(ll) by the Smectite rich clay from western India has been studied in detail under the varying experimental conditions, viz., pH, ionic strength, and metal ion concentration. The experimental data on sorption have been modeled using the surface complexation model. Am(llI) sorption by smectite rich clay was found to increase with the pH of the suspension. At lower pH values, the sorption decreased with increasing ionic strength of the suspension, but remained constant at higher pH values. This is reminiscent of the ion exchange mechanism at lower pH and predominantly inner sphere complexation at higher pH. Surface complexation modeling using FITEQL could successfully explain these two mechanisms operating in the different pH values. Sorption of Cs(I) and Sr(II) by the smectite rich clay was studied under the varying experimental conditions. Though the sorption of both the metal ions increased with pH, it decreased with the increasing ionic strength, at all pH values, suggesting ion exchange as the predominant mechanism at all pH values. Further, the ionic strength dependence was different in the case of Cs(I) and Sr(II) depending upon the metal ion concentration. At same metal ion concentration of Cs(I) and Sr(II) (10 -5 M) the extent of decrease with ionic strength was same in both cases, while at 10 -9 M, Cs(I), the decrease was much smaller than that at 10 -5 M. This indicates the existence of ion exchange sites having different affinities. These studies have shown high retention capacity of the clay for actinides and long lived fission products with the sorption following ion exchange mechanism in the case of Cs(I) and Sr(II) and a combination of ion exchange and surface complexation in the case of Am(III) depending upon the pH. The sorption data could be successfully explained within the framework of FITEQL, taking into account both the types of binding sites

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

    Science.gov (United States)

    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.

  20. Terahertz time-domain spectroscopy response of amines and amino acids intercalated smectites in far-infrared region

    Energy Technology Data Exchange (ETDEWEB)

    Janek, M., E-mail: marian.janek@fns.uniba.sk [Comenius University, Faculty of Natural Sciences, Department of Physical and Theoretical Chemistry, Mlynská dolina CH1, SK-84215 Bratislava (Slovakia); Zich, D. [Comenius University, Faculty of Natural Sciences, Department of Physical and Theoretical Chemistry, Mlynská dolina CH1, SK-84215 Bratislava (Slovakia); Naftaly, M., E-mail: mira.naftaly@npl.co.uk [National Physical Laboratory, Hampton Rd, Teddington, Middlesex TW11 0LW (United Kingdom)

    2014-06-01

    Layered clay minerals from the smectite group with different chemical composition and resulting layer charge (e.g. pyrophyllite, illite, hectorite and montmorillonite) were characterised for their dielectric properties in the far-infrared region using terahertz-time domain spectroscopy (THz-TDS). Samples with distinct cation exchange capacity such as hectorite and montmorillonite were modified using cation exchange reaction with alkylamines or amino acids. The presence of these species in 2D gallery was proved by X-ray diffraction and Fourier transform infrared spectroscopy. The frequency-dependent refractive index of these minerals was determined in the experimentally accessible range of 0.1–3.0 THz (3–100 cm{sup −1}) using THz-TDS. Pristine samples revealed their refractive indices to be 1.82–2.15 at about 1 THz while the modified montmorillonite samples had their refractive indices changed by organic molecules used for their modification to 1.70–2.35 for amines and 1.97–2.36 for amino acids. The presence of organic substances in 2D gallery of clays was detectable despite the relatively high absorption of smectites with magnitude of 100 cm{sup −1}. - Graphical abstract: Display Omitted - Highlights: • “Guest” molecules in “host” layered material were investigated. • Amines and amino-acids were selected as guest molecules. • Natural and synthetic host with smectite phyllosilicate structure were used. • Dielectric properties were investigated by terahertz time domain spectroscopy. • Resonance absorption peaks of guest were detected in far infrared region.

  1. Obtaining and Organophilisation of Smectite Clays with Reduced Iron Oxide Content

    Directory of Open Access Journals (Sweden)

    Karasa Jūlija

    2016-05-01

    Full Text Available Raw clays from the Baltic region are characterized as smectite containing clays with significant amount of naturally occurring impurities that limiting the potential applications of crude Baltic clay resources. Purification of clay samples from Šaltiškių deposit (Venta basin was carried out by varied concentration hydrochloric acid solutions and resulted in fine removal of carbonates and iron oxide. The main idea of this work is to widen the possible applications of local clay resources providing a new type of raw material for further organoclay production.

  2. 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

    Science.gov (United States)

    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.

  3. Characteristics of organoclays obtained from Paraibas's smectites; Caracteristicas de argilas organofilicas obtidas de esmectitas da Paraiba

    Energy Technology Data Exchange (ETDEWEB)

    Martin-Cortes, G.R.; Almeida, A.; Esper, F.J.; Alves Junior, P.; Valenzuela-Diaz, F.R., E-mail: germac@usp.br [Universidade de Sao Paulo (PMT/EP/USP), Sao Paulo, SP (Brazil). Escola Politecnica. Dept. de Engenharia Meralurgica e de Materiais; Hennies, W.T. [Universidade de Sao Paulo (PMT/EP/USP), Sao Paulo, SP (Brazil). Escola Politecnica. Dept. de Engenharia de Minas e de Petroleo

    2011-07-01

    Organoclay (AO) applies in the industry due to its particular technical characteristics. They are used as rheological additives in drilling fluids for oil, by adding viscosity solutions in which it participates: in paints, adhesives, lubricants, cosmetics and others. Recently grows its use as reinforcing filler in structuring polymer nanocomposites. The organoclays are obtained by the modification with quaternary ammonium of smectites. This paper presents the characteristics of a organoclay product of modified smectite from the State of Paraiba by quaternary ammonium. These studies were done in the PMT-EPUSP - Metallurgical and Materials Engineering Dept. of the Polytechnic School, University of Sao Paulo. The paper presents the results of studies through the techniques of X-ray diffraction, thermal analysis, infrared spectroscopy Foster swelling in oils and organic solvents tests and Scanning Electronic Microscopy. (author)

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2011-01-01

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

  6. Study of smectite clays of the city Pedra Lavrada - PB for use in water-based drilling fluids

    International Nuclear Information System (INIS)

    Silva, I.A. da; Costa, J.M.R.; Cardoso, M.A.F.; Neves, G.A.; Ferreira, H.C.

    2011-01-01

    Paraiba has large reserves of bentonite clays, with the largest deposits in Boa Vista, PB. Recently new deposits were discovered in the cities of Cubati and Pedra Lavrada-PB, creating great expectations for further expansion of reserves for industrial production. The aim of this work is the study of smectite clays from the city of Pedra Lavrada, PB for use in drilling fluids water based. The characterization was made by the diffraction of laser (AG), thermogravimetric and differential thermal analysis (TGA and DTA), chemical composition by X-ray fluorescence (EDX), X-ray diffraction (XRD), exchange capacity of cations (ECC) and surface area (SA). The results obtained so far showed that the samples presented at its mineral composition smectite, kaolinite and quartz. In relation to rheological properties showed that the bentonite clay sample Dark presents promising features for use in water based drilling fluids. (author)

  7. Analysis of the structural stability of the smectite submitted to high pressures and temperatures; Analise da estabilidade estrutural da esmectita sob altas pressoes e altas temperaturas

    Energy Technology Data Exchange (ETDEWEB)

    Alabarse, Frederico Gil

    2009-10-15

    The thermal stability of bentonite is of particular interest for containment barrier in nuclear waste disposal facilities. However, very little is known about the stability of smectite (principal component of bentonite) under high-pressure and high-temperature conditions (HPHT). The objective of this work was to investigate the stability of the smectite structure under HP-HT conditions. The HP-HT experiments were performed on toroidal chambers (TC) with pressure up 7.7 GPa and temperatures of 1000 deg C. The samples were characterized by X-ray diffraction after the HP-HT processing. Furthermore, one sample from the original material was analyzed using Fourier transformed infra-red (FTIR) in situ measurements on a diamond anvil cell (DAC) in experiments up to 12 GPa. The original sample of bentonite, calcium dioctahedral montmorillonite with small fraction of quartz, was characterized by FTIR, XRD, X-ray fluorescence (XRF), scanning electron microscopy (SEM), surface area, thermogravimetric analysis (TGA) and differential thermal analysis (DTA). In the experiment performed using the DAC up to 12 GPa, the FTIR in situ measurements analysis showed that the smectite structure is stable with a reversible deformation in the Si-O bond and that the smectite did not loose water. Experiments performed in TC at 7.7 GPa of pressure and 250 deg C of temperature, during 3.5 h showed, after analysis by XRD and FTIR, that the smectite structure is stable and did not loose water. Experiments performed in TC at 7.7 GPa of pressure and 1000 deg C of temperature, during 3.5 h showed, after analysis by XRD and SEM, the transformation of bentonite to the mineral assemblage: Coesite, Quartz, Kyanite and Pyrope. (author)

  8. Modification of a Brazilian smectite clay with different quaternary ammonium salts

    Directory of Open Access Journals (Sweden)

    Maria Flávia Delbem

    2010-01-01

    Full Text Available In this work, a smectite clay from the State of Paraiba, Brazil, was treated with six different types of ammonium salts, which is an usual method to enhance the affinity between the clay and polymer for the preparation of nanocomposites. The clays, before and after modification, were characterized by X ray diffraction. The conformation of the salts within the platelets of the clay depended on the number of long alkyl chains of the salt. The thermal stability of the clays was also studied. The ammonium salts thermal decomposition was explained in light of their position within the organoclays.

  9. Variances as order parameter and complexity measure for random Boolean networks

    International Nuclear Information System (INIS)

    Luque, Bartolo; Ballesteros, Fernando J; Fernandez, Manuel

    2005-01-01

    Several order parameters have been considered to predict and characterize the transition between ordered and disordered phases in random Boolean networks, such as the Hamming distance between replicas or the stable core, which have been successfully used. In this work, we propose a natural and clear new order parameter: the temporal variance. We compute its value analytically and compare it with the results of numerical experiments. Finally, we propose a complexity measure based on the compromise between temporal and spatial variances. This new order parameter and its related complexity measure can be easily applied to other complex systems

  10. Variances as order parameter and complexity measure for random Boolean networks

    Energy Technology Data Exchange (ETDEWEB)

    Luque, Bartolo [Departamento de Matematica Aplicada y EstadIstica, Escuela Superior de Ingenieros Aeronauticos, Universidad Politecnica de Madrid, Plaza Cardenal Cisneros 3, Madrid 28040 (Spain); Ballesteros, Fernando J [Observatori Astronomic, Universitat de Valencia, Ed. Instituts d' Investigacio, Pol. La Coma s/n, E-46980 Paterna, Valencia (Spain); Fernandez, Manuel [Departamento de Matematica Aplicada y EstadIstica, Escuela Superior de Ingenieros Aeronauticos, Universidad Politecnica de Madrid, Plaza Cardenal Cisneros 3, Madrid 28040 (Spain)

    2005-02-04

    Several order parameters have been considered to predict and characterize the transition between ordered and disordered phases in random Boolean networks, such as the Hamming distance between replicas or the stable core, which have been successfully used. In this work, we propose a natural and clear new order parameter: the temporal variance. We compute its value analytically and compare it with the results of numerical experiments. Finally, we propose a complexity measure based on the compromise between temporal and spatial variances. This new order parameter and its related complexity measure can be easily applied to other complex systems.

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

    Science.gov (United States)

    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.; hide

    2016-01-01

    Mars Exploration Rover Opportunity has been exploring Mars for 12+ years, and is presently investigating the geology of a western rim segment of 22 kilometers diameter, Noachian- aged Endeavour crater. The Alpha Particle X-ray Spectrometer has determined the compositions of a pre-impact lithology, the Matijevic fm., and polymict impact breccias ejected from the crater, the Shoemaker fm. Opportunity is now investigating a region named Marathon Valley that cuts southwest-northeast through the central portion of the rim segment and provides a window into the lower stratigraphic record. (Geographic names used here are informal.) At the head of Marathon Valley, referred to here as Upper Marathon Valley, is a shallow, ovoid depression approximately 25×35 millimeters in size, named Spirit of Saint Louis. Layering inside Spirit of Saint Louis appears continuous with the Upper Marathon Valley rocks outside, indicating they are coeval. Spirit of Saint Louis is partly bounded by approximately 10-20 centimeters wide zone containing reddish altered rocks (red zone). Red zones also form prominent curvilinear features in Marathon Valley. Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) spectra provide evidence for a really extensive Fe-Mg smectite in the Marathon Valley region, indicating distinct styles of aqueous alteration. The CRISM detections of smectites are based on metal-OH absorptions at approximately 2.3 and 2.4 micron that are at least two times the background noise level.

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

    Science.gov (United States)

    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.

  13. Na-smectite s in the Cala de Tomate bentonite deposit (Spain): a natural analogue of the salinity effect on the bentonite barrier of a rad waste disposal

    Energy Technology Data Exchange (ETDEWEB)

    Perez del Villar, L.; Pelayo, M.; Fernandez, A.M.; Cozar, J.S. [CIEMAT - Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas (CIEMAT/DIRE/CEAGP), Madrid (Spain); Delgado, A.; Reyes, E. [Ciencias de la Tierra y Quimica Ambiental Estacion Experimental del Zaidin Dpt., Granada (Spain); Fernandez-Soler, J.M. [Granada Univ., Dpt. de Mineralogia y Petrologia (Spain); Tsige, M. [Facultad de Ciencias Geologicas, Dpt. de Geodinamica, Madrid (Spain)

    2005-07-01

    Within the framework of the ENRESA programme for the assessment of the long-term behaviour of the bentonite-engineered barrier for a deep radwaste geological repository, analogue studies on several bentonite deposits are conducted at CIEMAT. Among these analogue studies, the thermal effect induced by volcanic intrusions on bentonite deposits is highlighted. In the Cabo de Gata volcanic region, there are several analogue scenarios where these studies have been performed, such as the Cala de Tomate bentonite deposit that was intruded by a pyroxene andesite volcanic dome. However, geological, mineralogical, physicochemical, geochemical and stable isotopic data obtained from the smectites do not allow to establish any analogy with the thermal effect expected on the bentonite-engineered barrier of a deep geological repository after burial. Thus, the bentonitisation processes took place after the intrusion of the dome, as a result of meteoric diagenesis intensively developed on faulting zone affecting the parent pyroclastic acid tuffs. This faulting process occurred after the dome intrusion. However, the physicochemical characteristics of these smectites, specially the exchangeable cations, allow to consider this bentonite deposit as a natural analogue of the saline effect on the clayey barrier. This analogy has been established because Na-smectites are present in this deposit and, up to our present knowledge, it is the first time that these smectites occur naturally in the Cabo de Gata-La Serrata de Nijar volcanic region. As a consequence, the main objectives of this work are: i) to characterise these smectites; ii) to establish their genesis and processes affecting them after their formation and iii) to identify the effects on the bentonite-engineered barrier should it were affected by a Na-rich saline waterfront. (authors)

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  16. Order out of Randomness: Self-Organization Processes in Astrophysics

    Science.gov (United States)

    Aschwanden, Markus J.; Scholkmann, Felix; Béthune, William; Schmutz, Werner; Abramenko, Valentina; Cheung, Mark C. M.; Müller, Daniel; Benz, Arnold; Chernov, Guennadi; Kritsuk, Alexei G.; Scargle, Jeffrey D.; Melatos, Andrew; Wagoner, Robert V.; Trimble, Virginia; Green, William H.

    2018-03-01

    Self-organization is a property of dissipative nonlinear processes that are governed by a global driving force and a local positive feedback mechanism, which creates regular geometric and/or temporal patterns, and decreases the entropy locally, in contrast to random processes. Here we investigate for the first time a comprehensive number of (17) self-organization processes that operate in planetary physics, solar physics, stellar physics, galactic physics, and cosmology. Self-organizing systems create spontaneous " order out of randomness", during the evolution from an initially disordered system to an ordered quasi-stationary system, mostly by quasi-periodic limit-cycle dynamics, but also by harmonic (mechanical or gyromagnetic) resonances. The global driving force can be due to gravity, electromagnetic forces, mechanical forces (e.g., rotation or differential rotation), thermal pressure, or acceleration of nonthermal particles, while the positive feedback mechanism is often an instability, such as the magneto-rotational (Balbus-Hawley) instability, the convective (Rayleigh-Bénard) instability, turbulence, vortex attraction, magnetic reconnection, plasma condensation, or a loss-cone instability. Physical models of astrophysical self-organization processes require hydrodynamic, magneto-hydrodynamic (MHD), plasma, or N-body simulations. Analytical formulations of self-organizing systems generally involve coupled differential equations with limit-cycle solutions of the Lotka-Volterra or Hopf-bifurcation type.

  17. Robust Fuzzy Control for Fractional-Order Uncertain Hydroturbine Regulating System with Random Disturbances

    OpenAIRE

    Fengjiao Wu; Guitao Zhang; Zhengzhong Wang

    2016-01-01

    The robust fuzzy control for fractional-order hydroturbine regulating system is studied in this paper. First, the more practical fractional-order hydroturbine regulating system with uncertain parameters and random disturbances is presented. Then, on the basis of interval matrix theory and fractional-order stability theorem, a fuzzy control method is proposed for fractional-order hydroturbine regulating system, and the stability condition is expressed as a group of linear matrix inequalities. ...

  18. Backfilling with mixtures of bentonite/ballast materials or natural smectitic clay?

    International Nuclear Information System (INIS)

    Pusch, R.

    1998-10-01

    Comparison of the performance of backfills of mixed MX-80 and crushed rock ballast, and a natural smectitic clay, represented by the German Friedland clay, shows that the latter performs better than mixtures with up to 30 % MX-80. Considering cost, Friedland clay prepared to yield air-dry powder grains is cheaper than mixtures of 30 % MX-80 and crushed ballast. Both technically and economically it appears that the Friedland clay is a competitive alternative to mixtures of 30 % MX-80 and crushed ballast. However, it remains to be demonstrated on a full scale that Friedland clay ground to a suitable grain size distribution can be acceptably compacted on site

  19. Spectroscopic characterization of schiff base-copper complexes immobilized in smectite clays

    Directory of Open Access Journals (Sweden)

    Patrícia M. Dias

    2010-01-01

    Full Text Available Herein, the immobilization of some Schiff base-copper(II complexes in smectite clays is described as a strategy for the heterogenization of homogeneous catalysts. The obtained materials were characterized by spectroscopic techniques, mostly UV/Vis, EPR, XANES and luminescence spectroscopy. SWy-2 and synthetic Laponite clays were used for the immobilization of two different complexes that have previously shown catalytic activity in the dismutation of superoxide radicals, and disproportionation of hydrogen peroxide. The obtained results indicated the occurrence of an intriguing intramolecular redox process involving copper and the imine ligand at the surface of the clays. These studies are supported by computational calculations.

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

    International Nuclear Information System (INIS)

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

    2009-01-01

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

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

    Science.gov (United States)

    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.

  2. Sr and Ar isotope studies of detrital smectites from the Atlantic Ocean (D.S.D.P., Legs 43, 48 and 50)

    International Nuclear Information System (INIS)

    Clauer, N.; Lucas, J.

    1984-01-01

    Mineralogical, morphological and isotopic (Rb-Sr and K-Ar) determinations were made on some detrital smectites of Palaeocene and Cenomanian ages from D.S.D.P. drillings in the Atlantic Ocean. These minerals are not inert in their depositional environment; authigenic laths grow on detrital sheets with sharp borders. This authigenesis could occur slightly after deposition in a closed system, for some of these smectites. It has been tentatively quantified by the Rb-Sr and K-Ar isotopic methods, which seem also well suited to evaluate the chemical extent of this authigenesis. At least, no preferential loss of 40 Ar vs. 87 Sr could be detected in the minerals, even in those which are smaller than 0.2 μm. (Auth.)

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

    Science.gov (United States)

    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...

  4. Experimental study of the effect of high porewater salinity on the physical properties of a natural smectitic clay

    Energy Technology Data Exchange (ETDEWEB)

    Pusch, Roland [Geodevelopment AB, Lund (Sweden)

    2001-03-01

    Natural smectitic clays for backfilling tunnels and shafts in deep repositories may be an alternative to mixtures of bentonite and ballast. Very salt groundwater is known to raise the hydraulic conductivity and reduce the expandability of clay materials in general and of bentonite/ballast mixtures in particular and the present study aimed at determining the impact of salt water on the major physical properties of natural smectitic clays, represented by the German Friedland Ton. The investigation showed that the compactability of the investigated clay is not significantly affected by the water content in contrast to bentonite/ballast fills, and that the conductivity and expandability are acceptable even at salt contents of up to 20 % if the bulk density at saturation is slightly higher than 2000 kg/m{sup 3} . For salt contents up to 3. 5 % the corresponding density is around 1900 kg/m{sup 3}. In general, the investigated clay offers better physical properties than mixtures of bentonite/ballast mixtures with up to 30 % bentonite content.

  5. Experimental study of the effect of high porewater salinity on the physical properties of a natural smectitic clay

    International Nuclear Information System (INIS)

    Pusch, Roland

    2001-03-01

    Natural smectitic clays for backfilling tunnels and shafts in deep repositories may be an alternative to mixtures of bentonite and ballast. Very salt groundwater is known to raise the hydraulic conductivity and reduce the expandability of clay materials in general and of bentonite/ballast mixtures in particular and the present study aimed at determining the impact of salt water on the major physical properties of natural smectitic clays, represented by the German Friedland Ton. The investigation showed that the compactability of the investigated clay is not significantly affected by the water content in contrast to bentonite/ballast fills, and that the conductivity and expandability are acceptable even at salt contents of up to 20 % if the bulk density at saturation is slightly higher than 2000 kg/m 3 . For salt contents up to 3. 5 % the corresponding density is around 1900 kg/m 3 . In general, the investigated clay offers better physical properties than mixtures of bentonite/ballast mixtures with up to 30 % bentonite content

  6. First-order corrections to random-phase approximation GW calculations in silicon and diamond

    NARCIS (Netherlands)

    Ummels, R.T.M.; Bobbert, P.A.; van Haeringen, W.

    1998-01-01

    We report on ab initio calculations of the first-order corrections in the screened interaction W to the random-phase approximation polarizability and to the GW self-energy, using a noninteracting Green's function, for silicon and diamond. It is found that the first-order vertex and self-consistency

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2009-01-01

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

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

    Science.gov (United States)

    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 .

  10. Measuring order in disordered systems and disorder in ordered systems: Random matrix theory for isotropic and nematic liquid crystals and its perspective on pseudo-nematic domains

    Science.gov (United States)

    Zhao, Yan; Stratt, Richard M.

    2018-05-01

    Surprisingly long-ranged intermolecular correlations begin to appear in isotropic (orientationally disordered) phases of liquid crystal forming molecules when the temperature or density starts to close in on the boundary with the nematic (ordered) phase. Indeed, the presence of slowly relaxing, strongly orientationally correlated, sets of molecules under putatively disordered conditions ("pseudo-nematic domains") has been apparent for some time from light-scattering and optical-Kerr experiments. Still, a fully microscopic characterization of these domains has been lacking. We illustrate in this paper how pseudo-nematic domains can be studied in even relatively small computer simulations by looking for order-parameter tensor fluctuations much larger than one would expect from random matrix theory. To develop this idea, we show that random matrix theory offers an exact description of how the probability distribution for liquid-crystal order parameter tensors converges to its macroscopic-system limit. We then illustrate how domain properties can be inferred from finite-size-induced deviations from these random matrix predictions. A straightforward generalization of time-independent random matrix theory also allows us to prove that the analogous random matrix predictions for the time dependence of the order-parameter tensor are similarly exact in the macroscopic limit, and that relaxation behavior of the domains can be seen in the breakdown of the finite-size scaling required by that random-matrix theory.

  11. Heterogeneous photo-Fenton decolorization of Orange II over Al-pillared Fe-smectite: Response surface approach, degradation pathway, and toxicity evaluation

    Energy Technology Data Exchange (ETDEWEB)

    Li, Huiyuan; Li, Yanli [Department of Environmental Engineering, Wuhan University, Wuhan 430079 (China); Xiang, Luojing [Department of Environmental Engineering, Wuhan University, Wuhan 430079 (China); Université de Poitiers, UMR CNRS 7285, IC2MP, ENSIP, B1, 1 rue Marcel Doré, TSA 41105, Poitiers 86073 Cedex 9 (France); Huang, Qianqian; Qiu, Juanjuan [Department of Environmental Engineering, Wuhan University, Wuhan 430079 (China); Zhang, Hui, E-mail: eeng@whu.edu.cn [Department of Environmental Engineering, Wuhan University, Wuhan 430079 (China); Sivaiah, Matte Venkata; Baron, Fabien; Barrault, Joel; Petit, Sabine [Université de Poitiers, UMR CNRS 7285, IC2MP, ENSIP, B1, 1 rue Marcel Doré, TSA 41105, Poitiers 86073 Cedex 9 (France); Valange, Sabine, E-mail: sabine.valange@univ-poitiers.fr [Université de Poitiers, UMR CNRS 7285, IC2MP, ENSIP, B1, 1 rue Marcel Doré, TSA 41105, Poitiers 86073 Cedex 9 (France)

    2015-04-28

    Highlights: • Al-pillared Fe-smectite was synthesized and used as the photo-Fenton catalyst. • Response surface methodology was used to study the effects of reaction parameters. • The main intermediate products were identified by GC–MS technique. • A possible degradation pathway of Orange II was proposed. • All the generated products of Orange II were less toxic than the original dye. - Abstract: A ferric smectite clay material was synthesized and further intercalated with Al{sub 2}O{sub 3} 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 0.5 g/L and hydrogen peroxide concentration of 13.5 mM 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 160 mg/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 150 min reaction, indicating that the effluent was suitable for sequential biological treatment.

  12. Backfilling with mixtures of bentonite/ballast materials or natural smectitic clay?

    Energy Technology Data Exchange (ETDEWEB)

    Pusch, R. [Geodevelopment AB, (Sweden)

    1998-10-01

    Comparison of the performance of backfills of mixed MX-80 and crushed rock ballast, and a natural smectitic clay, represented by the German Friedland clay, shows that the latter performs better than mixtures with up to 30 % MX-80. Considering cost, Friedland clay prepared to yield air-dry powder grains is cheaper than mixtures of 30 % MX-80 and crushed ballast. Both technically and economically it appears that the Friedland clay is a competitive alternative to mixtures of 30 % MX-80 and crushed ballast. However, it remains to be demonstrated on a full scale that Friedland clay ground to a suitable grain size distribution can be acceptably compacted on site 14 refs, 32 figs, 6 tabs

  13. Long range order and giant components of quantum random graphs

    CERN Document Server

    Ioffe, D

    2006-01-01

    Mean field quantum random graphs give a natural generalization of classical Erd\\H{o}s-R\\'{e}nyi percolation model on complete graph $G_N$ with $p =\\beta /N$. Quantum case incorporates an additional parameter $\\lambda\\geq 0$, and the short-long range order transition should be studied in the $(\\beta ,\\lambda)$-quarter plane. In this work we explicitly compute the corresponding critical curve $\\gamma_c$, and derive results on two-point functions and sizes of connected components in both short and long range order regions. In this way the classical case corresponds to the limiting point $(\\beta_c ,0) = (1,0)$ on $\\gamma_c$.

  14. Ordering statistics of four random walkers on a line

    Science.gov (United States)

    Helenbrook, Brian; ben-Avraham, Daniel

    2018-05-01

    We study the ordering statistics of four random walkers on the line, obtaining a much improved estimate for the long-time decay exponent of the probability that a particle leads to time t , Plead(t ) ˜t-0.91287850 , and that a particle lags to time t (never assumes the lead), Plag(t ) ˜t-0.30763604 . Exponents of several other ordering statistics for N =4 walkers are obtained to eight-digit accuracy as well. The subtle correlations between n walkers that lag jointly, out of a field of N , are discussed: for N =3 there are no correlations and Plead(t ) ˜Plag(t) 2 . In contrast, our results rule out the possibility that Plead(t ) ˜Plag(t) 3 for N =4 , although the correlations in this borderline case are tiny.

  15. Randomized and quantum algorithms for solving initial-value problems in ordinary differential equations of order k

    Directory of Open Access Journals (Sweden)

    Maciej Goćwin

    2008-01-01

    Full Text Available The complexity of initial-value problems is well studied for systems of equations of first order. In this paper, we study the \\(\\varepsilon\\-complexity for initial-value problems for scalar equations of higher order. We consider two models of computation, the randomized model and the quantum model. We construct almost optimal algorithms adjusted to scalar equations of higher order, without passing to systems of first order equations. The analysis of these algorithms allows us to establish upper complexity bounds. We also show (almost matching lower complexity bounds. The \\(\\varepsilon\\-complexity in the randomized and quantum setting depends on the regularity of the right-hand side function, but is independent of the order of equation. Comparing the obtained bounds with results known in the deterministic case, we see that randomized algorithms give us a speed-up by \\(1/2\\, and quantum algorithms by \\(1\\ in the exponent. Hence, the speed-up does not depend on the order of equation, and is the same as for the systems of equations of first order. We also include results of some numerical experiments which confirm theoretical results.

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

    Science.gov (United States)

    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 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

  17. Magnetic ordering at low temperatures in some random superconducting and insulating compounds

    International Nuclear Information System (INIS)

    Hueser, D.

    1985-01-01

    This thesis presents the results of some investigations on the magnetic ordering phenomena in some random superconducting and insulating materials. The results are described of an investigation of the coexistence of superconductivity and random magnetic freezing in (Th,Nd)Ru 2 . On the basis of various measurements as function of temperature and external magnetic field the author found that spin glass-like freezing can occur far below the superconductivity and even that a sample may re-enter the superconducting state below a freezing temperature. Associated with the isothermal remanent magnetization of a random magnetic material he observed strong anomalies in the critical field versus temperature curves. Also a magnetic field memory effect has been found. (Auth.)

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

    Science.gov (United States)

    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.

  19. SOERP, Statistics and 2. Order Error Propagation for Function of Random Variables

    International Nuclear Information System (INIS)

    Cox, N. D.; Miller, C. F.

    1985-01-01

    1 - Description of problem or function: SOERP computes second-order error propagation equations for the first four moments of a function of independently distributed random variables. SOERP was written for a rigorous second-order error propagation of any function which may be expanded in a multivariable Taylor series, the input variables being independently distributed. The required input consists of numbers directly related to the partial derivatives of the function, evaluated at the nominal values of the input variables and the central moments of the input variables from the second through the eighth. 2 - Method of solution: The development of equations for computing the propagation of errors begins by expressing the function of random variables in a multivariable Taylor series expansion. The Taylor series expansion is then truncated, and statistical operations are applied to the series in order to obtain equations for the moments (about the origin) of the distribution of the computed value. If the Taylor series is truncated after powers of two, the procedure produces second-order error propagation equations. 3 - Restrictions on the complexity of the problem: The maximum number of component variables allowed is 30. The IBM version will only process one set of input data per run

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

    Science.gov (United States)

    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

  1. Fuzzy Random Walkers with Second Order Bounds: An Asymmetric Analysis

    Directory of Open Access Journals (Sweden)

    Georgios Drakopoulos

    2017-03-01

    Full Text Available Edge-fuzzy graphs constitute an essential modeling paradigm across a broad spectrum of domains ranging from artificial intelligence to computational neuroscience and social network analysis. Under this model, fundamental graph properties such as edge length and graph diameter become stochastic and as such they are consequently expressed in probabilistic terms. Thus, algorithms for fuzzy graph analysis must rely on non-deterministic design principles. One such principle is Random Walker, which is based on a virtual entity and selects either edges or, like in this case, vertices of a fuzzy graph to visit. This allows the estimation of global graph properties through a long sequence of local decisions, making it a viable strategy candidate for graph processing software relying on native graph databases such as Neo4j. As a concrete example, Chebyshev Walktrap, a heuristic fuzzy community discovery algorithm relying on second order statistics and on the teleportation of the Random Walker, is proposed and its performance, expressed in terms of community coherence and number of vertex visits, is compared to the previously proposed algorithms of Markov Walktrap, Fuzzy Walktrap, and Fuzzy Newman–Girvan. In order to facilitate this comparison, a metric based on the asymmetric metrics of Tversky index and Kullback–Leibler divergence is used.

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

    Science.gov (United States)

    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.

  3. Piecewise linearisation of the first order loss function for families of arbitrarily distributed random variables

    NARCIS (Netherlands)

    Rossi, R.; Hendrix, E.M.T.

    2014-01-01

    We discuss the problem of computing optimal linearisation parameters for the first order loss function of a family of arbitrarily distributed random variable. We demonstrate that, in contrast to the problem in which parameters must be determined for the loss function of a single random variable,

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

    Science.gov (United States)

    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.

  5. Simulation-based production planning for engineer-to-order systems with random yield

    NARCIS (Netherlands)

    Akcay, Alp; Martagan, Tugce

    2018-01-01

    We consider an engineer-to-order production system with unknown yield. We model the yield as a random variable which represents the percentage output obtained from one unit of production quantity. We develop a beta-regression model in which the mean value of the yield depends on the unique

  6. Single order soft X-ray diffraction with quasi-random radius pinhole array spectroscopic photon sieves

    International Nuclear Information System (INIS)

    Zhang Qiang-Qiang; Wei Lai; Yang Zu-Hua; Qian Feng; Fan Quan-Ping; Zhang Bo; Gu Yu-Qiu; Cao Lei-Feng

    2014-01-01

    A novel single order diffraction grating in the soft X-ray region, called quasi-random radius pinhole array spectroscopic photon sieves (QRSPS), is proposed in this paper. This new grating is composed of pinholes on a substrate, whose radii are quasi-random, while their centers are regular. Analysis proves that its transmittance function across the grating bar is similar to that of sinusoidal transmission gratings. Simulation results show that the QRSPS can suppress higher-order diffraction effectively. And the QRSPS would still retain its characteristic of single order diffraction when we take the effect of X-ray penetration into account. These properties indicate that the QRSPS can be used in the soft X-ray spectra measurement. (electromagnetism, optics, acoustics, heat transfer, classical mechanics, and fluid dynamics)

  7. Does quasi-long-range order in the two-dimensional XY model really survive weak random phase fluctuations?

    International Nuclear Information System (INIS)

    Mudry, Christopher; Wen Xiaogang

    1999-01-01

    Effective theories for random critical points are usually non-unitary, and thus may contain relevant operators with negative scaling dimensions. To study the consequences of the existence of negative-dimensional operators, we consider the random-bond XY model. It has been argued that the XY model on a square lattice, when weakly perturbed by random phases, has a quasi-long-range ordered phase (the random spin wave phase) at sufficiently low temperatures. We show that infinitely many relevant perturbations to the proposed critical action for the random spin wave phase were omitted in all previous treatments. The physical origin of these perturbations is intimately related to the existence of broadly distributed correlation functions. We find that those relevant perturbations do enter the Renormalization Group equations, and affect critical behavior. This raises the possibility that the random XY model has no quasi-long-range ordered phase and no Kosterlitz-Thouless (KT) phase transition

  8. Dechlorination of chlorinated phenols by subnanoscale Pd{sup 0}/Fe{sup 0} intercalated in smectite: pathway, reactivity, and selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Jia, Hanzhong; Wang, Chuanyi, E-mail: jiahz0143@aliyun.com

    2015-12-30

    Graphical abstract: Dechlorination process of pentachlorophenol (PCP) by smectite-templated Pd{sup 0}/Fe{sup 0}. - Highlights: • Smectite was employed as templated matrix to prepare subnanoscale Pd{sup 0}/Fe{sup 0} particles. • Dechlorination rate depends linearly on the Pd content as its loadings <0.065 wt.%. • Dechlorination rates correlate with the total charge of C on chlorinated phenols. • The dechlorination selectivity relies on charges of individual C in aromatic ring. - Abstract: Smectite clay was employed as templated matrix to prepare subnanoscale Pd{sup 0}/Fe{sup 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{sup 0}/Fe{sup 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 6 h, 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

  9. Batch and flow-through continuous stirred reactor experiments of Sr2+-adsorption onto smectite: influence of pH, concentration and ionic strength

    International Nuclear Information System (INIS)

    Guimaraes, V.; Azenha, M.; Silva, A.F.; Bobos, I.

    2012-01-01

    Document available in extended abstract form only. Strontium-90 (t 1/2 = 29.1 years) resulting from the nuclear fission process is one of the main constituents connected with nuclear waste fuel. Concerning the physical properties and sorption behaviour one of the suitable buffer materials used as a backfill in the geological disposal systems for high-level radioactive wastes is smectite. The 2 μm clay fractions of di-octahedral smectite were used for adsorption experiments in batch and flow-through experiments. Flow-through experiments were carried out at different pH (4 and 8) and concentrations (8.00x10 -2 mmolSr 2+ /L, 2.0x10 -1 mmolSr 2+ /L, 3.3x10 -1 mmolSr 2+ /L and 4.1 x10 -1 mmol Sr 2+ /L). Batch experiments were carried out at different ionic strength ([KNO 3 ]=10 -2 M and [KNO 3 ]=10 -3 M), pH (4 and 8), whereas the concentration ranged between 0.19 mmolSr 2+ /L and 9.60 mmolSr 2+ /L. The adsorption strontium rate in flow-through experiments was found higher at pH 4 than at pH 8, where less of 20% amount of strontium was adsorbed on clay surface after 34 hours. This is explained by the surface charge of smectite layers with a permanent negative charge on the basal planes due essentially to isomorphic substitution. Also additional polar sites are conditionally charged by direct protonation of outer edge surfaces. Therefore, more negative sites become available for the strontium ions sorption, as the pH increasing. After adsorption, the clays were submitted to a desorption process. The rate of desorption at pH 4 is initially too fast due to the elevated amount of strontium released by smectite. After 255 min, the strontium amount desorbed is very low and the rate of desorption approached to zero. By contrast at pH 8 the rate of desorption is practically constant, and after 255 min there is a significant amount of strontium released by clay. Due to these different behaviors in different pH conditions, after 10 hours of desorption, the amount of strontium

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

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

    2013-01-01

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

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

    Science.gov (United States)

    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

  13. Acid–base properties of pillared interlayered clays with single and mixed Zr–Al oxide pillars prepared from Tunisian-interstratified illite–smectite

    Directory of Open Access Journals (Sweden)

    Saida Mnasri

    2017-12-01

    Full Text Available Interstratified illite–smectite clay samples from Tunisia have been used in order to prepare Al, Zr and Zr–Al-pillared clays. Several Al/metal, OH/metal ratios were used in order to investigate the effect on the chemical and physical properties, specifically the point of zero charge (PZC of the synthesized pillared clays. The structure of the pillared materials is studied by XRD and cationic exchange capacity. The textural property is investigated by the nitrogen adsorption/desorption method. The acid–base chemistry “surface acidity” of these products was analysed by using mass and potentiometric titration in order to determine the PZC and the equilibrium constants (pKa of each sample. The resulting materials exhibited basal spacings in the range of 17.4–20.5 Å, with high surface areas (134–199 m2 g−1. Titration curves obtained by acid–base potentiometric titration for the starting material showed an indistinct cross-over point at about pH = 7.3, whereas in the case of pillared samples, points were observed at the acidic region between 4 and 6. In addition, the calculated pKas values of pillared clays show a shifting to the acidic values compared to the untreated sample.

  14. Clinical Efficacy of Dioctahedral Smectite in the Complex Therapy of Acute Intestinal Infections in Children

    Directory of Open Access Journals (Sweden)

    A. A. Novokshonov

    2016-01-01

    Full Text Available The article presents the results of research on the study of clinical effectiveness and impact on intestinal microbiocenosis dioctahedral smectite (Neosmektin® of acute intestinal infectious of bacterial, viral, and mixt etiology. The clinical studies have shown that the additional inclusion in the complex therapy for children this enterosorbent has a pronounced detoxification and antidiarrheal effect, reducing the duration of the acute period of the disease increases sanitize effectiveness of the therapy against pathogens and contributes to the normalization of microbiocenosis intestine.

  15. Effect of smectite clays storage in their rheological properties

    International Nuclear Information System (INIS)

    Silva, I.A. da; Sousa, F.K.A. de; Neves, G. de A.; Ferreira, H.C.; Ferreira, H.S.; Ferreira, H.S.

    2017-01-01

    This work investigates the storage influence of natural and industrial smectite clays in their rheological properties, since the salt metathesis reaction that occurs following treatment of polycationic clays with Na_2 CO_3 is reversible. The phenomena involved in this reaction are not yet fully known and previous studies show improvement in some properties. The rheological properties were determined in sodium-clays in 1995 and polycationic clays added with sodium carbonate (Na_2 CO_3 ) in 2015. Physical, chemical and mineralogical characterizations of the samples were performed using the following techniques: particle size analysis by laser diffraction, chemical composition by X-ray fluorescence, X-ray diffraction and thermal analysis (DTA and TGA). The rheology of dispersions was determined by the apparent viscosity, plastic viscosity and filtrate volume, which were later considered the oil industry standards only as a benchmark. The results showed that the storage conditions, humidity and particle size of the samples resulted in improvements in their rheological properties over the years, indicating the non-reversibility of the reaction of cation exchange, which is important in their validity after manufacturing. (author)

  16. Nanocomposite microcapsules from powders of polyhydroxybutyrate (PHB) and smectite clays

    International Nuclear Information System (INIS)

    Silva-Valenzuela, Maria das Gracas da; Wang, Shu Hui; Wiebeck, Helio; Valenzuela-Diaz, Francisco R.

    2009-01-01

    Drug delivery systems involving microcapsules provide an attractive way to improve the performance of many chemical and biological substances. These systems may be used for several industrial segments, especially medical, pharmaceuticals and cosmetics. PHB is a polyhydroxyalkanoate available in powder form, biocompatible, biodegradable and inert towards animal tissues. The obtained PHB/smectite clay nanocomposite improved the physical-chemical properties of PHB, including its biodegradability. In this work, we describe the preparation of microcapsules from two nanocomposites systems: a) PHB and Cloisite 20A organoclay (PHB1) and b) PHB and natural Brazilian green polycationic clay (PHB2). When analyzed by XRD, the films and microcapsules did not show a d (001) peak, demonstrating an exfoliated structure for the nanocomposites. The films have shown by SEM an homogeneous distribution with the clay mineral particles spread homogeneously by the PHB film. The new microcapsules/nanocomposites showed an 'hydrangea' morphology. The diameter of the microcapsules was variable between 0.5-15 μm. (author)

  17. Numerical solution of second-order stochastic differential equations with Gaussian random parameters

    Directory of Open Access Journals (Sweden)

    Rahman Farnoosh

    2014-07-01

    Full Text Available In this paper, we present the numerical solution of ordinary differential equations (or SDEs, from each orderespecially second-order with time-varying and Gaussian random coefficients. We indicate a complete analysisfor second-order equations in specially case of scalar linear second-order equations (damped harmonicoscillators with additive or multiplicative noises. Making stochastic differential equations system from thisequation, it could be approximated or solved numerically by different numerical methods. In the case oflinear stochastic differential equations system by Computing fundamental matrix of this system, it could becalculated based on the exact solution of this system. Finally, this stochastic equation is solved by numericallymethod like E.M. and Milstein. Also its Asymptotic stability and statistical concepts like expectationand variance of solutions are discussed.

  18. Adsorption of sulphuric acid on smectite from acidic aqueous solutions Adsorção de ácido sulfúrico em esmectita de soluções aquosas ácidas

    Directory of Open Access Journals (Sweden)

    E. L. Tavani

    1999-05-01

    Full Text Available The adsorption of sulphuric acid on smectite from acidic aqueous solutions was studied. The amounts of cations dissolved in each equilibrium solution were determined by chemical analysis. Simultaneously, the original smectite and the smectite after each test were characterized by infrared, X-ray diffraction and swelling index. The results obtained permitted us to determine that the substitutions of the exchange cations and the chemical attack occurred at very different acid concentrations and treatment times. It was established that during the acid treatment of the smectite, a progressive damage of its crystalline structure was produced. Finally, the influences of the substitution of exchange cations and of the chemical attack in the swelling index were determined.A adsorção de ácido sulfúrico em esmectita de soluções aquosas ácidas é estudada. As concentrações de cátions dissolvidos em cada solução em equilíbrio foram determinadas por análise química. As esmectitas original e após cada teste foram simultaneamente caracterizadas por infravermelho, difração de raios X e índice de crescimento. Os resultados obtidos permitiram determinar que as substituições dos cátions de troca e o ataque químico ocorreram em diferentes concentrações de ácido e tempos de tratamento. Foi verificado que durante o tratamento em ácido da esmectita foi produzido um dano progressivo da sua estrutura cristalina. Finalmente foram determinadas as influências da substituição dos cátions de troca e do ataque químico no índice de crescimento.

  19. Residual and Past Entropy for Concomitants of Ordered Random Variables of Morgenstern Family

    Directory of Open Access Journals (Sweden)

    M. M. Mohie EL-Din

    2015-01-01

    Full Text Available For a system, which is observed at time t, the residual and past entropies measure the uncertainty about the remaining and the past life of the distribution, respectively. In this paper, we have presented the residual and past entropy of Morgenstern family based on the concomitants of the different types of generalized order statistics (gos and give the linear transformation of such model. Characterization results for these dynamic entropies for concomitants of ordered random variables have been considered.

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

    Energy Technology Data Exchange (ETDEWEB)

    Jia, Hanzhong, E-mail: jiahz0143@yahoo.com.cn [Laboratory of Eco-Materials and Sustainable Technology (LEMST), Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi, Xinjiang 830011 (China); Li, Li [Laboratory of Eco-Materials and Sustainable Technology (LEMST), Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi, Xinjiang 830011 (China); The Graduate School of Chinese Academy of Science, Beijing 100049 (China); Fan, Xiaoyun [Laboratory of Eco-Materials and Sustainable Technology (LEMST), Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi, Xinjiang 830011 (China); Liu, Mingdeng [Laboratory of Eco-Materials and Sustainable Technology (LEMST), Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi, Xinjiang 830011 (China); The Graduate School of Chinese Academy of Science, Beijing 100049 (China); Deng, Wenye [Laboratory of Eco-Materials and Sustainable Technology (LEMST), Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi, Xinjiang 830011 (China); Wang, Chuanyi, E-mail: cywang@ms.xjb.ac.cn [Laboratory of Eco-Materials and Sustainable Technology (LEMST), Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi, Xinjiang 830011 (China)

    2013-07-15

    Highlights: • Soil organic matter (SOM) has significant influence on the transformation of PAHs. • Photodegradation rate is strongly dependent on the SOM fractions and their content. • Photolysis is determined by the interaction between phenanthrene, clay and SOM. -- Abstract: 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 (0.70 mg/g) and HA (0.65 mg/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.

  1. An MGF-based unified framework to determine the joint statistics of partial sums of ordered random variables

    KAUST Repository

    Nam, Sungsik; Alouini, Mohamed-Slim; Yang, Hongchuan

    2010-01-01

    Order statistics find applications in various areas of communications and signal processing. In this paper, we introduce an unified analytical framework to determine the joint statistics of partial sums of ordered random variables (RVs

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  4. Some Limit Properties of Random Transition Probability for Second-Order Nonhomogeneous Markov Chains Indexed by a Tree

    Directory of Open Access Journals (Sweden)

    Shi Zhiyan

    2009-01-01

    Full Text Available We study some limit properties of the harmonic mean of random transition probability for a second-order nonhomogeneous Markov chain and a nonhomogeneous Markov chain indexed by a tree. As corollary, we obtain the property of the harmonic mean of random transition probability for a nonhomogeneous Markov chain.

  5. Random textures of the order parameter of superfluid sup 3 He-B in aerogel

    CERN Document Server

    Fomin, Yu A

    2002-01-01

    The scheme for describing the properties of the superfluid sup 3 He in the aerogel is proposed in accordance with the Ginzburg and Landau theory. The aerogel effect on the order parameter is described by the random tensor field. This field exerts desorientation effect on the order parameter in the sup 3 He A-phase, but it does not influence the order parameter orientation in the B-phase, if there is no magnetic field. The change in the order parameter texture, originating in the B-phase in the aerogel in the magnetic field, is considered. Fluctuations of the sup 3 He-B anisotropy axis direction are correlated on the length, inversely proportional to the field intensity and having the macroscopic scale

  6. High-temperature X-ray powder diffraction as a tool for characterization of smectites, layered double hydroxides, and their intercalates with porphyrins

    Czech Academy of Sciences Publication Activity Database

    Píšková, A.; Bezdička, Petr; Hradil, David; Káfuňková, E.; Lang, Kamil; Večerníková, Eva; Kovanda, F.; Grygar, Tomáš

    2010-01-01

    Roč. 49, č. 4 (2010), s. 363-371 ISSN 0169-1317 R&D Projects: GA ČR(CZ) GA203/06/1244; GA AV ČR KAN100500651; GA AV ČR IAA3032401 Institutional research plan: CEZ:AV0Z40320502 Keywords : smectite * Layered double hydroxides * thermal decomposition Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.303, year: 2010

  7. A stochastic collocation method for the second order wave equation with a discontinuous random speed

    KAUST Repository

    Motamed, Mohammad; Nobile, Fabio; Tempone, Raul

    2012-01-01

    In this paper we propose and analyze a stochastic collocation method for solving the second order wave equation with a random wave speed and subjected to deterministic boundary and initial conditions. The speed is piecewise smooth in the physical

  8. Inner-sphere, outer-sphere and ternary surface complexes: a TRLFS study of the sorption process of europium(III) onto smectite

    International Nuclear Information System (INIS)

    Stumpf, Th.; Fanghaenel, Th.; Bauer, A.; Kim, J.I.

    2002-01-01

    The surface sorption process of Eu(III) onto smectite was investigated by TRLFS in the trace concentration range. With increasing pH the formation of an inner-sphere Eu(III) surface complex was observed. The differences in the spectra and the fluorescence emission lifetimes of the surface sorbed Eu(III) in presence and absence of carbonate indicate the formation of ternary clay/Eu(III)/carbonate complexes /1/. (orig.)

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

    Science.gov (United States)

    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

  10. A multi-tier higher order Conditional Random Field for land cover classification of multi-temporal multi-spectral Landsat imagery

    CSIR Research Space (South Africa)

    Salmon, BP

    2015-07-01

    Full Text Available In this paper the authors present a 2-tier higher order Conditional Random Field which is used for land cover classification. The Conditional Random Field is based on probabilistic messages being passed along a graph to compute efficiently...

  11. The Schwinger Dyson equations and the algebra of constraints of random tensor models at all orders

    International Nuclear Information System (INIS)

    Gurau, Razvan

    2012-01-01

    Random tensor models for a generic complex tensor generalize matrix models in arbitrary dimensions and yield a theory of random geometries. They support a 1/N expansion dominated by graphs of spherical topology. Their Schwinger Dyson equations, generalizing the loop equations of matrix models, translate into constraints satisfied by the partition function. The constraints have been shown, in the large N limit, to close a Lie algebra indexed by colored rooted D-ary trees yielding a first generalization of the Virasoro algebra in arbitrary dimensions. In this paper we complete the Schwinger Dyson equations and the associated algebra at all orders in 1/N. The full algebra of constraints is indexed by D-colored graphs, and the leading order D-ary tree algebra is a Lie subalgebra of the full constraints algebra.

  12. Neutron Transport in Spatially Random Media: An Assessment of the Accuracy of First Order Smoothing

    International Nuclear Information System (INIS)

    Williams, M.M.R.

    2000-01-01

    A formalism has been developed for studying the transmission of neutrons through a spatially stochastic medium. The stochastic components are represented by absorbing plates of randomly varying strength and random position. This type of geometry enables the Feinberg-Galanin-Horning method to be employed and leads to the solution of a coupled set of linear equations for the flux at the plate positions. The matrix of the coefficients contains members that are random and these are solved by simulation. That is, the strength and plate positions are sampled from uniform distributions and the equations solved many times (in this case 10 5 simulations are carried out). Probability distributions for the plate transmission and reflection factors are constructed from which the mean and variance can be computed.These essentially exact solutions enable closure approximations to be assessed for accuracy. To this end, we have compared the mean and variance obtained from the first order smoothing approximation of Keller with the exact results and have found excellent agreement for the mean values but note deviations of up to 40% for the variance. Nevertheless, for the problems considered here, first order smoothing appears to be of practical value and is very efficient numerically in comparison with simulation

  13. Competing order parameters in quenched random alloys: Fe/sub 1-x/Co/sub x/Cl2

    International Nuclear Information System (INIS)

    Wong, P.; Horn, P.M.; Birgeneau, R.J.; Safinya, C.R.; Shirane, G.

    1980-01-01

    A study is reported of the magnetic properties of the random alloy Fe/sub 1-x/Co/sub x/Cl 2 , which represents an archetypal example of a system with competing orthogonal spin anisotropies. Behavior similar to previous experiments and theoretical predictions is found, but with important qualitative and quantitative differences; in particular the phase transition in one variable is drastically altered by the existence of long-range order in the other variable. It is hypothesized that this is due to microscopic random-field effects

  14. Smectite in mangrove soils of the State of São Paulo, Brazil Esmectitas em solos de mangue no Estado de São Paulo

    Directory of Open Access Journals (Sweden)

    Valdomiro Severino de Souza-Júnior

    2010-02-01

    Full Text Available Smectitic clay minerals are frequently identified in mangrove soils, but there is little information about their types and origins. Besides their importance in the agronomical and geotechnical areas, smectites play an important environmental role by adsorbing nutrients, organic pollutants and heavy metals. Smectites found in mangrove soils can be of marine or continental detrital origin, or of neoformation origin. Thus, the objective of this study was to identify the types of smectites present in the State of São Paulo mangrove soils (Brazil, and to relate them to their possible origins. Soil samples were taken in five mangroves along the State of Sao Paulo State coast line. The mineral composition of the clay fraction was identified by X-ray Diffractometry (XRD applying the Greene-Kelly test and by Fourier transform infrared spectroscopy (FTIR. Highlighting the peaks in the 3,560 cm-1 band and in the region near 798 and 820 cm-1, there was a predominance of nontronite in the soil at the Sítio Grande River, Pai Matos Island, Caranguejo Island and Itapanhaú River mangroves, and possibly a lower concentration of ferric montmorillonite in the Escuro River mangrove. Since the continental sediments in these environments are very poor in smectite, the origin of these minerals in the mangrove soils studied is related to sedimentation left by past marine transgressions, to neoformation processes, or yet to a combination of both origins.Minerais de argila esmectíticos são freqüentemente identificados em solos de manguezais, mas são escassas as informações sobre os tipos encontrados e suas origens. A despeito da importância para a agronomia e geotecnia, as esmectitas desempenham também importante papel no âmbito ambiental, atuando na adsorção de nutrientes, poluentes orgânicos e metais pesados. Esmectitas em solos de manguezais podem ser de origem detrítica, marinha ou continental, e também de neoformação. Assim, este estudo objetivou

  15. Will electrical cyber-physical interdependent networks undergo first-order transition under random attacks?

    Science.gov (United States)

    Ji, Xingpei; Wang, Bo; Liu, Dichen; Dong, Zhaoyang; Chen, Guo; Zhu, Zhenshan; Zhu, Xuedong; Wang, Xunting

    2016-10-01

    Whether the realistic electrical cyber-physical interdependent networks will undergo first-order transition under random failures still remains a question. To reflect the reality of Chinese electrical cyber-physical system, the "partial one-to-one correspondence" interdependent networks model is proposed and the connectivity vulnerabilities of three realistic electrical cyber-physical interdependent networks are analyzed. The simulation results show that due to the service demands of power system the topologies of power grid and its cyber network are highly inter-similar which can effectively avoid the first-order transition. By comparing the vulnerability curves between electrical cyber-physical interdependent networks and its single-layer network, we find that complex network theory is still useful in the vulnerability analysis of electrical cyber-physical interdependent networks.

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

    Science.gov (United States)

    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.

  17. Quantifying porosity, compressibility and permeability in Shale

    DEFF Research Database (Denmark)

    Mbia, Ernest Ncha; Fabricius, Ida Lykke; Frykman, Peter

    strain data. We found that Kozeny's modelled permeability fall in the same order of magnitude with measured permeability for shale rich in kaolinite but overestimates permeability by two to three orders of magnitudes for shale with high content of smectite. The empirical Yang and Aplin model gives good...... permeability estimate comparable to the measured one for shale rich in smectite. This is probably because Yang and Aplin model was calibrated in London clay which is rich in smectite....

  18. Evaluation of past and future alterations in tuff at Yucca Mountain, Nevada, based on the clay mineralogy of drill cores USW G-1, G-2, and G-3

    International Nuclear Information System (INIS)

    Bish, D.L.

    1989-03-01

    The tuffs at Yucca Mountain in south-central Nevada are being studied by the Yucca Mountain Project (YMP) to determine their suitability for a high-level radioactive waste repository. For predictive purposes, it is important to understand the alteration history of Yucca Mountain and to know how the minerals in Yucca Mountain tuffs respond to changing conditions such as elevated temperatures. The clay mineralogy of these tuffs has been examined using x-ray powder diffraction, and approximation temperatures of alteration have been determined using available clay mineral data and fluid inclusion analyses. Also, several illites from drill holes USW G-1 and G-2 have been dated using K/Ar techniques, yielding ages of about 11 Myr. The clay mineral in Yucca Mountain tuffs are predominantly interstratified illite/smectites, with minor amounts of chloride, kaolinite, and interstratified chlorite/smectite at depth in USW G-1 and G-2. The reactions observed for these illite/smectites are similar to those observed in pelitic rocks. With depths, the illite/smectites transform from random interstratifications (R = 0) through ordered intermediates (R = 1) to illite in USW G-2 and to Kalkberg (R ≥ 3) interstratifications in USW G-1. The illite/smectites in USW G-3 have not significantly transformed. It appears that the illites in deeper rock results from hydrothermal and diagenetic reactions of earlier-formed smectites. These data demonstrate that the rocks at depth in the northern end of Yucca Mountain were significantly altered about 11 Myr ago. Both clay mineralogy and fluid inclusions suggest that the rocks at depth in USW G-2 have been subjected to postdepositional temperatures of at least 275/degree/C, those in USW G-1 have reached 200/degree/C, and USW G-3 rocks probably have not exceeded 100/degree/C. 64 refs., 9 figs., 3 tabs

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

    Science.gov (United States)

    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.

  20. Radiation-induced segregation behavior in random and ordered face-centered cubic materials

    International Nuclear Information System (INIS)

    Bui, T.X.; Robertson, I.M.; Klatt, J.L.; Averback, R.S.; Kirk, M.A.

    1993-01-01

    Radiation-induced segregation has been studied in random solid solution alloys Ni-10%Al and Ni-6%Si, and in the ordered (L1 2 structure) intermetallics Ni 3 Si and Ni 3 Al. These materials were irradiated with 2 MeV He + ions at a temperature between 0.45 and 0.55T m and at an ion dose rate of approximately 1x10 -4 dpa per second. Subsequent Auger Electron Spectroscopy analysis showed that silicon segregated to the surface in the Ni-6% Si and Ni 3 Si alloys, and aluminum segregated away from the near surface region in the Ni-10% Al alloy. The Ni 3 Al samples exhibited no detectable segregation with respect to depth from the sample surface. The mechanisms that may give rise to this resistance to radiation induced segregation will be examined in terms of the mobility of the alloying constituents, ordering energies and atomic sizes. (orig.)

  1. From illite/smectite clay to mesoporous silicate adsorbent for efficient removal of chlortetracycline from water.

    Science.gov (United States)

    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.

  2. An MGF-based unified framework to determine the joint statistics of partial sums of ordered i.n.d. random variables

    KAUST Repository

    Nam, Sungsik

    2014-08-01

    The joint statistics of partial sums of ordered random variables (RVs) are often needed for the accurate performance characterization of a wide variety of wireless communication systems. A unified analytical framework to determine the joint statistics of partial sums of ordered independent and identically distributed (i.i.d.) random variables was recently presented. However, the identical distribution assumption may not be valid in several real-world applications. With this motivation in mind, we consider in this paper the more general case in which the random variables are independent but not necessarily identically distributed (i.n.d.). More specifically, we extend the previous analysis and introduce a new more general unified analytical framework to determine the joint statistics of partial sums of ordered i.n.d. RVs. Our mathematical formalism is illustrated with an application on the exact performance analysis of the capture probability of generalized selection combining (GSC)-based RAKE receivers operating over frequency-selective fading channels with a non-uniform power delay profile. © 1991-2012 IEEE.

  3. Defining Higher-Order Turbulent Moment Closures with an Artificial Neural Network and Random Forest

    Science.gov (United States)

    McGibbon, J.; Bretherton, C. S.

    2017-12-01

    Unresolved turbulent advection and clouds must be parameterized in atmospheric models. Modern higher-order closure schemes depend on analytic moment closure assumptions that diagnose higher-order moments in terms of lower-order ones. These are then tested against Large-Eddy Simulation (LES) higher-order moment relations. However, these relations may not be neatly analytic in nature. Rather than rely on an analytic higher-order moment closure, can we use machine learning on LES data itself to define a higher-order moment closure?We assess the ability of a deep artificial neural network (NN) and random forest (RF) to perform this task using a set of observationally-based LES runs from the MAGIC field campaign. By training on a subset of 12 simulations and testing on remaining simulations, we avoid over-fitting the training data.Performance of the NN and RF will be assessed and compared to the Analytic Double Gaussian 1 (ADG1) closure assumed by Cloudy Layers Unified By Binormals (CLUBB), a higher-order turbulence closure currently used in the Community Atmosphere Model (CAM). We will show that the RF outperforms the NN and the ADG1 closure for the MAGIC cases within this diagnostic framework. Progress and challenges in using a diagnostic machine learning closure within a prognostic cloud and turbulence parameterization will also be discussed.

  4. Solution Methods for Structures with Random Properties Subject to Random Excitation

    DEFF Research Database (Denmark)

    Köylüoglu, H. U.; Nielsen, Søren R. K.; Cakmak, A. S.

    This paper deals with the lower order statistical moments of the response of structures with random stiffness and random damping properties subject to random excitation. The arising stochastic differential equations (SDE) with random coefficients are solved by two methods, a second order...... the SDE with random coefficients with deterministic initial conditions to an equivalent nonlinear SDE with deterministic coefficient and random initial conditions. In both methods, the statistical moment equations are used. Hierarchy of statistical moments in the markovian approach is closed...... by the cumulant neglect closure method applied at the fourth order level....

  5. Probability calculus of fractional order and fractional Taylor's series application to Fokker-Planck equation and information of non-random functions

    International Nuclear Information System (INIS)

    Jumarie, Guy

    2009-01-01

    A probability distribution of fractional (or fractal) order is defined by the measure μ{dx} = p(x)(dx) α , 0 α (D x α h α )f(x) provided by the modified Riemann Liouville definition, one can expand a probability calculus parallel to the standard one. A Fourier's transform of fractional order using the Mittag-Leffler function is introduced, together with its inversion formula; and it provides a suitable generalization of the characteristic function of fractal random variables. It appears that the state moments of fractional order are more especially relevant. The main properties of this fractional probability calculus are outlined, it is shown that it provides a sound approach to Fokker-Planck equation which are fractional in both space and time, and it provides new results in the information theory of non-random functions.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-10-12

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

  7. REGULAR METHOD FOR SYNTHESIS OF BASIC BENT-SQUARES OF RANDOM ORDER

    Directory of Open Access Journals (Sweden)

    A. V. Sokolov

    2016-01-01

    Full Text Available The paper is devoted to the class construction of the most non-linear Boolean bent-functions of any length N = 2k (k = 2, 4, 6…, on the basis of their spectral representation – Agievich bent squares. These perfect algebraic constructions are used as a basis to build many new cryptographic primitives, such as generators of pseudo-random key sequences, crypto graphic S-boxes, etc. Bent-functions also find their application in the construction of C-codes in the systems with code division multiple access (CDMA to provide the lowest possible value of Peak-to-Average Power Ratio (PAPR k = 1, as well as for the construction of error-correcting codes and systems of orthogonal biphasic signals. All the numerous applications of bent-functions relate to the theory of their synthesis. However, regular methods for complete class synthesis of bent-functions of any length N = 2k are currently unknown. The paper proposes a regular synthesis method for the basic Agievich bent squares of any order n, based on a regular operator of dyadic shift. Classification for a complete set of spectral vectors of lengths (l = 8, 16, … based on a criterion of the maximum absolute value and set of absolute values of spectral components has been carried out in the paper. It has been shown that any spectral vector can be a basis for building bent squares. Results of the synthesis for the Agievich bent squares of order n = 8 have been generalized and it has been revealed that there are only 3 basic bent squares for this order, while the other 5 can be obtained with help the operation of step-cyclic shift. All the basic bent squares of order n = 16 have been synthesized that allows to construct the bent-functions of length N = 256. The obtained basic bent squares can be used either for direct synthesis of bent-functions and their practical application or for further research in order to synthesize new structures of bent squares of orders n = 16, 32, 64, …

  8. Aqueous alteration of Japanese simulated waste glass P0798: Effects of alteration-phase formation on alteration rate and cesium retention

    International Nuclear Information System (INIS)

    Inagaki, Y.; Shinkai, A.; Idemistu, K.; Arima, T.; Yoshikawa, H.; Yui, M.

    2006-01-01

    Aqueous alteration tests were performed with a Japanese simulated waste glass P0798 in alkaline solutions as a function of pH or species/concentration of alkaline metals in the solution in order to evaluate the alteration conditions determining whether smectite (2:1 clay mineral) or analcime (zeolite) forms as the major alteration-phase. XRD analysis of the alteration-phases showed that smectite forms at any pH between 9.5 and 12, and analcime forms at pH above 11, though the formation also depends on species and concentrations of alkaline metals in the solution. These results cannot agree with the thermodynamically predicted phase stability, e.g., smectite is more stable than the thermodynamic prediction shows. On the basis of the results of alteration conditions, the alteration tests were performed under smectite forming conditions, where only smectite forms or no crystalline phases form, in order to evaluate the alteration rate and the mechanism of cesium release/retention. The results showed that the glass alteration proceeds slowly in proportion to square root of time under smectite forming conditions, which indicates that the alteration rate can be controlled by a diffusion process. It was suggested that the alteration rate under smectite forming conditions is independent of the pH, alkaline metal species/concentration in the solution and whether smectite actually forms or not. The results also indicated that most of cesium dissolved from the glass can be retained in the alteration-phases by reversible sorption onto smectite or irreversible incorporation into analcime, pollucite or solid solutions of them

  9. An MGF-based unified framework to determine the joint statistics of partial sums of ordered random variables

    KAUST Repository

    Nam, Sungsik

    2010-11-01

    Order statistics find applications in various areas of communications and signal processing. In this paper, we introduce an unified analytical framework to determine the joint statistics of partial sums of ordered random variables (RVs). With the proposed approach, we can systematically derive the joint statistics of any partial sums of ordered statistics, in terms of the moment generating function (MGF) and the probability density function (PDF). Our MGF-based approach applies not only when all the K ordered RVs are involved but also when only the Ks(Ks < K) best RVs are considered. In addition, we present the closed-form expressions for the exponential RV special case. These results apply to the performance analysis of various wireless communication systems over fading channels. © 2006 IEEE.

  10. [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].

    Science.gov (United States)

    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.

  11. Study of the sorption of actinide analogues on calcite and smectite as a model to predict the evolution of radioactive waste disposal in geological sites

    International Nuclear Information System (INIS)

    Budiman Sastrowardoyo, Pratomo

    1991-01-01

    In the framework of the problem of the radioactive waste disposal in deep geological sites, the purpose of this study is to predict the sorption of radionuclides on minerals within the geological barrier, after the rupture of the containers and the release of the radionuclides into underground water. Neodymium labelled by 147 Nd was used as an analogue of trivalent actinides. Calcite and smectite were used as examples of altered minerals of granitic sites. In simple media, neodymium is retained with a high affinity on both minerals. Fast kinetics of fixation, high distribution coefficients and sorption capacities are favorable factors for the slowing down of radionuclide migration in underground water. Fixation on calcite is quasi irreversible. A second kinetic step was observed, leading to an increase of the retention capacity. In the first step, this is probably a superficial sorption, but with a non-homogeneous affinity for sorption sites. An exchange mechanism of Nd 3+ with Na + et Ca 2+ ions of smectite occurs. The Freundlich isotherm observed for both minerals can be used for predicting the retention of radioelements as a function of their concentration and introducing these data in a migration model after comparison with the results of dynamic and field experiments. (author) [fr

  12. Animated molecular dynamics simulations of hydrated caesium-smectite interlayers

    Directory of Open Access Journals (Sweden)

    Sposito Garrison

    2002-09-01

    Full Text Available 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.

  13. Animated molecular dynamics simulations of hydrated caesium-smectite interlayers

    Science.gov (United States)

    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.

  14. Heterogeneous photo-Fenton decolorization of Orange II over Al-pillared Fe-smectite: response surface approach, degradation pathway, and toxicity evaluation.

    Science.gov (United States)

    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.

  15. Application of random coherence order selection in gradient-enhanced multidimensional NMR

    International Nuclear Information System (INIS)

    Bostock, Mark J.; Nietlispach, Daniel

    2016-01-01

    Development of multidimensional NMR is essential to many applications, for example in high resolution structural studies of biomolecules. Multidimensional techniques enable separation of NMR signals over several dimensions, improving signal resolution, whilst also allowing identification of new connectivities. However, these advantages come at a significant cost. The Fourier transform theorem requires acquisition of a grid of regularly spaced points to satisfy the Nyquist criterion, while frequency discrimination and acquisition of a pure phase spectrum require acquisition of both quadrature components for each time point in every indirect (non-acquisition) dimension, adding a factor of 2 N -1 to the number of free- induction decays which must be acquired, where N is the number of dimensions. Compressed sensing (CS) ℓ 1 -norm minimisation in combination with non-uniform sampling (NUS) has been shown to be extremely successful in overcoming the Nyquist criterion. Previously, maximum entropy reconstruction has also been used to overcome the limitation of frequency discrimination, processing data acquired with only one quadrature component at a given time interval, known as random phase detection (RPD), allowing a factor of two reduction in the number of points for each indirect dimension (Maciejewski et al. 2011 PNAS 108 16640). However, whilst this approach can be easily applied in situations where the quadrature components are acquired as amplitude modulated data, the same principle is not easily extended to phase modulated (P-/N-type) experiments where data is acquired in the form exp (iωt) or exp (-iωt), and which make up many of the multidimensional experiments used in modern NMR. Here we demonstrate a modification of the CS ℓ 1 -norm approach to allow random coherence order selection (RCS) for phase modulated experiments; we generalise the nomenclature for RCS and RPD as random quadrature detection (RQD). With this method, the power of RQD can be extended

  16. Stability fields of smectites and illites as a function of temperature and chemical composition

    International Nuclear Information System (INIS)

    Tardy, Y.; Duplay, J.; Fritz, B.; Strasbourg-1 Univ., 67

    1987-04-01

    A thermodynamic ideal solid solution analogue is proposed which accounts the correlations which clearly reflect the temperatures at which the nonmineralic population are supposed to have been formed. The solid solution is considered, at a particle scale, as an ideal mixture of individual layers, weakly bent each to the next. Each layer presents the chemical composition of a given end member, so that the proportions of the different end members change from one particle to another. Considering one particle of a given chemical composition, the multipole solid solution theory allows to calculate the wheighted contributions of each end member into the ideal clay solid solution along with the chemical composition of the aqueous solutions in equilibrium with the considered particle in its independent microenvironment. This model is able to predict the nature of the chemical correlations which are expected, at a given temperature, within a given population. This model is also applied to the prediction of the temperature required for the conversion of smectite into illite during the burial diagenesis. (orig./HP)

  17. Contact-metamorphic illitization and related consequences for the functioning of backfill barriers in high level radioactive waste repositories (South Africa)

    International Nuclear Information System (INIS)

    Buehmann, C.

    2000-01-01

    A clay barrier, consisting of smectite, is common to most disposal designs for HLW repositories. Concerns are that elevated temperatures and long time periods may alter the two properties, the barrier is employed: a high swelling as well as cation exchange capacity (CEC). A ''natural analogue'' approach has therefore been attempted to predict smectite characteristics and stability in relation to time/temperature. The following investigations were performed in order to determine changes in swelling capacity and CEC: (1) Conversion of smectite to other clay minerals. (2) Changes in the layer charge characteristics of the clay minerals. (3) Swelling potential measurements of the smectitic interlayer. Smectite was thermally unstable and transformed into illite via illite/smectite interstratifications (I/S) and chlorite at temperature exceeding about 100 deg. C. The swelling potential was directly related to the proportion of smectite. As a conclusion it can be stated that elevated temperatures (> 70 deg. C) result in the transformation of smectite into illite. For backfill purposes it is recommended that the clay content in the backfill barrier should be as high as technically possible and that mixing the bentonite with K-bearing minerals (granite) should be avoided. (author)

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

    Science.gov (United States)

    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.

  19. Smectite clays of Serbia and their application in adsorption of organic dyes

    Science.gov (United States)

    Milošević, Maja; Logar, Mihovil

    2014-05-01

    Colorants and dyes are currently available in over a 100.000 different species and several biggest industries are using them daily in their manufacture processes (textile, cosmetics, food industry, etc.). Since colorants are easily dissoluble in water they pass through filter membranes without further decomposing and in that manner they end up in the environment. The main goal of this work is to apply certain methods in determining the suitability of individual clay in adsorbing and removing colorants from polluted waters. For this study we have chosen four different raw clays from three regions in Serbia: Svrljig (B), Bogovina (Bo) and Slatina-Ub (C and V) and as colorant - methylene blue dye (MB (MERCK, for analytical purposes)). Experiments where carried out to determine the sample structure (XRD and IR), grain size (granulometry), cationic exchange capacity (CEC via spectrophotometry using MB) and adsorption capabilities (spectrophotometry and fluorimetry using MB). XRD and IR data are showing that the samples are smectite clays where samples B i Bo are mainly montmorillonite while C and V are montmorillonite-illite clays. Granulometric distribution results indicate that samples B i Bo have smaller grain size, less that 1μ (over 60%) whereas the samples C and V are more coarse grained (40% over 20μ). This grain distribution is affecting their specific surface area in the manner that those coarse grained samples have smaller specific surface area. Cationic exchange capacity determined with methylene blue indicate that montmorillonite samples have larger CEC (B = 37 meq/100g, Bo = 50 meq/100g) and montmorillonite-illite samples smaller CEC (V = 5 meq/100g, V = 3 meq/100g). Fluorimetry measurement results gave us a clear distinction between those with higher and smaller adsorption capability. Montmorillonite samples (B and Bo) with higher CEC values and smaller grain size are adsorbing large amounts of methylene blue witch is visible by absence of fluorimetric

  20. Natural gels: crystal-chemistry of short range ordered components in Al, Fe, and Si systems

    International Nuclear Information System (INIS)

    Ildefonse, Ph.; Calas, G.

    1997-01-01

    In this review, the most important inorganic natural gels are presented: opal, aluminosilicate (allophanes) and hydrous iron oxides and silicates. It is demonstrated that natural gels are ordered at the atomic scale. In allophanes, Al is distributed between octahedral and tetrahedral sites. The amount of Al increases as Al/Si ratio decreases. Si-rich allophane have a local structure around Al and Si very different of that is known in kaolinite or halloysite. Transformation of Si-rich allophanes to crystallized minerals implies dissolution-recrystallization processes. On the contrary, in iron silicate with Fe/Si = 0.72, Si and Fe environments are close to those found in nontronite. The gel transformation to Fe-smectite may occur by long range ordering during ageing. In ferric silicate gels, the similarity of local structure around Fe in poorly ordered precursors and what is known in crystallized minerals suggests a solid transformation during ageing. This difference between iron and aluminium is mainly due to the ability of Al to enter both tetrahedral and octahedral sites, while the affinity of iron for octahedral sites is higher at low temperature

  1. First-order reversal curves of single domain particles: diluted random assemblages and chains

    Science.gov (United States)

    Egli, R.

    2009-04-01

    Exact magnetic models can be used to calculate first-order reversal curves (FORC) of single domain (SD) particle assemblages, as shown by Newell [2005] for the case of isolated Stoner-Wohlfarth particles. After overcoming experimental difficulties, a FORC diagram sharing many similarities to Newell's model has been measured on a lake sediment sample (see A.P. Chen et al., "Quantification of magnetofossils using first-order reversal curves", EGU General Assembly 2009, Abstracts Vol. 11, EGU2009-10719). This sample contains abundant magnetofossils, as shown by coercivity analysis and electron microscopy, therefore suggesting that well dispersed, intact magnetosome chains are the main SD carriers. Subtle differences between the reversible and the irreversible contributions of the measured FORC distribution suggest that magnetosome chains might not be correctly described by the Stoner-Wohlfarth model. To better understand the hysteresis properties of such chains, a simple magnetic model has been implemented, taking dipole-dipole interactions between particles within the same chain into account. The model results depend on the magnetosome elongation, the number of magnetosomes in a chain, and the gap between them. If the chain axis is subparallel to the applied field, the magnetic moment reverses by a pseudo-fanning mode, which is replaced by a pseudo-coherent rotation mode at greater angles. These reversal modes are intrinsically different from coherent rotation assumed Stoner-Wohlfarth model, resulting in FORC diagrams with a smaller reversible component. On the other hand, isolated authigenic SD particles can precipitate in the sediment matrix, as it might occur for pedogenic magnetite. In this case, an assembly of randomly located particles provides a possible model for the resulting FORC diagram. If the concentration of the particles is small, each particle is affected by a random interaction field whose statistical distribution can be calculated from first

  2. Active control on high-order coherence and statistic characterization on random phase fluctuation of two classical point sources.

    Science.gov (United States)

    Hong, Peilong; Li, Liming; Liu, Jianji; Zhang, Guoquan

    2016-03-29

    Young's double-slit or two-beam interference is of fundamental importance to understand various interference effects, in which the stationary phase difference between two beams plays the key role in the first-order coherence. Different from the case of first-order coherence, in the high-order optical coherence the statistic behavior of the optical phase will play the key role. In this article, by employing a fundamental interfering configuration with two classical point sources, we showed that the high- order optical coherence between two classical point sources can be actively designed by controlling the statistic behavior of the relative phase difference between two point sources. Synchronous position Nth-order subwavelength interference with an effective wavelength of λ/M was demonstrated, in which λ is the wavelength of point sources and M is an integer not larger than N. Interestingly, we found that the synchronous position Nth-order interference fringe fingerprints the statistic trace of random phase fluctuation of two classical point sources, therefore, it provides an effective way to characterize the statistic properties of phase fluctuation for incoherent light sources.

  3. IRFK2D: a computer program for simulating intrinsic random functions of order k

    Science.gov (United States)

    Pardo-Igúzquiza, Eulogio; Dowd, Peter A.

    2003-07-01

    IRFK2D is an ANSI Fortran-77 program that generates realizations of an intrinsic function of order k (with k equal to 0, 1 or 2) with a permissible polynomial generalized covariance model. The realizations may be non-conditional or conditioned to the experimental data. The turning bands method is used to generate realizations in 2D and 3D from simulations of an intrinsic random function of order k along lines that span the 2D or 3D space. The program generates two output files, the first containing the simulated values and the second containing the theoretical generalized variogram for different directions together with the theoretical model. The experimental variogram is calculated from the simulated values while the theoretical variogram is the specified generalized covariance model. The generalized variogram is used to assess the quality of the simulation as measured by the extent to which the generalized covariance is reproduced by the simulation. The examples given in this paper indicate that IRFK2D is an efficient implementation of the methodology.

  4. A stochastic collocation method for the second order wave equation with a discontinuous random speed

    KAUST Repository

    Motamed, Mohammad

    2012-08-31

    In this paper we propose and analyze a stochastic collocation method for solving the second order wave equation with a random wave speed and subjected to deterministic boundary and initial conditions. The speed is piecewise smooth in the physical space and depends on a finite number of random variables. The numerical scheme consists of a finite difference or finite element method in the physical space and a collocation in the zeros of suitable tensor product orthogonal polynomials (Gauss points) in the probability space. This approach leads to the solution of uncoupled deterministic problems as in the Monte Carlo method. We consider both full and sparse tensor product spaces of orthogonal polynomials. We provide a rigorous convergence analysis and demonstrate different types of convergence of the probability error with respect to the number of collocation points for full and sparse tensor product spaces and under some regularity assumptions on the data. In particular, we show that, unlike in elliptic and parabolic problems, the solution to hyperbolic problems is not in general analytic with respect to the random variables. Therefore, the rate of convergence may only be algebraic. An exponential/fast rate of convergence is still possible for some quantities of interest and for the wave solution with particular types of data. We present numerical examples, which confirm the analysis and show that the collocation method is a valid alternative to the more traditional Monte Carlo method for this class of problems. © 2012 Springer-Verlag.

  5. 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)

    Science.gov (United States)

    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

  6. Challenges in higher order mode Raman amplifiers

    DEFF Research Database (Denmark)

    Rottwitt, Karsten; Nielsen, Kristian; Friis, Søren Michael Mørk

    2015-01-01

    A higher order Raman amplifier model that take random mode coupling into account ispresented. Mode dependent gain and signal power fluctuations at the output of the higher order modeRaman amplifier are discussed......A higher order Raman amplifier model that take random mode coupling into account ispresented. Mode dependent gain and signal power fluctuations at the output of the higher order modeRaman amplifier are discussed...

  7. Settlement of Canisters with smectite clay envelopes in deposition holes

    International Nuclear Information System (INIS)

    Pusch, R.

    1986-12-01

    Settlement of canisters containing radioactive waste and being surrounded by dense smectite clay is caused by the stresses and heat induced in the clay. Consolidation by water expulsion of the clay underlying a model canister with 5 cm diameter and 30 cm length would theoretically account for a maximum finite settlement of about 70 my m in a few weeks, while shear-induced creep would yield a settlement of only a few microns in the same time period. These predictions were checked by running a laboratory test in which a dead load of 80 kg was applied to a small cylindrical copper canister embedded in Na bentonite. The settlement, which increased in proportion to log time, turned out to be about 6 my m in the first 2.5 months. After the first loading period at room temperature, heating to 50 degrees C and, after a 4 months long 'room temperature' period, to 70 degrees C took place. This cycling gave strong, instant settlement and upheaval because of the different thermal expansion of the interacting components of the system. After the development of constant temperature conditions in the entire system and completion of the consolidation or expansion that followed from the thermo-mechanical interactions, the settlement proceeded at a rather high rate at 70 degrees C, still following a log time creep law, but with somewhat stronger retardation. At room temperature, i.e. in the post-heating periods, the settlement seemed to cease, on the other hand. The conclusion from the study is that the canister movements under isothermal conditions were in accordance with the log t-type creep settlement that was predicted in theoretical grounds. Pre-heating and low stresses may account for extraordinary retardation of the settlement. (author)

  8. Toward a Principled Sampling Theory for Quasi-Orders.

    Science.gov (United States)

    Ünlü, Ali; Schrepp, Martin

    2016-01-01

    Quasi-orders, that is, reflexive and transitive binary relations, have numerous applications. In educational theories, the dependencies of mastery among the problems of a test can be modeled by quasi-orders. Methods such as item tree or Boolean analysis that mine for quasi-orders in empirical data are sensitive to the underlying quasi-order structure. These data mining techniques have to be compared based on extensive simulation studies, with unbiased samples of randomly generated quasi-orders at their basis. In this paper, we develop techniques that can provide the required quasi-order samples. We introduce a discrete doubly inductive procedure for incrementally constructing the set of all quasi-orders on a finite item set. A randomization of this deterministic procedure allows us to generate representative samples of random quasi-orders. With an outer level inductive algorithm, we consider the uniform random extensions of the trace quasi-orders to higher dimension. This is combined with an inner level inductive algorithm to correct the extensions that violate the transitivity property. The inner level correction step entails sampling biases. We propose three algorithms for bias correction and investigate them in simulation. It is evident that, on even up to 50 items, the new algorithms create close to representative quasi-order samples within acceptable computing time. Hence, the principled approach is a significant improvement to existing methods that are used to draw quasi-orders uniformly at random but cannot cope with reasonably large item sets.

  9. Toward a Principled Sampling Theory for Quasi-Orders

    Science.gov (United States)

    Ünlü, Ali; Schrepp, Martin

    2016-01-01

    Quasi-orders, that is, reflexive and transitive binary relations, have numerous applications. In educational theories, the dependencies of mastery among the problems of a test can be modeled by quasi-orders. Methods such as item tree or Boolean analysis that mine for quasi-orders in empirical data are sensitive to the underlying quasi-order structure. These data mining techniques have to be compared based on extensive simulation studies, with unbiased samples of randomly generated quasi-orders at their basis. In this paper, we develop techniques that can provide the required quasi-order samples. We introduce a discrete doubly inductive procedure for incrementally constructing the set of all quasi-orders on a finite item set. A randomization of this deterministic procedure allows us to generate representative samples of random quasi-orders. With an outer level inductive algorithm, we consider the uniform random extensions of the trace quasi-orders to higher dimension. This is combined with an inner level inductive algorithm to correct the extensions that violate the transitivity property. The inner level correction step entails sampling biases. We propose three algorithms for bias correction and investigate them in simulation. It is evident that, on even up to 50 items, the new algorithms create close to representative quasi-order samples within acceptable computing time. Hence, the principled approach is a significant improvement to existing methods that are used to draw quasi-orders uniformly at random but cannot cope with reasonably large item sets. PMID:27965601

  10. The sink strengths of voids and the expected swelling for both random and ordered void distributions

    International Nuclear Information System (INIS)

    Quigley, T.M.; Murphy, S.M.; Bullough, R.; Wood, M.H.

    1981-10-01

    The sink strength of a void has been obtained when the void is a member of a random or ordered distribution of voids. The former sink strength derivation has employed the embedding model and the latter the cellular model. In each case the spatially varying size-effect interaction between the intrinsic point defects and the voids has been included together with the presence of other sink types in addition to the voids. The results are compared with previously published sink strengths that have made use of an approximate representation for the size-effect interactions, and indicate the importance of using the exact form of the interaction. In particular the bias for interstitials compared with vacancies of small voids is now much reduced and contamination of the surfaces of such voids no longer appears essential to facilitate the nucleation and growth of the voids. These new sink strengths have been used, in conjunction with recently published dislocation sink strengths, to calculate the expected swelling of materials containing network dislocations and voids. Results are presented for both the random and the void lattice situations. (author)

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

    Science.gov (United States)

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

    2013-01-01

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

  12. Higher order moments of a sum of random variables: remarks and applications.

    Directory of Open Access Journals (Sweden)

    Luisa Tibiletti

    1996-02-01

    Full Text Available The moments of a sum of random variables depend on both the pure moments of each random addendum and on the addendum mixed moments. In this note we introduce a simple measure to evaluate the relative impedance to attach to the latter. Once the pure moments are fixed, the functional relation between the random addenda leading to the extreme values is also provided. Applications to Finance, Decision Theory and Actuarial Sciences are also suggested.

  13. Water retention, gas transport, and pore network complexity during short-term regeneration of soil structure

    DEFF Research Database (Denmark)

    Arthur, Emmanuel; Møldrup, Per; Schjønning, Per

    2013-01-01

    mm sieved) samples of varying clay mineralogy (illite, kaolinite, and smectite) amended with organic material (7.5 t ha–1). Also, the newly-formed structure was compared with that of sieved repacked (SR) and natural intact samples. Assessment and comparison of structure complexity and organization....... The proportion of pores > 100 1m increased in order: smectite

  14. Randomness in preference orderings, outcomes and attribute tastes: An application to journey time risk

    DEFF Research Database (Denmark)

    Batley, Richard; Ibáñez Rivas, Juan Nicolás

    2012-01-01

    estimate a mean ‘reliability ratio’ (ratio of the value of standard deviation of journey time to the value of scheduled journey time) of 2.07, against a median of 0.85. The properties of the distribution of the reliability ratio suggest a predominant behaviour of aversion to journey time risk.......Within the broad area of probabilistic modelling of individual discrete choice, we develop three strands of discussion. First, we outline a theoretical framework for the modelling of individual discrete choice under risk, distinguishing between three specific sources of randomness; in preference...... orderings, in outcomes, and in attribute tastes. Second, we apply this theoretical modelling framework to the domain of journey time risk (or ‘reliability’), a subject which has acquired prominence in the transportation policies of many countries. Third, we apply the modelling framework empirically, based...

  15. The Relationship of Dynamical Heterogeneity to the Adam-Gibbs and Random First-Order Transition Theories of Glass Formation

    OpenAIRE

    Starr, Francis W.; Douglas, Jack F.; Sastry, Srikanth

    2013-01-01

    We carefully examine common measures of dynamical heterogeneity for a model polymer melt and test how these scales compare with those hypothesized by the Adam and Gibbs (AG) and random first-order transition (RFOT) theories of relaxation in glass-forming liquids. To this end, we first analyze clusters of highly mobile particles, the string-like collective motion of these mobile particles, and clusters of relative low mobility. We show that the time scale of the high-mobility clusters and stri...

  16. A dynamic model for smectite clay swelling, expansion and colloid generation

    International Nuclear Information System (INIS)

    Liu, Longcheng; Neretnieks, Ivars; Moreno, Luis

    2010-01-01

    Document available in extended abstract form only. A force balance model that describes the dynamic expansion of colloidal bentonite gels/sols is presented. The colloidal particles are assumed to consist of one or several thin sheets with the other dimensions much larger than their thickness. The forces considered include van der Waals force, diffuse double layer force, thermal force giving rise to Brownian motion, gravity as well as friction force. The model results in an expression that resembles the un-stationary diffusion equation but with an immensely variable diffusivity. This diffusivity is strongly influenced by the concentration of counterions as well as by the particle concentration in the colloid gel/sol. At high particle densities, i.e. when the distance between the particles is less than their length or width, they will not be able to rotate freely and they must essentially be aligned parallel to each other, for purely geometrical reasons, to have the so called columnar phase. In addition, for an average distance between two particles, the energy minimum is found only when the particles are parallel, due to the fact that the diffuse double layer force decays nearly exponentially with distance. This suggests that our model is expected to be valid down to volume fractions of less than one percent, possibly down to a few tenths of a percent in low ionic strength waters, when the diffuse double layer force extends to very large distances. At lower volume fractions, particle diffusion (Brownian motion) will govern the movement and then the diffusivity will approach a constant defined by the Einstein's equation. The model is deemed to be valid also within the large clusters of a multitude of smectite particles, containing perhaps hundred or more sheets. These clusters can be oriented randomly but still allow very small voids to exist between the sheets, and therefore it would not permit the volume fraction of the particles to approach unity when the

  17. Utilization of certain chemical and physical properties of smectite for isolation of radioactive waste in Sweden

    International Nuclear Information System (INIS)

    Karlsson, F.

    1990-01-01

    The use of swelling clays as a buffer and backfill in an underground repository for radioactive waste is part of many design concepts from different countries. The Swedish concept KBS-3, for disposal of spent fuel is an underground repository foresees the use of sodium bentonite. The deposition holes with spent fuel containing copper canisters will be backfilled with a mixture of sand and bentonite and the tunnels and shafts will be surrounded by a buffer of highly compact bentonite. The already constructed and licensed repository for low and medium level waste SFR, in Forsmark has a backfill of smectite rich clay between: the rock and an underground concrete silo for reactor operation waste. The clay barriers have a series of protective functions, both mechanically and chemically. This presentation concentrates on the last mentioned aspect and summarizes the experience of clay as an engineered near field barrier to radionuclide release and transport gained by the safety analyses of KBS-3 and SFR. It is concluded that the use of swelling clays adds considerably to the waste isolation function of the engineered near field barriers. 29 refs., 2 figs., 3 tabs

  18. Immobilization of soil cadmium using combined amendments of illite/smectite clay with bone chars.

    Science.gov (United States)

    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.

  19. Experimental study of the iron - smectite system in the presence of a solution at 80 at 300 deg

    International Nuclear Information System (INIS)

    Guillaume, D.

    2002-04-01

    One of the concepts proposed for the storage of nuclear wastes consists in the use of several confining barriers placed between the waste and the biosphere. Vitrified wastes are placed in steel containers surrounded by compacted smectite (engineered barrier). The whole is placed in the geological deep site (geological barrier, granite or argilite). The prediction of the evolution of the performances of the engineered barrier (low permeability, high swelling and sorption capacities) necessitates the study of the long-term stability of its mineral constituents under the conditions of the repository. The aim is to determine the nature and the chemistry of potential newly-formed phases resulting from the temperature increase due to disintegration reactions of the wastes, the presence of fluids coming from the geological barrier, and from the liberation of iron due to the degradation of the containers. Natural systems (in particular geothermal systems and sedimentary basins) give information concerning the possible evolutions of clay minerals. However, the potential availability of metallic iron makes a particular case of the nuclear waste storage. The aim of this experimental study is to put to evidence the chemical and mineralogical transformations of the iron-clay system at 80 deg C and 300 deg C, in the presence of a solution, so as to predict the possible transformations of a bentonite placed in the deep storage conditions of radioactive wastes. Several sets of experiments were carried out to study the reactivity of the MX80 bentonite in the presence of a solution ([CI]=3.10 -2 molal, Na/Ca=5,5 and liquid/rock ratio of 10) in absence or in presence of iron (magnetite + hematite or iron + magnetite) at 80 deg C or 300 deg C, and over periods ranging from 1 day to 9 months. Run products were submitted to multi-technique and multi-scale characterisation: X-ray diffraction, scanning electron microscopy, transmission electron microscopy (HR imaging, EDS and EELS

  20. An Authenticated Key Agreement Scheme Based on Cyclic Automorphism Subgroups of Random Orders

    Directory of Open Access Journals (Sweden)

    Yang Jun

    2017-01-01

    Full Text Available Group-based cryptography is viewed as a modern cryptographic candidate solution to blocking quantum computer attacks, and key exchange protocols on the Internet are one of the primitives to ensure the security of communication. In 2016 Habeeb et al proposed a “textbook” key exchange protocol based on the semidirect product of two groups, which is insecure for use in real-world applications. In this paper, after discarding the unnecessary disguising notion of semidirect product in the protocol, we establish a simplified yet enhanced authenticated key agreement scheme based on cyclic automorphism subgroups of random orders by making hybrid use of certificates and symmetric-key encryption as challenge-and-responses in the public-key setting. Its passive security is formally analyzed, which is relative to the cryptographic hardness assumption of a computational number-theoretic problem. Cryptanalysis of this scheme shows that it is secure against the intruder-in-the-middle attack even in the worst case of compromising the signatures, and provides explicit key confirmation to both parties.

  1. Study of colloidal properties of natural and Al-pillared smectite and removal of copper ions from an aqueous solution.

    Science.gov (United States)

    Sartor, Lucas Resmini; de Azevedo, Antonio Carlos; Andrade, Gabriel Ramatis Pugliese

    2015-01-01

    In this study, an Al-pillared smectite was synthesized and changes in its colloidal properties were investigated. The pillaring solution was prepared by mixing 0.4 mol L(-1) NaOH and 0.2 mol L(-1) AlCl3.6H2O solutions. Intercalated clays were heated to obtain the pillared clay, and X-ray diffractometry (XRD), X-ray fluorescence (XRF), Fourier transform infrared (FTIR) spectroscopy and N2 sorption/desorption isotherms analysis were done to characterize the changes in clay properties. Moreover, adsorption experiments were carried out in order to evaluate the capacity of the pillared clays to remove Cu2+ from an aqueous solution and to characterize the interaction between adsorbent and adsorbate. The results indicate that the natural clay has a basal spacing of 1.26 nm, whereas the pillared clays reached 1.78 nm (500°C) and 1.80 nm (350°C) after calcination. XRF analysis revealed an increase in the Al3+ in the pillared clay as compared to the natural clay. The surface area and pore volume (micro and mesoporous) were higher for the pillared clays. Experimental data from the adsorption experiment were fit to Langmuir and Freundlich and Temkin adsorption models, and the former one was the best fit (highest r2 value) for all the clays and lower standard deviation (Δg%) for the natural clay. On the other hand, the Temkin model exhibited Δg% value lower for the pillared clays. Thermodynamics parameters demonstrate that the Cu2+ adsorption process is spontaneous for all the clays, but with higher values for the pillared materials. In addition, application of the Dubinin-Radushkevich model revealed that the bond between the metal and the clay are weak, characterizing a physisorption.

  2. Waiting time analysis for MX/G/1 priority queues with/without vacations under random order of service discipline

    Directory of Open Access Journals (Sweden)

    Norikazu Kawasaki

    2000-01-01

    Full Text Available We study MX/G/1 nonpreemptive and preemptive-resume priority queues with/without vacations under random order of service (ROS discipline within each class. By considering the conditional waiting times given the states of the system, which an arbitrary message observes upon arrival, we derive the Laplace-Stieltjes transforms of the waiting time distributions and explicitly obtain the first two moments. The relationship for the second moments under ROS and first-come first-served disciplines extends the one found previously by Takacs and Fuhrmann for non-priority single arrival queues.

  3. A microstructure insight into the water retention properties of the Callovo-Oxfordian claystone

    Directory of Open Access Journals (Sweden)

    Menaceur Hamza

    2016-01-01

    Full Text Available The effect of changes in suction on the microstructure of the Callovo-Oxfordian claystone along wetting and drying paths was investigated by using mercury intrusion porosimetry. Based on a simplified brick model, the changes of the average thickness of the platelets that constitute the clay matrix (50% are interpreted as the consequence of the successive adsorption of ordered layers of water molecules along the smectite surfaces, as demonstrated on pure smectites for a long time. This shows the predominant role played by the smectite phase in the overall response of the Callovo-Oxfordian claystone when submitted to suction changes under no stress.

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

    Energy Technology Data Exchange (ETDEWEB)

    Palchik, N. A., E-mail: nadezhda@igm.nsc.ru; Grigorieva, T. N.; Moroz, T. N. [Russian Academy of Sciences, Sobolev Institute of Geology and Mineralogy, Siberian Branch (Russian Federation)

    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 extreme terms of dioctahedral smectite representatives: nontronites.

  5. Approximate Forward Difference Equations for the Lower Order Non-Stationary Statistics of Geometrically Non-Linear Systems subject to Random Excitation

    DEFF Research Database (Denmark)

    Köylüoglu, H. U.; Nielsen, Søren R. K.; Cakmak, A. S.

    Geometrically non-linear multi-degree-of-freedom (MDOF) systems subject to random excitation are considered. New semi-analytical approximate forward difference equations for the lower order non-stationary statistical moments of the response are derived from the stochastic differential equations...... of motion, and, the accuracy of these equations is numerically investigated. For stationary excitations, the proposed method computes the stationary statistical moments of the response from the solution of non-linear algebraic equations....

  6. Average-case analysis of incremental topological ordering

    DEFF Research Database (Denmark)

    Ajwani, Deepak; Friedrich, Tobias

    2010-01-01

    Many applications like pointer analysis and incremental compilation require maintaining a topological ordering of the nodes of a directed acyclic graph (DAG) under dynamic updates. All known algorithms for this problem are either only analyzed for worst-case insertion sequences or only evaluated...... experimentally on random DAGs. We present the first average-case analysis of incremental topological ordering algorithms. We prove an expected runtime of under insertion of the edges of a complete DAG in a random order for the algorithms of Alpern et al. (1990) [4], Katriel and Bodlaender (2006) [18], and Pearce...

  7. Ordered particles versus ordered pointers in the hybrid ordered plasma simulation (HOPS) code

    International Nuclear Information System (INIS)

    Anderson, D.V.; Shumaker, D.E.

    1993-01-01

    From a computational standpoint, particle simulation calculations for plasmas have not adapted well to the transitions from scalar to vector processing nor from serial to parallel environments. They have suffered from inordinate and excessive accessing of computer memory and have been hobbled by relatively inefficient gather-scatter constructs resulting from the use of indirect indexing. Lastly, the many-to-one mapping characteristic of the deposition phase has made it difficult to perform this in parallel. The authors' code sorts and reorders the particles in a spatial order. This allows them to greatly reduce the memory references, to run in directly indexed vector mode, and to employ domain decomposition to achieve parallelization. The field model solves pre-maxwell equations by interatively implicit methods. The OSOP (Ordered Storage Ordered Processing) version of HOPS keeps the particle tables ordered by rebuilding them after each particle pushing phase. Alternatively, the RSOP (Random Storage Ordered Processing) version keeps a table of pointers ordered by rebuilding them. Although OSOP is somewhat faster than RSOP in tests on vector-parallel machines, it is not clear this advantage will carry over to massively parallel computers

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

    International Nuclear Information System (INIS)

    Pons, Charles-Henri

    1980-01-01

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

  9. Process improvement approach to the acid activation of smectite using factorial and orthogonal central composite design methods

    Directory of Open Access Journals (Sweden)

    SRDJAN PETROVIC

    2008-04-01

    Full Text Available The purpose of this study was to determine the effective operating parameters and the optimum operating conditions of an acid activation process within the framework of improvement of the process. Full two-level factorial and orthogonal central composite design methods were used successively. The examined parameters were the main and interaction effects of temperature, leaching time, acid normality, solid-to-liquid ratio and stirring rate. The selected process response was the leaching yield of the MgO content because Mg is the element most readily removed from the octahedral sheet, which affects the tendency for activation. Statistical regression analysis and analysis of variance were applied to the experimental data to develop a predictive model, which revealed that temperature, leaching time and acid normality exert the strongest influence on the specific surface area of smectite, whilst the solid-to-liquid ratio and the stirring rate have a secondary effect. Furthermore, the highest leaching yield of MgO was found to be 41.86 %, which is responsible for the increase in the specific surface area of up to 221 m2 g-1.

  10. Interactive priming of biochar and labile organic matter mineralization in a smectite-rich soil.

    Science.gov (United States)

    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.

  11. Erosion of bentonite buffer in a KBS-3 repository

    International Nuclear Information System (INIS)

    Neretnieks, Ivars; Liu, Loncheng; Moreno, Luis

    2010-01-01

    Document available in extended abstract form only. We have developed a Dynamic model for sodium gel expansion in fractures where the gel soaks up non-saline water as it expands. The model is based on a force balance between and on smectite particles, which move in the water. The Dynamic model of gel expansion showing the evolution in time and space of a gel was successfully tested against expansion experiments in test tubes. The expansion was measured with high resolution and in great detail over many months by Magnetic Resonance Imaging, MRI. The model also predicted the gel expansion through filters with very narrow pores well. In addition the model predicts the CCC fairly well, order to orders of magnitude better than the conventional DLVO theory. A gel viscosity model of dilute gels was derived, which accounts for ion concentration influence as well as the volume fraction of smectite in the gel. The model accounts for the presence of the DDL, which seemingly makes the particles larger so that they interact at lower particle densities. The viscosity model uses experimental data to obtain the necessary fitting parameters but is otherwise based on established theories of suspension viscosity. These models form the core of the erosion model. Both show a strong dependence on the ionic strength of the pore water. Simulations were performed for a case where the gel expands outward into the fracture that intersects the deposition hole. Fresh groundwater approaches and passes the gel/water interface. Smectite colloids move out into the water due to the repulsive forces between the particle and by Brownian motion. The dilute gel/sol is mobilised and flows downstream in a thin region where the viscosity is low enough to permit flow. Sodium diffuses from the compacted bentonite into and through the expanding gel towards the gel/water interface and further out into the seeping water. Mass transfer resistance for ions as well as smectite particles in the seeping water is

  12. Examination of competitive lanthanide sorption onto smectites and its significance in the management of radioactive waste

    Energy Technology Data Exchange (ETDEWEB)

    Galunin, Evgeny [Departament de Quimica Analitica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Alba, Maria D. [Instituto de Ciencia de Materiales de Sevilla, Consejo Superior de Investigaciones Cientificas - Universidad de Sevilla, Av. Americo Vespucio 49, 41092 Sevilla (Spain); Santos, Maria J. [Departamento de Quimica, Universidade Estadual de Londrina, Londrina, PR 86051-990 (Brazil); Abrao, Taufik [Instituto de Ciencia de Materiales de Sevilla, Consejo Superior de Investigaciones Cientificas - Universidad de Sevilla, Av. Americo Vespucio 49, 41092 Sevilla (Spain); Vidal, Miquel, E-mail: miquel.vidal@ub.edu [Departament de Quimica Analitica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain)

    2011-02-28

    The competitive effect of La and Lu (analogues of radionuclides appearing in radioactive waste) in the sorption in four smectites was examined. Sorption and desorption distribution coefficients (K{sub d}; K{sub d,des}), and desorption rates (R{sub des}) were determined from batch tests in two media: deionized water and, to consider the influence of cement leachates, 0.02 mol L{sup -1} Ca. The competitive effect was lower when high-affinity sites were available, as in the water medium at the lowest range of initial lanthanide concentration, with high K{sub d} for La and for Lu (5-63 x 10{sup 4} L kg{sup -1}). Lower K{sub d} was measured at higher initial concentrations and in the Ca medium, where Lu showed a stronger competitive effect. This was confirmed by fitting the sorption data to a two-solute Langmuir isotherm. The desorption data indicated that sorption was virtually irreversible for the scenarios with high sorption, with an excellent correlation between K{sub d} and K{sub d,des} (R{sup 2} around 0.9 for the two lanthanides). Assuming that radioactive waste is a mixture of radionuclides, and that Ca ions will be provided by the cement leachates, this would reduce the retention capacity of clay engineered barriers.

  13. Evaluation of the mineralogical characterization of several smectite clay deposits of the state of Paraiba, Brazil using statistical analysis of variance

    International Nuclear Information System (INIS)

    Gama, A.J.A.; Menezes, R.R.; Neves, G.A.; Brito, A.L.F. de

    2015-01-01

    Currently over 80% of industrialized bentonite clay produced in Brazil in sodium form for use in various industrial applications come from the deposits in Boa Vista - PB. Recently they were discovered new bentonite deposits situated in the municipalities of Cubati - PB, Drawn Stone - PB, Sossego - PB, and last in olive groves - PB, requiring systematic studies to develop all its industrial potential. Therefore, this study aimed to evaluate chemical characterization several deposits of smectite clays from various regions of the state of Paraíba through the analysis of statistical variance. Chemical analysis form determined by fluorescence x-ray (EDX). Then analyzes were carried out of variance statistics and Tukey test using the statistical soft MINITAB® 17.0. The results showed that the chemical composition of bentonite clay of new deposits showed different amounts of silica, aluminum, magnesium and calcium in relation clays in Boa Vista, and clays imported. (author)

  14. Optimal Order of Successive Office Hysteroscopy and Endometrial Biopsy for the Evaluation of Abnormal Uterine Bleeding: A Randomized Controlled Trial.

    Science.gov (United States)

    Sarkar, Papri; Mikhail, Emad; Schickler, Robyn; Plosker, Shayne; Imudia, Anthony N

    2017-09-01

    To estimate the optimal order of office hysteroscopy and endometrial biopsy when performed successively for evaluation of abnormal uterine bleeding. Patients undergoing successive office hysteroscopy and endometrial biopsy were included in a single-blind, prospective, randomized trial. The primary outcome was to evaluate the effect of order of procedures on patients' pain score. Prespecified secondary outcomes include procedure duration, hysteroscopic visualization of the uterine cavity, endometrial sample adequacy, and number of attempts at biopsy. Pain scores were assessed using a visual analog scale from 0 to 10 and endometrial sample adequacy was determined from the histopathology report. Hysteroscopy images were recorded. Sample size of 34 per group (n=68) was determined to be adequate to detect a difference of 20% in visual analog scale score between hysteroscopy first (group A) and biopsy first (group B) at α of 0.05 and 80% power. Between October 2015 and January 2017, 78 women were randomized to group A (n=40) and group B (n=38). There was no difference in global pain perception [7 (0-10) vs 7 (0-10); P=.57, 95% CI 5.8-7.1]. Procedure duration [3 (1-9) vs 3 (2-10), P=.32, 95% CI 3.3-4.1] and endometrial sample adequacy (78.9% vs 75.7%, P=.74) were similar in both groups. Group A patients had better endometrial visualization (Pabnormal uterine bleeding, the global pain perception, and time required are independent of the order in which procedures are performed. Performing hysteroscopy first ensures better image, whereas biopsy first yields adequate tissue sample with fewer attempts. ClinicalTrials.gov, NCT02472184.

  15. Partially ordered models

    NARCIS (Netherlands)

    Fernandez, R.; Deveaux, V.

    2010-01-01

    We provide a formal definition and study the basic properties of partially ordered chains (POC). These systems were proposed to model textures in image processing and to represent independence relations between random variables in statistics (in the later case they are known as Bayesian networks).

  16. Ordered Consumer Search

    OpenAIRE

    Armstrong, Mark

    2016-01-01

    The paper discusses situations in which consumers search through their options in a deliberate order, in contrast to more familiar models with random search. Topics include: network effects (consumers may be better off following the same search order as other consumers); the use of price and non-price advertising to direct search; the impact of consumers starting a new search with their previous supplier; the incentive sellers have to merge or co-locate with other sellers; and the incentive a...

  17. Étude des effets d'irradiation dans les montmorillonites. Application au stockage des déchets radioactifs.

    OpenAIRE

    Sorieul , Stéphanie

    2003-01-01

    Smectite is a major component of bentonite, a material considered for engineered barriers in high level nuclear wastes repositories (HLNWR). In order to predict the long-term performance of the bentonite, various physical and chemical factors such as, e.g., thermal gradient, redox potential or mechanical stresses are currently considered. By contrast, little is known about radiation effects in smectite, although it might affect the properties of this mineral through cumulative radiation damag...

  18. Anisotropy of the monomer random walk in a polymer melt: local-order and connectivity effects

    International Nuclear Information System (INIS)

    Bernini, S; Leporini, D

    2016-01-01

    The random walk of a bonded monomer in a polymer melt is anisotropic due to local order and bond connectivity. We investigate both effects by molecular-dynamics simulations on melts of fully-flexible linear chains ranging from dimers (M  =  2) up to entangled polymers (M  =  200). The corresponding atomic liquid is also considered a reference system. To disentangle the influence of the local geometry and the bond arrangements, and to reveal their interplay, we define suitable measures of the anisotropy emphasising either the former or the latter aspect. Connectivity anisotropy, as measured by the correlation between the initial bond orientation and the direction of the subsequent monomer displacement, shows a slight enhancement due to the local order at times shorter than the structural relaxation time. At intermediate times—when the monomer displacement is comparable to the bond length—a pronounced peak and then decays slowly as t −1/2 , becoming negligible when the displacement is as large as about five bond lengths, i.e. about four monomer diameters or three Kuhn lengths. Local-geometry anisotropy, as measured by the correlation between the initial orientation of a characteristic axis of the Voronoi cell and the subsequent monomer dynamics, is affected at shorter times than the structural relaxation time by the cage shape with antagonistic disturbance by the connectivity. Differently, at longer times, the connectivity favours the persistence of the local-geometry anisotropy, which vanishes when the monomer displacement exceeds the bond length. Our results strongly suggest that the sole consideration of the local order is not enough to understand the microscopic origin of the rattling amplitude of the trapped monomer in the cage of the neighbours. (paper)

  19. Transient modeling of non-Fickian transport and first-order reaction using continuous time random walk

    Science.gov (United States)

    Burnell, Daniel K.; Hansen, Scott K.; Xu, Jie

    2017-09-01

    Contaminants in groundwater may experience a broad spectrum of velocities and multiple rates of mass transfer between mobile and immobile zones during transport. These conditions may lead to non-Fickian plume evolution which is not well described by the advection-dispersion equation (ADE). Simultaneously, many groundwater contaminants are degraded by processes that may be modeled as first-order decay. It is now known that non-Fickian transport and reaction are intimately coupled, with reaction affecting the transport operator. However, closed-form solutions for these important scenarios have not been published for use in applications. In this paper, we present four new Green's function analytic solutions in the uncoupled, uncorrelated continuous time random walk (CTRW) framework for reactive non-Fickian transport, corresponding to the quartet of conservative tracer solutions presented by Kreft and Zuber (1978) for Fickian transport. These consider pulse injection for both resident and flux concentration combined with detection in both resident and flux concentration. A pair of solutions for resident concentration temporal pulses with detection in both flux and resident concentration is also presented. We also derive the relationship between flux and resident concentration for non-Fickian transport with first-order reaction for this CTRW formulation. An explicit discussion of employment of the new solutions to model transport with arbitrary upgradient boundary conditions as well as mobile-immobile mass transfer is then presented. Using the new solutions, we show that first-order reaction has no effect on the anomalous spatial spreading rate of concentration profiles, but produces breakthrough curves at fixed locations that appear to have been generated by Fickian transport. Under the assumption of a Pareto CTRW transition distribution, we present a variety of numerical simulations including results showing coherence of our analytic solutions and CTRW particle

  20. On stochastic differential equations with random delay

    International Nuclear Information System (INIS)

    Krapivsky, P L; Luck, J M; Mallick, K

    2011-01-01

    We consider stochastic dynamical systems defined by differential equations with a uniform random time delay. The latter equations are shown to be equivalent to deterministic higher-order differential equations: for an nth-order equation with random delay, the corresponding deterministic equation has order n + 1. We analyze various examples of dynamical systems of this kind, and find a number of unusual behaviors. For instance, for the harmonic oscillator with random delay, the energy grows as exp((3/2) t 2/3 ) in reduced units. We then investigate the effect of introducing a discrete time step ε. At variance with the continuous situation, the discrete random recursion relations thus obtained have intrinsic fluctuations. The crossover between the fluctuating discrete problem and the deterministic continuous one as ε goes to zero is studied in detail on the example of a first-order linear differential equation

  1. Sample size adjustments for varying cluster sizes in cluster randomized trials with binary outcomes analyzed with second-order PQL mixed logistic regression.

    Science.gov (United States)

    Candel, Math J J M; Van Breukelen, Gerard J P

    2010-06-30

    Adjustments of sample size formulas are given for varying cluster sizes in cluster randomized trials with a binary outcome when testing the treatment effect with mixed effects logistic regression using second-order penalized quasi-likelihood estimation (PQL). Starting from first-order marginal quasi-likelihood (MQL) estimation of the treatment effect, the asymptotic relative efficiency of unequal versus equal cluster sizes is derived. A Monte Carlo simulation study shows this asymptotic relative efficiency to be rather accurate for realistic sample sizes, when employing second-order PQL. An approximate, simpler formula is presented to estimate the efficiency loss due to varying cluster sizes when planning a trial. In many cases sampling 14 per cent more clusters is sufficient to repair the efficiency loss due to varying cluster sizes. Since current closed-form formulas for sample size calculation are based on first-order MQL, planning a trial also requires a conversion factor to obtain the variance of the second-order PQL estimator. In a second Monte Carlo study, this conversion factor turned out to be 1.25 at most. (c) 2010 John Wiley & Sons, Ltd.

  2. Perturbation Solutions for Random Linear Structural Systems subject to Random Excitation using Stochastic Differential Equations

    DEFF Research Database (Denmark)

    Köyluoglu, H.U.; Nielsen, Søren R.K.; Cakmak, A.S.

    1994-01-01

    perturbation method using stochastic differential equations. The joint statistical moments entering the perturbation solution are determined by considering an augmented dynamic system with state variables made up of the displacement and velocity vector and their first and second derivatives with respect......The paper deals with the first and second order statistical moments of the response of linear systems with random parameters subject to random excitation modelled as white-noise multiplied by an envelope function with random parameters. The method of analysis is basically a second order...... to the random parameters of the problem. Equations for partial derivatives are obtained from the partial differentiation of the equations of motion. The zero time-lag joint statistical moment equations for the augmented state vector are derived from the Itô differential formula. General formulation is given...

  3. Neutron scattering study of unstable magnetic long-range order in the random two-dimensional Ising antiferromagnets Rb/sub 2/Cosub(c)Mgsub(1-c)F/sub 4/

    Energy Technology Data Exchange (ETDEWEB)

    Ikeda, H; Suzuki, M [Ochanomizu Univ., Tokyo (Japan). Dept. of Physics; Hutchings, M T [UKAEA Atomic Energy Research Establishment, Harwell. Materials Physics Div.

    1979-01-01

    The spin correlation between two-dimensionally (2D) ordered antiferromagnetic layers in the random antiferromagnets Rb/sub 2/Cosub(c)Mgsub(1-c)F/sub 4/ depends strongly on the rate at which the sample is cooled through the Neel point Tsub(N) and decreases markedly with decreasing Co/sup 2 +/ ion concentration c. Preliminary data are presented which indicate that the order below sub(N) is metastable and relaxes to a fully correlated 3D ordered state on a finite, measurable, time-scale.

  4. Mineralogical and chemical characterization of various bentonite and smectite-rich clay materials Part A: Comparison and development of mineralogical characterization methods Part B: Mineralogical and chemical characterization of clay materials

    International Nuclear Information System (INIS)

    Kumpulainen, S.; Kiviranta, L.

    2010-06-01

    Mineralogy is an essential issue in understanding thermo-hydro-mechanical-chemical (THMC) behavior of bentonite materials. Mineralogy affects, among others, chemical composition of pore water, susceptibility for erosion, and transport of radionuclides. Consequently, mineralogy affects the designs of the buffer and backfill components. The objective of this work was to implement and develop mineralogical and chemical methods for characterization of reference clays considered for use as buffer and backfill materials in nuclear waste disposal. In this work, different methods were tested, compared, developed, and best available techniques selected. An additional aim was to characterize reference materials that are used in various nuclear waste disposal supporting studies, e.g., the SKB's alternative buffer material (ABM) experiment. Materials studied included three Wyoming-bentonites, two bentonites from Milos, four bentonites from Kutch district, and two Friedland clays. Minerals were identified using x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and polarizing microscopy. Mineralogical composition was estimated using Rietveld-analysis. Chemical methods were used to support and validate mineralogical interpretation. Total chemical composition was determined from decomposed samples using spectrometry (ICP-AES) and combustion (Leco-S, Leco-C). Ferric and ferrous iron species were distinguished titrimetrically and the amount of soluble sulphate was determined using ion chromatography. In addition, cation exchange capacity and original exchangeable cations were determined. Chemical composition of fine (<2 μ m) fractions and poorly crystalline Fe-, Al- and Si-phases determined by selective extractions were used in structural calculations of smectite. XRD is a basic method for all mineralogical characterization, but it is insensitive for detecting trace minerals and variations in the structural chemical composition of clay minerals. Polarizing

  5. Self-correcting random number generator

    Science.gov (United States)

    Humble, Travis S.; Pooser, Raphael C.

    2016-09-06

    A system and method for generating random numbers. The system may include a random number generator (RNG), such as a quantum random number generator (QRNG) configured to self-correct or adapt in order to substantially achieve randomness from the output of the RNG. By adapting, the RNG may generate a random number that may be considered random regardless of whether the random number itself is tested as such. As an example, the RNG may include components to monitor one or more characteristics of the RNG during operation, and may use the monitored characteristics as a basis for adapting, or self-correcting, to provide a random number according to one or more performance criteria.

  6. Much of the variation in breast pathology quality assurance data in the UK can be explained by the random order in which cases arrive at individual centres, but some true outliers do exist.

    Science.gov (United States)

    Cross, Simon S; Stephenson, Timothy J; Harrison, Robert F

    2011-10-01

    To investigate the role of random temporal order of patient arrival at screening centres in the variability seen in rates of node positivity and breast cancer grade between centres in the NHS Breast Screening Programme. Computer simulations were performed of the variation in node positivity and breast cancer grade with the random temporal arrival of patients at screening centres based on national UK audit data. Cumulative mean graphs of these data were plotted. Confidence intervals for the parameters were generated, using the binomial distribution. UK audit data were plotted on these control limit graphs. The results showed that much of the variability in the audit data could be accounted for by the effects of random order of arrival of cases at the screening centres. Confidence intervals of 99.7% identified true outliers in the data. Much of the variation in breast pathology quality assurance data in the UK can be explained by the random order in which cases arrive at individual centres. Control charts with confidence intervals of 99.7% plotted against the number of reported cases are useful tools for identification of true outliers. 2011 Blackwell Publishing Limited.

  7. Order acceptance in food processing systems with random raw material requirements

    NARCIS (Netherlands)

    Kilic, Onur A.; van Donk, Dirk Pieter; Wijngaard, Jacob; Tarim, S. Armagan

    This study considers a food production system that processes a single perishable raw material into several products having stochastic demands. In order to process an order, the amount of raw material delivery from storage needs to meet the raw material requirement of the order. However, the amount

  8. Hidden temporal order unveiled in stock market volatility variance

    Directory of Open Access Journals (Sweden)

    Y. Shapira

    2011-06-01

    Full Text Available When analyzed by standard statistical methods, the time series of the daily return of financial indices appear to behave as Markov random series with no apparent temporal order or memory. This empirical result seems to be counter intuitive since investor are influenced by both short and long term past market behaviors. Consequently much effort has been devoted to unveil hidden temporal order in the market dynamics. Here we show that temporal order is hidden in the series of the variance of the stocks volatility. First we show that the correlation between the variances of the daily returns and means of segments of these time series is very large and thus cannot be the output of random series, unless it has some temporal order in it. Next we show that while the temporal order does not show in the series of the daily return, rather in the variation of the corresponding volatility series. More specifically, we found that the behavior of the shuffled time series is equivalent to that of a random time series, while that of the original time series have large deviations from the expected random behavior, which is the result of temporal structure. We found the same generic behavior in 10 different stock markets from 7 different countries. We also present analysis of specially constructed sequences in order to better understand the origin of the observed temporal order in the market sequences. Each sequence was constructed from segments with equal number of elements taken from algebraic distributions of three different slopes.

  9. Creating, generating and comparing random network models with NetworkRandomizer.

    Science.gov (United States)

    Tosadori, Gabriele; Bestvina, Ivan; Spoto, Fausto; Laudanna, Carlo; Scardoni, Giovanni

    2016-01-01

    Biological networks are becoming a fundamental tool for the investigation of high-throughput data in several fields of biology and biotechnology. With the increasing amount of information, network-based models are gaining more and more interest and new techniques are required in order to mine the information and to validate the results. To fill the validation gap we present an app, for the Cytoscape platform, which aims at creating randomised networks and randomising existing, real networks. Since there is a lack of tools that allow performing such operations, our app aims at enabling researchers to exploit different, well known random network models that could be used as a benchmark for validating real, biological datasets. We also propose a novel methodology for creating random weighted networks, i.e. the multiplication algorithm, starting from real, quantitative data. Finally, the app provides a statistical tool that compares real versus randomly computed attributes, in order to validate the numerical findings. In summary, our app aims at creating a standardised methodology for the validation of the results in the context of the Cytoscape platform.

  10. Experimental investigation of smectite hydration from the simulation of 001 X-ray diffraction lines. Implications for the characterization of mineralogical modifications of the 'argilite' from the Meuse - Haute Marne site as a result of a thermal perturbation; Etude experimentale de l'hydratation des smectites par simulation des raies OOl de diffraction des rayons X. Implications pour l'etude d'une perturbation thermique sur la mineralogie de l'argilite du site Meuse-Haute Marne

    Energy Technology Data Exchange (ETDEWEB)

    Ferrage, E

    2004-10-15

    The structural modifications affecting the reactive mineral constituents of the clay barriers (smectite) and possibly resulting from the thermal pulse related to nuclear waste storage are essentially limited to the amount and location of the layer charge deficit. These modifications likely impact the hydration properties of these minerals, and a specific methodology has thus been developed to describe, using simulation of X-ray diffraction profiles (001 reflections), these hydration properties and specifically the heterogeneity resulting from the inter-stratification of different layer types, each exhibiting a specific hydration state. The detailed study of the hydration properties of a low-charge montmorillonite (octahedral charge) has shown that the affinity of the interlayer cation for water rules the hydration state and the thickness of hydrated smectite layers. If the layer charge is increased, the transition between the different hydration states is shifted, following a water desorption isotherm, towards lower relative humidities. In addition, the hydration of studied beidellites (tetrahedral charge) was shown to be more heterogeneous than that of montmorillonites. The developed methodology also allowed describing the structural modifications resulting from a chemical perturbation (chlorinated anionic background, pH). Finally, the link between the thickness of elementary layers and the amount of interlayer water molecules has been evidenced. A new structure model has also been determined for these interlayer species allowing an improved description of their positional distribution in bi-hydrated interlayers. (author)

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

    Science.gov (United States)

    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.

  12. Effect of smectite clays storage in their rheological properties; Efeito do armazenamento de argilas esmectiticas nas suas propriedades reologicas

    Energy Technology Data Exchange (ETDEWEB)

    Silva, I.A. da; Sousa, F.K.A. de; Neves, G. de A.; Ferreira, H.C., E-mail: isabelle_albuquerquecg@hotmail.com, E-mail: kegalves@gmail.com, E-mail: gelmires.neves@ufcg.edu.br, E-mail: heber.ferreira@ufcg.edu.br [Universidade Federal de Campina Grande (UFCG), PB (Brazil); Ferreira, H.S., E-mail: hsivini@terra.com.br [Universidade Federal Rural de Pernambuco (UFRPE), Recife, PE (Brazil). Departamento de Educacao; Ferreira, H.S., E-mail: heber@ct.ufpb.br [Universidade Federal da Paraiba (UFPB), Joao Pessoa (Brazil). Departamento de Engenharia de Materiais

    2017-01-15

    This work investigates the storage influence of natural and industrial smectite clays in their rheological properties, since the salt metathesis reaction that occurs following treatment of polycationic clays with Na{sub 2} CO{sub 3} is reversible. The phenomena involved in this reaction are not yet fully known and previous studies show improvement in some properties. The rheological properties were determined in sodium-clays in 1995 and polycationic clays added with sodium carbonate (Na{sub 2} CO{sub 3} ) in 2015. Physical, chemical and mineralogical characterizations of the samples were performed using the following techniques: particle size analysis by laser diffraction, chemical composition by X-ray fluorescence, X-ray diffraction and thermal analysis (DTA and TGA). The rheology of dispersions was determined by the apparent viscosity, plastic viscosity and filtrate volume, which were later considered the oil industry standards only as a benchmark. The results showed that the storage conditions, humidity and particle size of the samples resulted in improvements in their rheological properties over the years, indicating the non-reversibility of the reaction of cation exchange, which is important in their validity after manufacturing. (author)

  13. On reflexivity of random walks in a random environment on a metric space

    International Nuclear Information System (INIS)

    Rozikov, U.A.

    2002-11-01

    In this paper, we consider random walks in random environments on a countable metric space when jumps of the walks of the fractions are finite. The transfer probabilities of the random walk from x is an element of G (where G is the considering metric space) are defined by vector p(x) is an element of R k , k>1, where {p(x), x is an element of G} is the set of independent and indentically distributed random vectors. For the random walk, a sufficient condition of nonreflexivity is obtained. Examples for metric spaces Z d free groups and free product of finite numbers cyclic groups of the second order and some other metric spaces are considered. (author)

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

    Science.gov (United States)

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

    2017-12-01

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

  15. Photophysical and antibacterial properties of complex systems based on smectite, a cationic surfactant and methylene blue.

    Science.gov (United States)

    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.

  16. Dechlorination of chlorinated phenols by subnanoscale Pd 0 /Fe 0 intercalated in smectite: pathway, reactivity, and selectivity.

    Science.gov (United States)

    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.

  17. Loss of long-range magnetic order in a nanoparticle assembly due to random anisotropy

    International Nuclear Information System (INIS)

    Binns, C; Howes, P B; Baker, S H; Marchetto, H; Potenza, A; Steadman, P; Dhesi, S S; Roy, M; Everard, M J; Rushforth, A

    2008-01-01

    We have used soft x-ray photoemission electron microscopy (XPEEM) combined with x-ray magnetic circular dichroism (XMCD) and DC SQUID (superconducting quantum interference device) magnetometry to probe the magnetic ground state in Fe thin films produced by depositing size-selected gas-phase Fe nanoparticles with a diameter of 1.7 nm (∼200 atoms) onto Si substrates. The depositions were carried out in ultrahigh vacuum conditions and thicknesses of the deposited film in the range 5-50 nm were studied. The magnetometry data are consistent with the film forming a correlated super-spin glass with a magnetic correlation length ∼5 nm. The XPEEM magnetic maps from the cluster-assembled films were compared to those for a conventional thin Fe film with a thickness of 20 nm produced by a molecular beam epitaxy (MBE) source. Whereas a normal magnetic domain structure is observed in the conventional MBE thin film, no domain structure could be observed in any of the nanoparticle films down to the resolution limit of the XMCD based XPEEM (100 nm) confirming the ground state indicated by the magnetometry measurements. This observation is consistent with the theoretical prediction that an arbitrarily weak random anisotropy field will destroy long-range magnetic order

  18. Universal medium-range order of amorphous metal oxides.

    Science.gov (United States)

    Nishio, Kengo; Miyazaki, Takehide; Nakamura, Hisao

    2013-10-11

    We propose that the structure of amorphous metal oxides can be regarded as a dual-dense-random-packing structure, which is a superposition of the dense random packing of metal atoms and that of oxygen atoms. Our ab initio molecular dynamics simulations show that the medium-range order of amorphous HfO2, ZrO2, TiO2, In2O3, Ga2O3, Al2O3, and Cu2O is characterized by the pentagonal-bipyramid arrangement of metal atoms and that of oxygen atoms, and prove the validity of our dual-random-sphere-packing model. In other words, we find that the pentagonal medium-range order is universal independent of type of metal oxide.

  19. Random packing of colloids and granular matter

    NARCIS (Netherlands)

    Wouterse, A.

    2008-01-01

    This thesis deals with the random packing of colloids and granular matter. A random packing is a stable disordered collection of touching particles, without long-range positional and orientational order. Experimental random packings of particles with the same shape but made of different materials

  20. Experimental investigation of smectite hydration from the simulation of 001 X-ray diffraction lines. Implications for the characterization of mineralogical modifications of the 'argilite' from the Meuse - Haute Marne site as a result of a thermal perturbation

    International Nuclear Information System (INIS)

    Ferrage, E.

    2004-10-01

    The structural modifications affecting the reactive mineral constituents of the clay barriers (smectite) and possibly resulting from the thermal pulse related to nuclear waste storage are essentially limited to the amount and location of the layer charge deficit. These modifications likely impact the hydration properties of these minerals, and a specific methodology has thus been developed to describe, using simulation of X-ray diffraction profiles (001 reflections), these hydration properties and specifically the heterogeneity resulting from the inter-stratification of different layer types, each exhibiting a specific hydration state. The detailed study of the hydration properties of a low-charge montmorillonite (octahedral charge) has shown that the affinity of the interlayer cation for water rules the hydration state and the thickness of hydrated smectite layers. If the layer charge is increased, the transition between the different hydration states is shifted, following a water desorption isotherm, towards lower relative humidities. In addition, the hydration of studied beidellites (tetrahedral charge) was shown to be more heterogeneous than that of montmorillonites. The developed methodology also allowed describing the structural modifications resulting from a chemical perturbation (chlorinated anionic background, pH). Finally, the link between the thickness of elementary layers and the amount of interlayer water molecules has been evidenced. A new structure model has also been determined for these interlayer species allowing an improved description of their positional distribution in bi-hydrated interlayers. (author)

  1. Random Fields

    Science.gov (United States)

    Vanmarcke, Erik

    1983-03-01

    Random variation over space and time is one of the few attributes that might safely be predicted as characterizing almost any given complex system. Random fields or "distributed disorder systems" confront astronomers, physicists, geologists, meteorologists, biologists, and other natural scientists. They appear in the artifacts developed by electrical, mechanical, civil, and other engineers. They even underlie the processes of social and economic change. The purpose of this book is to bring together existing and new methodologies of random field theory and indicate how they can be applied to these diverse areas where a "deterministic treatment is inefficient and conventional statistics insufficient." Many new results and methods are included. After outlining the extent and characteristics of the random field approach, the book reviews the classical theory of multidimensional random processes and introduces basic probability concepts and methods in the random field context. It next gives a concise amount of the second-order analysis of homogeneous random fields, in both the space-time domain and the wave number-frequency domain. This is followed by a chapter on spectral moments and related measures of disorder and on level excursions and extremes of Gaussian and related random fields. After developing a new framework of analysis based on local averages of one-, two-, and n-dimensional processes, the book concludes with a chapter discussing ramifications in the important areas of estimation, prediction, and control. The mathematical prerequisite has been held to basic college-level calculus.

  2. Infinitely robust order and local order-parameter tulips in Apollonian networks with quenched disorder

    Science.gov (United States)

    Kaplan, C. Nadir; Hinczewski, Michael; Berker, A. Nihat

    2009-06-01

    For a variety of quenched random spin systems on an Apollonian network, including ferromagnetic and antiferromagnetic bond percolation and the Ising spin glass, we find the persistence of ordered phases up to infinite temperature over the entire range of disorder. We develop a renormalization-group technique that yields highly detailed information, including the exact distributions of local magnetizations and local spin-glass order parameters, which turn out to exhibit, as function of temperature, complex and distinctive tulip patterns.

  3. Random sets and random fuzzy sets as ill-perceived random variables an introduction for Ph.D. students and practitioners

    CERN Document Server

    Couso, Inés; Sánchez, Luciano

    2014-01-01

    This short book provides a unified view of the history and theory of random sets and fuzzy random variables, with special emphasis on its use for representing higher-order non-statistical uncertainty about statistical experiments. The authors lay bare the existence of two streams of works using the same mathematical ground, but differing form their use of sets, according to whether they represent objects of interest naturally taking the form of sets, or imprecise knowledge about such objects. Random (fuzzy) sets can be used in many fields ranging from mathematical morphology, economics, artificial intelligence, information processing and statistics per se, especially in areas where the outcomes of random experiments cannot be observed with full precision. This book also emphasizes the link between random sets and fuzzy sets with some techniques related to the theory of imprecise probabilities. This small book is intended for graduate and doctoral students in mathematics or engineering, but also provides an i...

  4. Correlation order, merging and diversification

    NARCIS (Netherlands)

    Dhaene, J.; Denuit, M.; Vanduffel, S.

    2009-01-01

    We investigate the influence of the dependence between random losses on the shortfall and on the diversification benefit that arises from merging these losses. We prove that increasing the dependence between losses, expressed in terms of correlation order, has an increasing effect on the shortfall,

  5. Final report of experiments with rock blocks interacting hydraulically with smectitic pellet fills

    Energy Technology Data Exchange (ETDEWEB)

    Pusch, Roland [Sweco Infrastructure AB, Stockholm (Sweden); Ramqvist, Gunnar [El-Tekno AB, Figeholm (Sweden); Hedin, Mikael [AaF, Stockholm (Sweden)

    2010-11-15

    The report describes the outcome of the work within the the project 'SU5 08.20 Impact of water inflow in deposition tunnels'. Project decision SKBdoc id 1178871 Version 3.0. Two activity plans have been used for the field work: AP TD SU50820-09-014 and AP TD SU50820-09-031. A problem in backfilling of KBS-3V tunnels with smectitic pellets surrounding highly compacted clay blocks is that water entering the fill have a very substantial effect on the manner in which water moves into or through a pellet-filled region in the period immediately following pellet placement. Channels will be formed that lead much water to the sloping front of the fill in the course of placing it. This can soften the fill and turn it into mud where the water is discharged as demonstrated by large-scale tests. The nature of such channels was investigated in the present study that comprised experiments with rock blocks equipped with nozzles for injecting water into contacting pellet fills at constant flow rates. The purpose was to identify the basic mechanisms in the first phase of hydration of pellet fills and to find out if there is a threshold flow rate for 'piping'. The question if channelling at breakthrough takes place along the contact with the confinement, as indicated by preceding tests with steel and plexiglass instead of rock, was in focus. While the mechanisms of water entering a fill from separate local spots in contacting rock are well understood, prediction of the entire wetting process of a larger pellet volume requires consideration of the interactive function of several inflow spots, representing single or networks of rock fractures. Experiments with pellet fills on a larger scale with simultaneous inflow from a number of fractures would provide further information on the wetting process. Such a test is outlined in the report.

  6. Decisions with Uncertain Consequences-A Total Ordering on Loss-Distributions.

    Science.gov (United States)

    Rass, Stefan; König, Sandra; Schauer, Stefan

    2016-01-01

    Decisions are often based on imprecise, uncertain or vague information. Likewise, the consequences of an action are often equally unpredictable, thus putting the decision maker into a twofold jeopardy. Assuming that the effects of an action can be modeled by a random variable, then the decision problem boils down to comparing different effects (random variables) by comparing their distribution functions. Although the full space of probability distributions cannot be ordered, a properly restricted subset of distributions can be totally ordered in a practically meaningful way. We call these loss-distributions, since they provide a substitute for the concept of loss-functions in decision theory. This article introduces the theory behind the necessary restrictions and the hereby constructible total ordering on random loss variables, which enables decisions under uncertainty of consequences. Using data obtained from simulations, we demonstrate the practical applicability of our approach.

  7. Doppler Radar Vital Signs Detection Method Based on Higher Order Cyclostationary.

    Science.gov (United States)

    Yu, Zhibin; Zhao, Duo; Zhang, Zhiqiang

    2017-12-26

    Due to the non-contact nature, using Doppler radar sensors to detect vital signs such as heart and respiration rates of a human subject is getting more and more attention. However, the related detection-method research meets lots of challenges due to electromagnetic interferences, clutter and random motion interferences. In this paper, a novel third-order cyclic cummulant (TOCC) detection method, which is insensitive to Gaussian interference and non-cyclic signals, is proposed to investigate the heart and respiration rate based on continuous wave Doppler radars. The k -th order cyclostationary properties of the radar signal with hidden periodicities and random motions are analyzed. The third-order cyclostationary detection theory of the heart and respiration rate is studied. Experimental results show that the third-order cyclostationary approach has better estimation accuracy for detecting the vital signs from the received radar signal under low SNR, strong clutter noise and random motion interferences.

  8. Diffusion of Na(I), Cs(I), Sr(II) and Eu(III) in smectite rich natural clay.

    Science.gov (United States)

    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.

  9. Effects of a randomized intervention promoting healthy children's meals on children's ordering and dietary intake in a quick-service restaurant.

    Science.gov (United States)

    Anzman-Frasca, Stephanie; Braun, Abbey C; Ehrenberg, Sarah; Epstein, Leonard H; Gampp, April; Leone, Lucia A; Singh, Anita; Tauriello, Sara

    2018-08-01

    Children's consumption of restaurant foods is associated with higher energy intake and lower nutritional quality compared to foods prepared at home. The aim of this pilot study was to test whether an in-restaurant intervention promoting healthy children's meals (i.e. two meals that met nutrition recommendations and were thus healthier than typical children's meal offerings across leading restaurants) affected children's meal selection and intake. Families with 4-to-8-year-old children were recruited from one location of Anderson's Frozen Custard, a regional quick-service restaurant chain. Families were randomly assigned to return to the restaurant during an intervention or control period and were blinded to group assignment. All families received free meals. During the intervention period families also received placemats featuring two healthy "Kids' Meals of the Day" upon restaurant entry. After families finished dining, researchers recorded children's orders and collected leftovers for quantifying dietary intake via weighed plate waste. Poisson regression and chi-square tests were used to compare children's orders between study groups, and t-tests were used to test for differences in dietary intake among children ordering a promoted healthy entrée (main dish) versus those who did not. Fifty-eight families participated. Children who were exposed to the study placemats prior to ordering ordered a significantly greater number of healthy food components compared to controls (p = 0.03). Overall, in the intervention group, 21% of children ordered a healthy entrée or side dish, versus 7% of controls. Children who ordered one of the promoted healthy entrées consumed less saturated fat across the total meal compared to those who did not (p = 0.04). Manipulating the prominence of healthy choices in restaurants may shift children's meal selections. Future research should build on these initial promising results, aiming to increase the potency of the intervention

  10. An unbiased estimator of the variance of simple random sampling using mixed random-systematic sampling

    OpenAIRE

    Padilla, Alberto

    2009-01-01

    Systematic sampling is a commonly used technique due to its simplicity and ease of implementation. The drawback of this simplicity is that it is not possible to estimate the design variance without bias. There are several ways to circumvent this problem. One method is to suppose that the variable of interest has a random order in the population, so the sample variance of simple random sampling without replacement is used. By means of a mixed random - systematic sample, an unbiased estimator o...

  11. Random magnetism

    International Nuclear Information System (INIS)

    Tsallis, C.

    1980-03-01

    The 'ingredients' which control a phase transition in well defined system as well as in random ones (e.g. random magnetic systems) are listed and discussed within a somehow unifying perspective. Among these 'ingredients' we find the couplings and elements responsible for the cooperative phenomenon, the topological connectivity as well as possible topological incompatibilities, the influence of new degrees of freedom, the order parameter dimensionality, the ground state degeneracy and finally the 'quanticity' of the system. The general trends, though illustrated in magnetic systems, essentially hold for all phase transitions, and give a basis for connection of this area with Field theory, Theory of dynamical systems, etc. (Author) [pt

  12. Random magnetism

    International Nuclear Information System (INIS)

    Tsallis, C.

    1981-01-01

    The 'ingredients' which control a phase transition in well defined systems as well as in random ones (e.q. random magnetic systems) are listed and discussed within a somehow unifying perspective. Among these 'ingredients' the couplings and elements responsible for the cooperative phenomenon, the topological connectivity as well as possible topological incompatibilities, the influence of new degrees of freedom, the order parameter dimensionality, the ground state degeneracy and finally the 'quanticity' of the system are found. The general trends, though illustrated in magnetic systems, essentially hold for all phase transitions, and give a basis for connection of this area with Field theory, Theory of dynamical systems, etc. (Author) [pt

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

    Science.gov (United States)

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

    2013-01-01

    Drill fines of mudstone (targets John Klein and Cumberland) from the Sheepbed unit at Yel-lowknife Bay were analyzed by MSL payload elements including the Chemistry and Mineralogy (CheMin), APXS (Alpha Particle X-Ray Spectrometer), and Sample Analysis at Mars (SAM) instruments. CheMin XRD results show a variety of crystalline phases including feldspar, pyroxene, olivine, oxides, oxyhydroxides, sulfates, sulfides, a tri-octahedral smectite, and XRD amorphous material. The drill fines are distinctly different from corresponding analyses of the global soil (target Rocknest) in that the mudstone samples contained detectable phyllosilicate. Here we focus on John Klein and combine CheMin and APXS data to calculate the chemical composition and concentration of the amorphous component. The chemical composition of the amorphous plus smectite component for John Klein was calculated by subtracting the abundance-weighted chemical composition of the individual XRD crystalline components from the bulk composition of John Kline as measured by APXS. The chemical composition of individual crystalline components was determined either by stoichiometry (e.g., hematite and magnetite) or from their unit cell parameters (e.g., feldspar, olivine, and pyroxene). The chemical composition of the amorphous + smectite component (approx 71 wt.% of bulk sample) and bulk chemical composition are similar. In order to calculate the chemical composition of the amorphous component, a chemical composition for the tri-octahedral smectite must be assumed. We selected two tri-octahedral smectites with very different MgO/(FeO + Fe2O3) ratios (34 and 1.3 for SapCa1 and Griffithite, respectively). Relative to bulk sample, the concentration of amorphous and smectite components are 40 and 29 wt.% for SapCa1 and 33 and 36 wt.% for Griffithite. The amount of smectite was calculated by requiring the MgO concentration to be approx 0 wt.% in the amorphous component. Griffithite is the preferred smectite because

  14. Decisions with Uncertain Consequences-A Total Ordering on Loss-Distributions.

    Directory of Open Access Journals (Sweden)

    Stefan Rass

    Full Text Available Decisions are often based on imprecise, uncertain or vague information. Likewise, the consequences of an action are often equally unpredictable, thus putting the decision maker into a twofold jeopardy. Assuming that the effects of an action can be modeled by a random variable, then the decision problem boils down to comparing different effects (random variables by comparing their distribution functions. Although the full space of probability distributions cannot be ordered, a properly restricted subset of distributions can be totally ordered in a practically meaningful way. We call these loss-distributions, since they provide a substitute for the concept of loss-functions in decision theory. This article introduces the theory behind the necessary restrictions and the hereby constructible total ordering on random loss variables, which enables decisions under uncertainty of consequences. Using data obtained from simulations, we demonstrate the practical applicability of our approach.

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

    Science.gov (United States)

    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.

  16. Properties of the bentonite from Lieskovec deposit and their possible environmental applications

    International Nuclear Information System (INIS)

    Andrejkovicova, S.

    2008-01-01

    The community increasingly focuses on broader uses of raw materials, occurring in relatively sufficient amounts. Among them, bentonite play very important role in the environmental applications. Results presented herein are related to the yet comprehensively unexplored Fe-rich bentonite from Lieskovec deposit, Central Slovakia. The objective of this study was complex investigation of Lieskovec bentonite deposit. This bentonite was developed from andesitic pyroclastics; the dominant mineral in all the samples is iron-rich montmorillonite, covering 29 to 56 mass % in the samples. The accessory minerals include kaolinite (5-17 mass %), quartz (3-28 mass %), muscovite/illite (3-16 mass %), volcanic glass (6-14 mass %), orthoclase (1-12 mass %), opal (1-8 mass %) and cristobalite (1-3 mass %). Structural Fe(III) is mainly in phyllosilicates accounting for 70 % to 90 % of the total Fe in the unfractionated samples; less than 5 % is Fe(II). The remainder of the Fe is present in oxide and/or oxyhydroxide phases dominated by poorly ordered goethite and hematite with possibly some maghemite. Basic properties of bentonites result from the structure of the smectites. Size fractionation did not lead to pure smectite. Kaolinite and mica were not successfully removed. Quartz and feldspars were dismantled effectively. Non-clay minerals contribution decreased. Smectite content increased after separation up to 75 mass %. Low cation exchange capacities between 35 and 61 meq/100 g are caused also by low magnesium content in the octahedral sheets of montmorillonite, suggesting lower isomorphic Mg for Al substitution in the octahedral sheets of smectite and thus its lower octahedral charge. The main factor influencing CECs is smectite content affecting dominantly also the geotechnical properties. Geotechnical properties of Lieskovec bentonite, such as liquid limit in range 64-80 % and water adsorption by Enslin test 123-265 % were insufficient for utilization in geo-synthetic clay

  17. E-learning in order to improve drug prescription for hospitalized older patients: a cluster-randomized controlled study.

    Science.gov (United States)

    Franchi, Carlotta; Tettamanti, Mauro; Djade, Codjo Dgnefa; Pasina, Luca; Mannucci, Pier Mannuccio; Onder, Graziano; Gussoni, Gualberto; Manfellotto, Dario; Bonassi, Stefano; Salerno, Francesco; Nobili, Alessandro

    2016-07-01

    The aim of the study was to evaluate the effect of an e-learning educational program meant to foster the quality of drug prescription in hospitalized elderly patients. Twenty geriatric and internal medicine wards were randomized to intervention (e-learning educational program) or control (basic geriatric pharmacology notions). Logistic regression analysis was used in order to assess the effect of the intervention on the use of potentially inappropriate medication (PIM, primary outcome) at hospital discharge. Secondary outcomes were a reduced prevalence of at least one potential drug-drug interaction (DDI) and potentially severe DDI at discharge. Mortality rate and incidence of re-hospitalizations were other secondary outcomes assessed at the 12-month follow-up. A total of 697 patients (347 in the intervention and 350 in the control arms) were enrolled. No difference in the prevalence of PIM at discharge was found between arms (OR 1.29 95%CI 0.87-1.91). We also found no decrease in the prevalence of DDI (OR 0.67 95%CI 0.34-1.28) and potentially severe DDI (OR 0.86 95%CI 0.63-1.15) at discharge, nor in mortality rates and incidence of re-hospitalization at 12-month follow-up. This e-learning educational program had no clear effect on the quality of drug prescription and clinical outcomes in hospitalized elderly patients. Given the high prevalence of PIMs and potential DDIs recorded in the frame of this study, other approaches should be developed in order to improve the quality of drug prescription in this population. © 2016 The British Pharmacological Society.

  18. A Solution Method for Linear and Geometrically Nonlinear MDOF Systems with Random Properties subject to Random Excitation

    DEFF Research Database (Denmark)

    Micaletti, R. C.; Cakmak, A. S.; Nielsen, Søren R. K.

    structural properties. The resulting state-space formulation is a system of ordinary stochastic differential equations with random coefficient and deterministic initial conditions which are subsequently transformed into ordinary stochastic differential equations with deterministic coefficients and random......A method for computing the lower-order moments of randomly-excited multi-degree-of-freedom (MDOF) systems with random structural properties is proposed. The method is grounded in the techniques of stochastic calculus, utilizing a Markov diffusion process to model the structural system with random...... initial conditions. This transformation facilitates the derivation of differential equations which govern the evolution of the unconditional statistical moments of response. Primary consideration is given to linear systems and systems with odd polynomial nonlinearities, for in these cases...

  19. Metaheuristic approaches to order sequencing on a unidirectional picking line

    Directory of Open Access Journals (Sweden)

    AP de Villiers

    2013-06-01

    Full Text Available In this paper the sequencing of orders on a unidirectional picking line is considered. The aim of the order sequencing is to minimise the number of cycles travelled by a picker within the picking line to complete all orders. A tabu search, simulated annealing, genetic algorithm, generalised extremal optimisation and a random local search are presented as possible solution approaches. Computational results based on real life data instances are presented for these metaheuristics and compared to the performance of a lower bound and the solutions used in practise. The random local search exhibits the best overall solution quality, however, the generalised extremal optimisation approach delivers comparable results in considerably shorter computational times.

  20. The Ising model coupled to 2d orders

    Science.gov (United States)

    Glaser, Lisa

    2018-04-01

    In this article we make first steps in coupling matter to causal set theory in the path integral. We explore the case of the Ising model coupled to the 2d discrete Einstein Hilbert action, restricted to the 2d orders. We probe the phase diagram in terms of the Wick rotation parameter β and the Ising coupling j and find that the matter and the causal sets together give rise to an interesting phase structure. The couplings give rise to five different phases. The causal sets take on random or crystalline characteristics as described in Surya (2012 Class. Quantum Grav. 29 132001) and the Ising model can be correlated or uncorrelated on the random orders and correlated, uncorrelated or anti-correlated on the crystalline orders. We find that at least one new phase transition arises, in which the Ising spins push the causal set into the crystalline phase.

  1. Computer generation of random deviates

    International Nuclear Information System (INIS)

    Cormack, John

    1991-01-01

    The need for random deviates arises in many scientific applications. In medical physics, Monte Carlo simulations have been used in radiology, radiation therapy and nuclear medicine. Specific instances include the modelling of x-ray scattering processes and the addition of random noise to images or curves in order to assess the effects of various processing procedures. Reliable sources of random deviates with statistical properties indistinguishable from true random deviates are a fundamental necessity for such tasks. This paper provides a review of computer algorithms which can be used to generate uniform random deviates and other distributions of interest to medical physicists, along with a few caveats relating to various problems and pitfalls which can occur. Source code listings for the generators discussed (in FORTRAN, Turbo-PASCAL and Data General ASSEMBLER) are available on request from the authors. 27 refs., 3 tabs., 5 figs

  2. Emergence of Lévy Walks from Second-Order Stochastic Optimization

    Science.gov (United States)

    Kuśmierz, Łukasz; Toyoizumi, Taro

    2017-12-01

    In natural foraging, many organisms seem to perform two different types of motile search: directed search (taxis) and random search. The former is observed when the environment provides cues to guide motion towards a target. The latter involves no apparent memory or information processing and can be mathematically modeled by random walks. We show that both types of search can be generated by a common mechanism in which Lévy flights or Lévy walks emerge from a second-order gradient-based search with noisy observations. No explicit switching mechanism is required—instead, continuous transitions between the directed and random motions emerge depending on the Hessian matrix of the cost function. For a wide range of scenarios, the Lévy tail index is α =1 , consistent with previous observations in foraging organisms. These results suggest that adopting a second-order optimization method can be a useful strategy to combine efficient features of directed and random search.

  3. First-order phase transition in the quantum spin glass at T=0

    Energy Technology Data Exchange (ETDEWEB)

    Viana, J. Roberto; Nogueira, Yamilles; Sousa, J. Ricardo de

    2003-05-26

    The van Hemmen model with transverse and random longitudinal field is studied to analyze the tricritical behavior in the quantum Ising spin glass at T=0. The free energy and order parameter are calculated for two types of probability distributions: Gaussian and bimodal. We obtain the phase diagram in the {omega}-H plane, where {omega} and H are the transverse and random longitudinal fields, respectively. For the case of Gaussian distribution the phase transition is of second order, while the bimodal distribution we observe second-order transition for high-transverse field and first-order transition for small transverse field, with a tricritical point in the phase diagram.

  4. First-order phase transition in the quantum spin glass at T=0

    International Nuclear Information System (INIS)

    Viana, J. Roberto; Nogueira, Yamilles; Sousa, J. Ricardo de

    2003-01-01

    The van Hemmen model with transverse and random longitudinal field is studied to analyze the tricritical behavior in the quantum Ising spin glass at T=0. The free energy and order parameter are calculated for two types of probability distributions: Gaussian and bimodal. We obtain the phase diagram in the Ω-H plane, where Ω and H are the transverse and random longitudinal fields, respectively. For the case of Gaussian distribution the phase transition is of second order, while the bimodal distribution we observe second-order transition for high-transverse field and first-order transition for small transverse field, with a tricritical point in the phase diagram

  5. Sampling problems for randomly broken sticks

    Energy Technology Data Exchange (ETDEWEB)

    Huillet, Thierry [Laboratoire de Physique Theorique et Modelisation, CNRS-UMR 8089 et Universite de Cergy-Pontoise, 5 mail Gay-Lussac, 95031, Neuville sur Oise (France)

    2003-04-11

    Consider the random partitioning model of a population (represented by a stick of length 1) into n species (fragments) with identically distributed random weights (sizes). Upon ranking the fragments' weights according to ascending sizes, let S{sub m:n} be the size of the mth smallest fragment. Assume that some observer is sampling such populations as follows: drop at random k points (the sample size) onto this stick and record the corresponding numbers of visited fragments. We shall investigate the following sampling problems: (1) what is the sample size if the sampling is carried out until the first visit of the smallest fragment (size S{sub 1:n})? (2) For a given sample size, have all the fragments of the stick been visited at least once or not? This question is related to Feller's random coupon collector problem. (3) In what order are new fragments being discovered and what is the random number of samples separating the discovery of consecutive new fragments until exhaustion of the list? For this problem, the distribution of the size-biased permutation of the species' weights, as the sequence of their weights in their order of appearance is needed and studied.

  6. The reactivity of clay materials in a context of metallic corrosion: application to disposal of radioactive wastes in deep argillaceous formations; Reactivite des materiaux argileux dans un contexte de corrosion metallique: application au stockage des dechets radioactifs en site argileux

    Energy Technology Data Exchange (ETDEWEB)

    Perronnet, M

    2004-10-15

    In order to confine radioactive wastes in deep settings, it is envisaged to use some natural clay materials and bentonites. Their stability when in contact with metallic iron, main component of the canisters, is studied. These studies show that the reactivity of such materials is mainly controlled by those of their di-octahedral smectites and kaolinites. On the contrary, the presence of sulfides stops the Fe(0)-clays reaction. The kind of reaction products depends on the quantity of available metallic iron. When pH is over 7, the Fe(0) is oxidized consecutive to a physical contact with the oxidant agents of the smectite (H{sup +}, OH{sup -} et Fe{sup 3+}). This reaction is favored by the heterogeneities of the lateral surfaces of the smectite, which then describes a micro-environments in which some serpentines grow up if the iron supply is sufficient. Such new-crystallization imply a decrease of the confinement properties of the clay barrier. (author)

  7. The reactivity of clay materials in a context of metallic corrosion: application to disposal of radioactive wastes in deep argillaceous formations

    International Nuclear Information System (INIS)

    Perronnet, M.

    2004-10-01

    In order to confine radioactive wastes in deep settings, it is envisaged to use some natural clay materials and bentonites. Their stability when in contact with metallic iron, main component of the canisters, is studied. These studies show that the reactivity of such materials is mainly controlled by those of their di-octahedral smectites and kaolinites. On the contrary, the presence of sulfides stops the Fe(0)-clays reaction. The kind of reaction products depends on the quantity of available metallic iron. When pH is over 7, the Fe(0) is oxidized consecutive to a physical contact with the oxidant agents of the smectite (H + , OH - et Fe 3+ ). This reaction is favored by the heterogeneities of the lateral surfaces of the smectite, which then describes a micro-environments in which some serpentines grow up if the iron supply is sufficient. Such new-crystallization imply a decrease of the confinement properties of the clay barrier. (author)

  8. Characterisation of bentonites from Kutch, India and Milos, Greece - some candidate tunnel back-fill materials?

    International Nuclear Information System (INIS)

    Olsson, Siv; Karnland, Ola

    2009-12-01

    During the past decades comprehensive investigations have been made on bentonite clays in order to find optimal components of the multi-barrier system of repositories for radioactive waste. The present study gives a mineralogical characterisation of some selected bentonites, in order to supply some of the necessary background data on the bentonites for evaluating their potential as tunnel back-fill materials. Two bentonites from the island of Milos, Greece (Milos BF 04 and BF 08), and two bentonites from Kutch, India (Kutch BF 04 and BF 08) were analysed for their grain size distribution, cation exchange properties and chemical composition. The mineralogical composition was determined by X-ray diffraction analysis and evaluated quantitatively by use of the Siroquant software. Both the bulk bentonite and the 63 μm. The bentonite is distinguished by a high content of dolomite and calcite, which make up almost 25% of the bulk sample. The major accessory minerals are K-feldspars and plagioclase, whereas the content of sulphur-bearing minerals is very low (0.06% total S). Smectite makes up around 60% of the bulk sample, which has a CEC value of 73 meq/100 g. The pool of interlayer cations has a composition Mg>Ca>>Na>>K. The X-ray diffraction characteristics and the high potassium content (1.03% K 2 O) of the Na>Mg>>K. The 2 O) which indicates that also this smectite may be interstratified with a few percent illitic layers. Based on the charge distribution the smectite should be classified as montmorillonite but in this case Fe predominates over Mg in the octahedral sheet. The structural formula suggests that this smectite has the lowest total layer charge of the smectites examined. Kutch BF 04 contains essentially no particles >63 μm. The bentonite has a high content of titanium and iron-rich accessory minerals, such as anatase, magnetite, hematite and goethite. Other accessory minerals of significance are feldspars and quartz, whereas the content of sulphur

  9. Multidemand Multisource Order Quantity Allocation with Multiple Transportation Alternatives

    Directory of Open Access Journals (Sweden)

    Jun Gang

    2015-01-01

    Full Text Available This paper focuses on a multidemand multisource order quantity allocation problem with multiple transportation alternatives. To solve this problem, a bilevel multiobjective programming model under a mixed uncertain environment is proposed. Two levels of decision makers are considered in the model. On the upper level, the purchaser aims to allocate order quantity to multiple suppliers for each demand node with the consideration of three objectives: total purchase cost minimization, total delay risk minimization, and total defect risk minimization. On the lower level, each supplier attempts to optimize the transportation alternatives with total transportation and penalty costs minimization as the objective. In contrast to prior studies, considering the information asymmetry in the bilevel decision, random and fuzzy random variables are used to model uncertain parameters of the construction company and the suppliers. To solve the bilevel model, a solution method based on Kuhn-Tucker conditions, sectional genetic algorithm, and fuzzy random simulation is proposed. Finally, the applicability of the proposed model and algorithm is evaluated through a practical case from a large scale construction project. The results show that the proposed model and algorithm are efficient in dealing with practical order quantity allocation problems.

  10. Multi-Criteria Model for Determining Order Size

    Directory of Open Access Journals (Sweden)

    Katarzyna Jakowska-Suwalska

    2013-01-01

    Full Text Available A multi-criteria model for determining the order size for materials used in production has been presented. It was assumed that the consumption rate of each material is a random variable with a known probability distribution. Using such a model, in which the purchase cost of materials ordered is limited, three criteria were considered: order size, probability of a lack of materials in the production process, and deviations in the order size from the consumption rate in past periods. Based on an example, it has been shown how to use the model to determine the order sizes for polyurethane adhesive and wood in a hard-coal mine. (original abstract

  11. Staggered chiral random matrix theory

    International Nuclear Information System (INIS)

    Osborn, James C.

    2011-01-01

    We present a random matrix theory for the staggered lattice QCD Dirac operator. The staggered random matrix theory is equivalent to the zero-momentum limit of the staggered chiral Lagrangian and includes all taste breaking terms at their leading order. This is an extension of previous work which only included some of the taste breaking terms. We will also present some results for the taste breaking contributions to the partition function and the Dirac eigenvalues.

  12. On the limit distribution of lower extreme generalized order statistics

    Indian Academy of Sciences (India)

    Abstract. In a wide subclass of generalized order statistics (gOs), which contains most of the known and important models of ordered random variables, weak conver- gence of lower extremes are developed. A recent result of extreme value theory of m−gOs (as well as the classical extreme value theory of ordinary order ...

  13. The swelling behavior of montmorillonite as affected by the grain size by in situ X-ray diffraction experiments

    International Nuclear Information System (INIS)

    Morodome, S.; Kawamura, K.; Owada, H.; Yahagi, R.; Kobayashi, I.

    2012-01-01

    Document available in extended abstract form only. In many existing researches, the swelling behavior and impermeability of smectitic engineered barrier materials in disposal facilities of radioactive waste was investigated. In the RWMC-project, the effect of smectite content on the mechanical and hydraulic behavior of smectitic materials is investigated and modeled to introduce into THMC analysis. However, since smectite is a natural resource, physical and chemical properties are different with places of production. In order to model the swelling behavior and impermeability of smectitic materials, not only the smectite content but also layer charge and crystal size will be the primary factors. In addition, smectite types and impurity minerals contents or soluble salts affect bentonite characteristic, as well. In this research, in order to focus on the effect of grain size of smectite, the swelling behavior of smectitic materials which are the same place of production but are different grain size were investigated. The smectitic material used in this study was Kunipia-F (Kunimine Industry Co. Ltd., Japan), which is from the Tukinuno Mine, Yamagata prefecture, Japan, and is purified montmorillonite produced by hydraulic elutriation. It is considered that the montmorillonite, Kunipia-F, has large crystal size, and for example Kunipia-F is able to make a sheet when drying weak solution. The grain size was conditioned by jet mill pulverizer. The pulverizing was conducted by making each other collide with high speed. The grain size of the intact and pulverized samples was measured by using of the laser scattering particle distribution analyzer and SEM. The swelling behavior was measured by in situ X-ray diffraction using of a sample chamber which can control the temperature and humidity precisely. The result of the laser scattering analysis denoted that the pulverized sample fined down expressly. The difference of the crystal aspect ratio of the pre- and post

  14. Discovery and Description of Giant Submarine Smectite Cones on the Seafloor in Eyjafjordur, Northern Iceland, and a Novel Thermal Microbial Habitat

    Science.gov (United States)

    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

  15. Search for a perfect generator of random numbers

    International Nuclear Information System (INIS)

    Musyck, E.

    1977-01-01

    Theoretical tests have been carried out by COVEYOU and MAC PHERSON to verify the applications of the LEHMER algorithm. In a similar way, a theoretical method is proposed to evaluate in a rigorous way the random character of numbers generated by a shift register. This theory introduces the concept of ''degree of randomness'' of the elements, taken in a definite order, of a shift register. It permits making the judicious choice of the elements of the shift register which will produce the bits of the random numbers. On the other hand, a calculation method is developed in order to verify the primitive character of any shift register of high complexity. A new test, called ''slice test'', of empirical and theoretical use is also described; it constitutes a significant contribution to the understanding of certain properties of pseudo-random sequences. As a practical example, a random number generator structure formed with 32 bits, built out of a shift register with 61 elements and 60 modulo-2 adder circuits was made. The author is convinced that this generator can be considered to be practically perfect for all empirical applications of random numbers, particularly for the solution of Monte-Carlo problems. (author)

  16. Characterisation of bentonites from Kutch, India and Milos, Greece - some candidate tunnel back-fill materials?

    Energy Technology Data Exchange (ETDEWEB)

    Olsson, Siv; Karnland, Ola (Clay Technology AB, Lund (Sweden))

    2009-12-15

    During the past decades comprehensive investigations have been made on bentonite clays in order to find optimal components of the multi-barrier system of repositories for radioactive waste. The present study gives a mineralogical characterisation of some selected bentonites, in order to supply some of the necessary background data on the bentonites for evaluating their potential as tunnel back-fill materials. Two bentonites from the island of Milos, Greece (Milos BF 04 and BF 08), and two bentonites from Kutch, India (Kutch BF 04 and BF 08) were analysed for their grain size distribution, cation exchange properties and chemical composition. The mineralogical composition was determined by X-ray diffraction analysis and evaluated quantitatively by use of the Siroquant software. Both the bulk bentonite and the <1mum fraction were analyzed when relevant. Prior to the chemical analyses the <1 mum fractions were converted to homo-ionic clays and purified by dialysis. The chemical data were used for calculating the structural formula of the smectites. Milos BF 04 contains ca. 10% particles >63 mum. The bentonite is distinguished by a high content of dolomite and calcite, which make up almost 25% of the bulk sample. The major accessory minerals are K-feldspars and plagioclase, whereas the content of sulphur-bearing minerals is very low (0.06% total S). Smectite makes up around 60% of the bulk sample, which has a CEC value of 73 meq/100 g. The pool of interlayer cations has a composition Mg>Ca>>Na>>K. The X-ray diffraction characteristics and the high potassium content (1.03% K{sub 2}O) of the <1 mum fraction suggest that the smectite is interstratified with ca. 10% illitic layers. Based on the charge distribution the smectite should be classified as montmorillonite and according to the structural formula, Mg predominates over Fe in the octahedral sheet. However, remnants of Mg-carbonates, if present, may be a source of error in the formula calculation. Milos BF 08 has a

  17. On the Limit Distribution of Lower Extreme Generalized Order Statistics

    Indian Academy of Sciences (India)

    In a wide subclass of generalized order statistics ( g O s ) , which contains most of the known and important models of ordered random variables, weak convergence of lower extremes are developed. A recent result of extreme value theory of m − g O s (as well as the classical extreme value theory of ordinary order statistics) ...

  18. Reconstructing random media

    International Nuclear Information System (INIS)

    Yeong, C.L.; Torquato, S.

    1998-01-01

    We formulate a procedure to reconstruct the structure of general random heterogeneous media from limited morphological information by extending the methodology of Rintoul and Torquato [J. Colloid Interface Sci. 186, 467 (1997)] developed for dispersions. The procedure has the advantages that it is simple to implement and generally applicable to multidimensional, multiphase, and anisotropic structures. Furthermore, an extremely useful feature is that it can incorporate any type and number of correlation functions in order to provide as much morphological information as is necessary for accurate reconstruction. We consider a variety of one- and two-dimensional reconstructions, including periodic and random arrays of rods, various distribution of disks, Debye random media, and a Fontainebleau sandstone sample. We also use our algorithm to construct heterogeneous media from specified hypothetical correlation functions, including an exponentially damped, oscillating function as well as physically unrealizable ones. copyright 1998 The American Physical Society

  19. Sensitivity analysis of ranked data: from order statistics to quantiles

    NARCIS (Netherlands)

    Heidergott, B.F.; Volk-Makarewicz, W.

    2015-01-01

    In this paper we provide the mathematical theory for sensitivity analysis of order statistics of continuous random variables, where the sensitivity is with respect to a distributional parameter. Sensitivity analysis of order statistics over a finite number of observations is discussed before

  20. Mechanisms and models for bentonite erosion

    International Nuclear Information System (INIS)

    Neretnieks, Ivars; Longcheng Liu; Moreno, Luis

    2009-12-01

    in earlier and present SKB investigations contain tens of percent of non-smectic accessory minerals. These materials do not exhibit the strong repulsive forces as the smectites do because the surface charge density is essentially negligible at the circum neutral pH expected. Furthermore the particle size of these materials is one to two orders of magnitude larger than those of the smectite particles, so they are much less mobile and they could not be lost as colloids in the water. It is highly likely that such particles will penetrate some distance into the fracture and form a porous network through which the smectite particles must pass. We have investigated the idea that the accessory particles left behind could form a porous bed with small enough pores to slow down smectite loss after a short initial period when some smectite is lost leaving the accessory mineral particles behind to form the filter bed. A few cm long region of detritus material in the fracture has a strong restraining effect on the rate of smectite loss by colloidal diffusion through the pores. A set of experiments where highly compacted beds of smectite between metal filters flushed by water on the outside show that sodium smectite readily penetrates filters with 2 μm pore size or larger but are stopped by 0.5 μm filters. A set of experiments where mm thick beds have been used to filter a suspension of smectite particles show very promising results. Our overall conclusions are that a buffer with practically only smectite cannot be proved not to erode significantly with the flowrates and water compositions expected. On the other hand, we strongly believe that the accessory minerals will effectively hinder major loss of buffer. There is also the possibility to add material with optimally chosen particle sizes to further strengthen the filtering and straining of smectite colloids

  1. Molecular dynamics simulations of the electrical double layer on smectite surfaces contacting concentrated mixed electrolyte (NaCl-CaCl2)

    Energy Technology Data Exchange (ETDEWEB)

    Bourg, I.C.; Sposito, G.

    2011-04-01

    We report new molecular dynamics results elucidating the structure of the electrical double layer (EDL) on smectite surfaces contacting mixed NaCl-CaCl{sup 2} electrolyte solutions in the range of concentrations relevant to pore waters in geologic repositories for CO{sub 2} or high-level radioactive waste (0.34-1.83 mol{sub c} dm{sup -3}). Our results confirm the existence of three distinct ion adsorption planes (0-, {beta}-, and d-planes), often assumed in EDL models, but with two important qualifications: (1) the location of the {beta}- 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{sup +} ion pairs. Therefore, at concentrations 0.34 mol{sub c} dm{sup -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.

  2. An introduction to random interlacements

    CERN Document Server

    Drewitz, Alexander; Sapozhnikov, Artëm

    2014-01-01

    This book gives a self-contained introduction to the theory of random interlacements. The intended reader of the book is a graduate student with a background in probability theory who wants to learn about the fundamental results and methods of this rapidly emerging field of research. The model was introduced by Sznitman in 2007 in order to describe the local picture left by the trace of a random walk on a large discrete torus when it runs up to times proportional to the volume of the torus. Random interlacements is a new percolation model on the d-dimensional lattice. The main results covered by the book include the full proof of the local convergence of random walk trace on the torus to random interlacements and the full proof of the percolation phase transition of the vacant set of random interlacements in all dimensions. The reader will become familiar with the techniques relevant to working with the underlying Poisson Process and the method of multi-scale renormalization, which helps in overcoming the ch...

  3. Fluctuation microscopy: a probe of medium range order

    International Nuclear Information System (INIS)

    Treacy, M M J; Gibson, J M; Fan, L; Paterson, D J; McNulty, I

    2005-01-01

    Fluctuation microscopy is a hybrid diffraction-imaging technique that detects medium range order in amorphous materials by examining spatial fluctuations in coherent scattering. These fluctuations appear as speckle in images and diffraction patterns. The volume of material contributing to the speckle is determined by the point-spread function (the resolution) of the imaging optics and the sample thickness. The spatial periodicities being probed are related to the diffraction vector. Statistical analysis of the speckle allows the random and non-random (ordered) contributions to be discriminated. The image resolution that gives the maximum speckle contrast, as determined by the normalized variance of the image intensity, is determined by the characteristic length scale of the ordering. Because medium range ordering length scales can extend out to about the tenth coordination shell, fluctuation microscopy tends to be a low image resolution technique. This review presents the kinematical scattering theory underpinning fluctuation microscopy and a description of fluctuation electron microscopy as it has been employed in the transmission electron microscope for studying amorphous materials. Recent results using soft x-rays for studying nanoscale materials are also presented. We summarize outstanding issues and point to possible future directions for fluctuation microscopy as a technique

  4. Discrete random walk models for space-time fractional diffusion

    International Nuclear Information System (INIS)

    Gorenflo, Rudolf; Mainardi, Francesco; Moretti, Daniele; Pagnini, Gianni; Paradisi, Paolo

    2002-01-01

    A physical-mathematical approach to anomalous diffusion may be based on generalized diffusion equations (containing derivatives of fractional order in space or/and time) and related random walk models. By space-time fractional diffusion equation we mean an evolution equation obtained from the standard linear diffusion equation by replacing the second-order space derivative with a Riesz-Feller derivative of order α is part of (0,2] and skewness θ (moduleθ≤{α,2-α}), and the first-order time derivative with a Caputo derivative of order β is part of (0,1]. Such evolution equation implies for the flux a fractional Fick's law which accounts for spatial and temporal non-locality. The fundamental solution (for the Cauchy problem) of the fractional diffusion equation can be interpreted as a probability density evolving in time of a peculiar self-similar stochastic process that we view as a generalized diffusion process. By adopting appropriate finite-difference schemes of solution, we generate models of random walk discrete in space and time suitable for simulating random variables whose spatial probability density evolves in time according to this fractional diffusion equation

  5. Ordering kinetics in quasi-one-dimensional Ising-like systems

    International Nuclear Information System (INIS)

    Mueller, M.; Paul, W.

    1993-01-01

    Results are presented of a Monte Carlo simulation of the kinetics of ordering in the two-dimensional nearest-neighbor Ising model in an L x M geometry with two free boundaries of length M much-gt L. This model can be viewed as representing an adsorbant on a stepped surface with mean terrace width L. The authors follow the ordering kinetics after quenches to temperatures 0.25 ≤T/T c ≤1 starting from a random initial configuration at a coverage of Θ=0.5 in the corresponding lattice gas picture. The systems evolve in time according to a Glauber kinetics with nonconserved order parameter. The equilibrium structure is given by a one-dimensional sequence of ordered domains. The ordering process evolves from a short initial two-dimensional ordering process through a crossover region to a quasi-one-dimensional behavior. The whole process is diffusive (inverse half-width of the structure factor peak 1/Δq parallel ∝ √t), in contrast to a model proposed by Kawasaki et al., where an intermediate logarithmic growth law is expected. All results are completely describable in the picture of an annihilating random walk (ARW) of domain walls. 36 refs., 16 figs

  6. Monomer-dimer problem on random planar honeycomb lattice

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Haizhen [School of Mathematical Sciences, Xiamen University, Xiamen 361005, Fujian (China); Department of Mathematics, Qinghai Normal University, Xining 810008, Qinghai (China); Zhang, Fuji; Qian, Jianguo, E-mail: jqqian@xmu.edu.cn [School of Mathematical Sciences, Xiamen University, Xiamen 361005, Fujian (China)

    2014-02-15

    We consider the monomer-dimer (MD) problem on a random planar honeycomb lattice model, namely, the random multiple chain. This is a lattice system with non-periodic boundary condition, whose generating process is inspired by the growth of single walled zigzag carbon nanotubes. By applying algebraic and combinatorial techniques we establish a calculating expression of the MD partition function for bipartite graphs, which corresponds to the permanent of a matrix. Further, by using the transfer matrix argument we show that the computing problem of the permanent of high order matrix can be converted into some lower order matrices for this family of lattices, based on which we derive an explicit recurrence formula for evaluating the MD partition function of multiple chains and random multiple chains. Finally, we analyze the expectation of the number of monomer-dimer arrangements on a random multiple chain and the asymptotic behavior of the annealed MD entropy when the multiple chain becomes infinite in width and length, respectively.

  7. Brain potentials index executive functions during random number generation.

    Science.gov (United States)

    Joppich, Gregor; Däuper, Jan; Dengler, Reinhard; Johannes, Sönke; Rodriguez-Fornells, Antoni; Münte, Thomas F

    2004-06-01

    The generation of random sequences is considered to tax different executive functions. To explore the involvement of these functions further, brain potentials were recorded in 16 healthy young adults while either engaging in random number generation (RNG) by pressing the number keys on a computer keyboard in a random sequence or in ordered number generation (ONG) necessitating key presses in the canonical order. Key presses were paced by an external auditory stimulus to yield either fast (1 press/800 ms) or slow (1 press/1300 ms) sequences in separate runs. Attentional demands of random and ordered tasks were assessed by the introduction of a secondary task (key-press to a target tone). The P3 amplitude to the target tone of this secondary task was reduced during RNG, reflecting the greater consumption of attentional resources during RNG. Moreover, RNG led to a left frontal negativity peaking 140 ms after the onset of the pacing stimulus, whenever the subjects produced a true random response. This negativity could be attributed to the left dorsolateral prefrontal cortex and was absent when numbers were repeated. This negativity was interpreted as an index for the inhibition of habitual responses. Finally, in response locked ERPs a negative component was apparent peaking about 50 ms after the key-press that was more prominent during RNG. Source localization suggested a medial frontal source. This effect was tentatively interpreted as a reflection of the greater monitoring demands during random sequence generation.

  8. On nonlinear reduced order modeling

    International Nuclear Information System (INIS)

    Abdel-Khalik, Hany S.

    2011-01-01

    When applied to a model that receives n input parameters and predicts m output responses, a reduced order model estimates the variations in the m outputs of the original model resulting from variations in its n inputs. While direct execution of the forward model could provide these variations, reduced order modeling plays an indispensable role for most real-world complex models. This follows because the solutions of complex models are expensive in terms of required computational overhead, thus rendering their repeated execution computationally infeasible. To overcome this problem, reduced order modeling determines a relationship (often referred to as a surrogate model) between the input and output variations that is much cheaper to evaluate than the original model. While it is desirable to seek highly accurate surrogates, the computational overhead becomes quickly intractable especially for high dimensional model, n ≫ 10. In this manuscript, we demonstrate a novel reduced order modeling method for building a surrogate model that employs only 'local first-order' derivatives and a new tensor-free expansion to efficiently identify all the important features of the original model to reach a predetermined level of accuracy. This is achieved via a hybrid approach in which local first-order derivatives (i.e., gradient) of a pseudo response (a pseudo response represents a random linear combination of original model’s responses) are randomly sampled utilizing a tensor-free expansion around some reference point, with the resulting gradient information aggregated in a subspace (denoted by the active subspace) of dimension much less than the dimension of the input parameters space. The active subspace is then sampled employing the state-of-the-art techniques for global sampling methods. The proposed method hybridizes the use of global sampling methods for uncertainty quantification and local variational methods for sensitivity analysis. In a similar manner to

  9. Comparison of tool feed influence in CNC polishing between a novel circular-random path and other pseudo-random paths.

    Science.gov (United States)

    Takizawa, Ken; Beaucamp, Anthony

    2017-09-18

    A new category of circular pseudo-random paths is proposed in order to suppress repetitive patterns and improve surface waviness on ultra-precision polished surfaces. Random paths in prior research had many corners, therefore deceleration of the polishing tool affected the surface waviness. The new random path can suppress velocity changes of the polishing tool and thus restrict degradation of the surface waviness, making it suitable for applications with stringent mid-spatial-frequency requirements such as photomask blanks for EUV lithography.

  10. Decomposition of conditional probability for high-order symbolic Markov chains

    Science.gov (United States)

    Melnik, S. S.; Usatenko, O. V.

    2017-07-01

    The main goal of this paper is to develop an estimate for the conditional probability function of random stationary ergodic symbolic sequences with elements belonging to a finite alphabet. We elaborate on a decomposition procedure for the conditional probability function of sequences considered to be high-order Markov chains. We represent the conditional probability function as the sum of multilinear memory function monomials of different orders (from zero up to the chain order). This allows us to introduce a family of Markov chain models and to construct artificial sequences via a method of successive iterations, taking into account at each step increasingly high correlations among random elements. At weak correlations, the memory functions are uniquely expressed in terms of the high-order symbolic correlation functions. The proposed method fills the gap between two approaches, namely the likelihood estimation and the additive Markov chains. The obtained results may have applications for sequential approximation of artificial neural network training.

  11. Numerical study of microphase separation in gels and random media

    International Nuclear Information System (INIS)

    Uchida, Nariya

    2004-01-01

    Microphase separation in gels and random media is numerically studied using a Ginzburg-Landau model. A random field destroys long-range orientational (lamellar) order and gives rise to a disordered bicontinuous morphology. The dependence of the correlation length on the field strength is distinct from that of random-field magnets

  12. Mechanisms and models for bentonite erosion

    Energy Technology Data Exchange (ETDEWEB)

    Neretnieks, Ivars; Longcheng Liu; Moreno, Luis (Dept. of Chemical Engineering and Technology, School of Chemical Science and Engineering, Royal Inst. of Technology, KTH, Stockholm (Sweden))

    2009-12-15

    in earlier and present SKB investigations contain tens of percent of non-smectic accessory minerals. These materials do not exhibit the strong repulsive forces as the smectites do because the surface charge density is essentially negligible at the circum neutral pH expected. Furthermore the particle size of these materials is one to two orders of magnitude larger than those of the smectite particles, so they are much less mobile and they could not be A few cm long region of detritus material in the fracture has a strong restraining effect on the rate of smectite loss by colloidal diffusion through the pores. A set of experiments where highly compacted beds of smectite between metal filters flushed by water on the outside show that sodium smectite readily penetrates filters with 2 mum pore size or larger but are stopped by 0.5 mum filters. A set of experiments where mm thick beds have been used to filter a suspension of smectite particles show very promising results.

  13. Reliability-based design optimization via high order response surface method

    International Nuclear Information System (INIS)

    Li, Hong Shuang

    2013-01-01

    To reduce the computational effort of reliability-based design optimization (RBDO), the response surface method (RSM) has been widely used to evaluate reliability constraints. We propose an efficient methodology for solving RBDO problems based on an improved high order response surface method (HORSM) that takes advantage of an efficient sampling method, Hermite polynomials and uncertainty contribution concept to construct a high order response surface function with cross terms for reliability analysis. The sampling method generates supporting points from Gauss-Hermite quadrature points, which can be used to approximate response surface function without cross terms, to identify the highest order of each random variable and to determine the significant variables connected with point estimate method. The cross terms between two significant random variables are added to the response surface function to improve the approximation accuracy. Integrating the nested strategy, the improved HORSM is explored in solving RBDO problems. Additionally, a sampling based reliability sensitivity analysis method is employed to reduce the computational effort further when design variables are distributional parameters of input random variables. The proposed methodology is applied on two test problems to validate its accuracy and efficiency. The proposed methodology is more efficient than first order reliability method based RBDO and Monte Carlo simulation based RBDO, and enables the use of RBDO as a practical design tool.

  14. Random balance designs for the estimation of first order global sensitivity indices

    International Nuclear Information System (INIS)

    Tarantola, S.; Gatelli, D.; Mara, T.A.

    2006-01-01

    We present two methods for the estimation of main effects in global sensitivity analysis. The methods adopt Satterthwaite's application of random balance designs in regression problems, and extend it to sensitivity analysis of model output for non-linear, non-additive models. Finite as well as infinite ranges for model input factors are allowed. The methods are easier to implement than any other method available for global sensitivity analysis, and reduce significantly the computational cost of the analysis. We test their performance on different test cases, including an international benchmark on safety assessment for nuclear waste disposal originally carried out by OECD/NEA

  15. Autonomous Byte Stream Randomizer

    Science.gov (United States)

    Paloulian, George K.; Woo, Simon S.; Chow, Edward T.

    2013-01-01

    Net-centric networking environments are often faced with limited resources and must utilize bandwidth as efficiently as possible. In networking environments that span wide areas, the data transmission has to be efficient without any redundant or exuberant metadata. The Autonomous Byte Stream Randomizer software provides an extra level of security on top of existing data encryption methods. Randomizing the data s byte stream adds an extra layer to existing data protection methods, thus making it harder for an attacker to decrypt protected data. Based on a generated crypto-graphically secure random seed, a random sequence of numbers is used to intelligently and efficiently swap the organization of bytes in data using the unbiased and memory-efficient in-place Fisher-Yates shuffle method. Swapping bytes and reorganizing the crucial structure of the byte data renders the data file unreadable and leaves the data in a deconstructed state. This deconstruction adds an extra level of security requiring the byte stream to be reconstructed with the random seed in order to be readable. Once the data byte stream has been randomized, the software enables the data to be distributed to N nodes in an environment. Each piece of the data in randomized and distributed form is a separate entity unreadable on its own right, but when combined with all N pieces, is able to be reconstructed back to one. Reconstruction requires possession of the key used for randomizing the bytes, leading to the generation of the same cryptographically secure random sequence of numbers used to randomize the data. This software is a cornerstone capability possessing the ability to generate the same cryptographically secure sequence on different machines and time intervals, thus allowing this software to be used more heavily in net-centric environments where data transfer bandwidth is limited.

  16. Rain dance: the role of randomization in clinical trials

    Directory of Open Access Journals (Sweden)

    Diniz JB

    2016-07-01

    Full Text Available Juliana Belo Diniz,1 Victor Fossaluza,2 Carlos Alberto de Bragança Pereira,1,2 Sergio Wechsler2 1Institute of Psychiatry, Clinics Hospital University of São Paulo Medical School, 2Department of Statistics, Institute of Mathematics and Statistics, University of São Paulo, São Paulo, Brazil Abstract: Randomized clinical trials are the gold standard for testing efficacy of treatment interventions. However, although randomization protects against deliberately biased samples, it does not guarantee random imbalances will not occur. Methods of intentional allocation that can overcome such deficiency of randomization have been developed, but are less frequently applied than randomization. Initially, we introduce a fictitious case example to revise and discuss the reasons of researchers' resistance to intentionally allocate instead of simply randomizing. We then introduce a real case example to evaluate the performance of an intentional protocol for allocation based on compositional data balance. A real case of allocation of 50 patients in two arms was compared with an optimal allocation of global instead of sequential arrivals. Performance was measured by a weighted average of Aitchison distances, between arms, of prognostic factors. To compare the intentional allocation with simple random allocation, 50,000 arrival orderings of 50 patients were simulated. To each one of the orders, both kinds of allocations into two arms were considered. Intentional allocation performed as well as optimal allocation in the case considered. In addition, out of the 50,000 simulated orders, 61% of them performed better with intentional allocation than random allocation. Hence, we conclude that intentional allocation should be encouraged in the design of future interventional clinical trials as a way to prevent unbalanced samples. Our sequential method is a viable alternative to overcome technical difficulties for study designs that require sequential inclusion of

  17. Encouraging GPs to undertake screening and a brief intervention in order to reduce problem drinking: a randomized controlled trial

    DEFF Research Database (Denmark)

    Hansen, Lars Jørgen; Olivarius, Niels de Fine; Beich, Anders

    1999-01-01

    intervention, problem drinking, randomized controlled trial, family practice, marketing of health services......intervention, problem drinking, randomized controlled trial, family practice, marketing of health services...

  18. Molecular dynamics simulations of the electrical double layer on smectite surfaces contacting concentrated mixed electrolyte (NaCl-CaCl2) solutions.

    Science.gov (United States)

    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.

  19. Fourth-Order Spatial Correlation of Thermal Light

    International Nuclear Information System (INIS)

    Wen Feng; Zhang Xun; Sun Jia; Song Jian-Ping; Zhang Yan-Peng; Xue Xin-Xin

    2014-01-01

    We investigate the fourth-order spatial correlation properties of pseudo-thermal light in the photon counting regime, and apply the Klyshko advanced-wave picture to describe the process of four-photon coincidence counting measurement. We deduce the theory of a proof-of-principle four-photon coincidence counting configuration, and find that if the four randomly radiated photons come from the same radiation area and are indistinguishable in principle, the fourth-order correlation of them is 24 times larger than that when four photons come from different radiation areas. In addition, we also show that the higher-order spatial correlation function can be decomposed into multiple lower-order correlation functions, and the contrast and visibility of low-order correlation peaks are less than those of higher orders, while the resolutions all are identical. This study may be useful for better understanding the four-photon interference and multi-channel correlation imaging

  20. Birth order, neuroticism, and psychoticism among Iranian children.

    Science.gov (United States)

    Makaremi, A

    1992-12-01

    To investigate the effects of birth order, parents' education, and parents' occupation on four dimensions of the Junior Eysenck Personality Questionnaire, 262 elementary school students (100 boys and 162 girls) were selected randomly from four elementary schools in Shiraz. Analyses showed the main effects of birth order were significant on Neuroticism and Lie scales. Further, the effects of mothers' occupation on the Lie scale and fathers' education on the Neuroticism scale were significant.

  1. On randomly interrupted diffusion

    International Nuclear Information System (INIS)

    Luczka, J.

    1993-01-01

    Processes driven by randomly interrupted Gaussian white noise are considered. An evolution equation for single-event probability distributions in presented. Stationary states are considered as a solution of a second-order ordinary differential equation with two imposed conditions. A linear model is analyzed and its stationary distributions are explicitly given. (author). 10 refs

  2. Random balance designs for the estimation of first order global sensitivity indices

    Energy Technology Data Exchange (ETDEWEB)

    Tarantola, S. [Joint Research Centre, European Commission, Institute of the Protection and Security of the Citizen, TP 361, Via E. Fermi 1, 21020 Ispra (Vatican City State, Holy See,) (Italy)]. E-mail: stefano.tarantola@jrc.it; Gatelli, D. [Joint Research Centre, European Commission, Institute of the Protection and Security of the Citizen, TP 361, Via E. Fermi 1, 21020 Ispra (VA) (Italy); Mara, T.A. [Laboratory of Industrial engineering, University of Reunion Island, BP 7151, 15 avenue Rene Cassin, 97 715 Saint-Denis (France)

    2006-06-15

    We present two methods for the estimation of main effects in global sensitivity analysis. The methods adopt Satterthwaite's application of random balance designs in regression problems, and extend it to sensitivity analysis of model output for non-linear, non-additive models. Finite as well as infinite ranges for model input factors are allowed. The methods are easier to implement than any other method available for global sensitivity analysis, and reduce significantly the computational cost of the analysis. We test their performance on different test cases, including an international benchmark on safety assessment for nuclear waste disposal originally carried out by OECD/NEA.

  3. Modelling of erosion of bentonite gel by gel/sol flow

    Energy Technology Data Exchange (ETDEWEB)

    Moreno, Luis; Neretnieks, Ivars; Longcheng Liu (Chemical Engineering and Technology, School of Chemical Science and Engineering, Royal Institute of Technology, Stockholm (Sweden))

    2010-11-15

    order of a metre per year the gel may penetrate several metres into the fracture when steady state is reached. The simulations were made with only sodium as counterion. Most simulations had sodium concentrations below the critical coagulation concentration, CCC. In the compacted bentonite at the fracture mouth it was 10 mM and 0.1 mM in the approaching water. At these concentrations the gel is expansive and can turn into a sol releasing colloidal particles. The low ion concentration has a strong impact on the fluid viscosity, which increases with decreasing ionic strength. At the same time, however the repulsion forces between the smectite particles increase causing a quicker expansion. Simulations with higher sodium concentrations had a marginal influence on the erosion rate. For the highest water flow rates the smectite loss could be up to 0.3 kg per year for one canister. This is more than one order of magnitude larger than what could be reached by smectite particle diffusion alone if fluid flow was neglected. In experiments in downward facing slits (fractures) it has been found that bentonite releases gel agglomerates much faster than expected. These are released and sediment also under conditions where it is expected that the smectite particles should have separated into individual smectite sheets, which would not noticeably be influenced by gravity. The reasons for this behaviour are not understood. In the modelling it is assumed that there are no other larger non-smectite particles that would be left behind to gradually build up a bed of particles that could act as filter, slowing down or even straining further smectite penetration into the fracture. The modelling results could therefore be highly pessimistic because bentonites contain tens of percent of accessory minerals that do not form colloids and the presence of which may cause the expansion to be slowed down by friction against the fracture walls

  4. Modelling of erosion of bentonite gel by gel/sol flow

    International Nuclear Information System (INIS)

    Moreno, Luis; Neretnieks, Ivars; Longcheng Liu

    2010-11-01

    order of a metre per year the gel may penetrate several metres into the fracture when steady state is reached. The simulations were made with only sodium as counterion. Most simulations had sodium concentrations below the critical coagulation concentration, CCC. In the compacted bentonite at the fracture mouth it was 10 mM and 0.1 mM in the approaching water. At these concentrations the gel is expansive and can turn into a sol releasing colloidal particles. The low ion concentration has a strong impact on the fluid viscosity, which increases with decreasing ionic strength. At the same time, however the repulsion forces between the smectite particles increase causing a quicker expansion. Simulations with higher sodium concentrations had a marginal influence on the erosion rate. For the highest water flow rates the smectite loss could be up to 0.3 kg per year for one canister. This is more than one order of magnitude larger than what could be reached by smectite particle diffusion alone if fluid flow was neglected. In experiments in downward facing slits (fractures) it has been found that bentonite releases gel agglomerates much faster than expected. These are released and sediment also under conditions where it is expected that the smectite particles should have separated into individual smectite sheets, which would not noticeably be influenced by gravity. The reasons for this behaviour are not understood. In the modelling it is assumed that there are no other larger non-smectite particles that would be left behind to gradually build up a bed of particles that could act as filter, slowing down or even straining further smectite penetration into the fracture. The modelling results could therefore be highly pessimistic because bentonites contain tens of percent of accessory minerals that do not form colloids and the presence of which may cause the expansion to be slowed down by friction against the fracture walls

  5. Random coil chemical shifts in acidic 8 M urea: Implementation of random coil shift data in NMRView

    International Nuclear Information System (INIS)

    Schwarzinger, Stephan; Kroon, Gerard J.A.; Foss, Ted R.; Wright, Peter E.; Dyson, H. Jane

    2000-01-01

    Studies of proteins unfolded in acid or chemical denaturant can help in unraveling events during the earliest phases of protein folding. In order for meaningful comparisons to be made of residual structure in unfolded states, it is necessary to use random coil chemical shifts that are valid for the experimental system under study. We present a set of random coil chemical shifts obtained for model peptides under experimental conditions used in studies of denatured proteins. This new set, together with previously published data sets, has been incorporated into a software interface for NMRView, allowing selection of the random coil data set that fits the experimental conditions best

  6. Highly selective direct determination of chlorate ions by using a newly developed potentiometric electrode based on modified smectite.

    Science.gov (United States)

    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.

  7. Alzheimer random walk

    Science.gov (United States)

    Odagaki, Takashi; Kasuya, Keisuke

    2017-09-01

    Using the Monte Carlo simulation, we investigate a memory-impaired self-avoiding walk on a square lattice in which a random walker marks each of sites visited with a given probability p and makes a random walk avoiding the marked sites. Namely, p = 0 and p = 1 correspond to the simple random walk and the self-avoiding walk, respectively. When p> 0, there is a finite probability that the walker is trapped. We show that the trap time distribution can well be fitted by Stacy's Weibull distribution b(a/b){a+1}/{b}[Γ({a+1}/{b})]-1x^a\\exp(-a/bx^b)} where a and b are fitting parameters depending on p. We also find that the mean trap time diverges at p = 0 as p- α with α = 1.89. In order to produce sufficient number of long walks, we exploit the pivot algorithm and obtain the mean square displacement and its Flory exponent ν(p) as functions of p. We find that the exponent determined for 1000 step walks interpolates both limits ν(0) for the simple random walk and ν(1) for the self-avoiding walk as [ ν(p) - ν(0) ] / [ ν(1) - ν(0) ] = pβ with β = 0.388 when p ≪ 0.1 and β = 0.0822 when p ≫ 0.1. Contribution to the Topical Issue "Continuous Time Random Walk Still Trendy: Fifty-year History, Current State and Outlook", edited by Ryszard Kutner and Jaume Masoliver.

  8. Residual Defect Density in Random Disks Deposits.

    Science.gov (United States)

    Topic, Nikola; Pöschel, Thorsten; Gallas, Jason A C

    2015-08-03

    We investigate the residual distribution of structural defects in very tall packings of disks deposited randomly in large channels. By performing simulations involving the sedimentation of up to 50 × 10(9) particles we find all deposits to consistently show a non-zero residual density of defects obeying a characteristic power-law as a function of the channel width. This remarkable finding corrects the widespread belief that the density of defects should vanish algebraically with growing height. A non-zero residual density of defects implies a type of long-range spatial order in the packing, as opposed to only local ordering. In addition, we find deposits of particles to involve considerably less randomness than generally presumed.

  9. Sorption behavior of neptunium on bentonite -- Effect of calcium ion on the sorption

    International Nuclear Information System (INIS)

    Kozai, Naofumi; Ohnuki, Toshihiko; Muraoka, Susumu

    1995-01-01

    The sorption behavior of neptunium on bentonite was studied with batch type sorption and desorption experiments over a pH range of 2 to 8. A series of parallel studies using Na-smectite, Ca-smectite and admixtures of Na-smectite and calcite quantified the capacity of Ca 2+ (which occurs in bentonite as an exchangeable cation of smectite and as a component of calcite) to inhibit the sorption of neptunium. The distribution coefficient (K d ) of neptunium for bentonite was constant from pH 2 to 7, while for pure Na-smectite K d increased below pH 5 due to specific sorption of neptunium on Na-smectite. Specific sorption was defined as occurring when neptunium could be desorbed by a strong acid (1 M HCl) but was stable in the presence of 1 M KCl. It was found that the quantity of neptunium sorbed on Na-smectite was inversely proportional to the concentration of Ca 2+ in solution, an effect most pronounced at pH 2+ limits the specific sorption capacity of Na-smectite for neptunium. Similarly, in the mixture of Na-smectite and calcite, sufficient Ca 2+ was solubilized to depress neptunium sorption. This investigation demonstrates that Ca 2+ contained in bentonite as exchangeable cation and released from calcite reduces the specific sorption of neptunium

  10. Monte Carlo studies of two-dimensional random-anisotropy magnets

    Science.gov (United States)

    Denholm, D. R.; Sluckin, T. J.

    1993-07-01

    We have carried out a systematic set of Monte Carlo simulations of the Harris-Plischke-Zuckermann lattice model of random magnetic anisotropy on a two-dimensional square lattice, using the classical Metropolis algorithm. We have considered varying temperature T, external magnetic field H (both in the reproducible and irreproducible limits), time scale of the simulation τ in Monte Carlo steps and anisotropy ratio D/J. In the absence of randomness this model reduces to the XY model in two dimensions, which possesses the familiar Kosterlitz-Thouless low-temperature phase with algebraic but no long-range order. In the presence of random anisotropy we find evidence of a low-temperature phase with some disordered features, which might be identified with a spin-glass phase. The low-temperature Kosterlitz-Thouless phase survives at intermediate temperatures for low randomness, but is no longer present for large D/J. We have also studied the high-H approach to perfect order, for which there are theoretical predictions due to Chudnovsky.

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

    Science.gov (United States)

    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®.

  12. Topological orders in rigid states

    International Nuclear Information System (INIS)

    Wen, X.G.

    1990-01-01

    The authors study a new kind of ordering topological order in rigid states (the states with no local gapless excitations). This paper concentrates on characterization of the different topological orders. As an example the authors discuss in detail chiral spin states of 2+1 dimensional spin systems. Chiral spin states are described by the topological Chern-Simons theories in the continuum limit. The authors show that the topological orders can be characterized by a non-Abelian gauge structure over the moduli space which parametrizes a family of the model Hamiltonians supporting topologically ordered ground states. In 2 + 1 dimensions, the non-Abelian gauge structure determines possible fractional statistics of the quasi-particle excitations over the topologically ordered ground states. The dynamics of the low lying global excitations is shown to be independent of random spatial dependent perturbations. The ground state degeneracy and the non-Abelian gauge structures discussed in this paper are very robust, even against those perturbations that break translation symmetry. The authors also discuss the symmetry properties of the degenerate ground states of chiral spin states. The authors find that some degenerate ground states of chiral spin states on torus carry non-trivial quantum numbers of the 90 degrees rotation

  13. Evidence of significant bias in an elementary random number generator

    International Nuclear Information System (INIS)

    Borgwaldt, H.; Brandl, V.

    1981-03-01

    An elementary pseudo random number generator for isotropically distributed unit vectors in 3-dimensional space has ben tested for bias. This generator uses the IBM-suplied routine RANDU and a transparent rejection technique. The tests show clearly that non-randomness in the pseudo random numbers generated by the primary IBM generator leads to bias in the order of 1 percent in estimates obtained from the secondary random number generator. FORTRAN listings of 4 variants of the random number generator called by a simple test programme and output listings are included for direct reference. (orig.) [de

  14. Effect of calorie or exercise labels on menus on calories and macronutrients ordered and calories from specific foods in Hispanic participants: a randomized study.

    Science.gov (United States)

    Shah, Meena; Bouza, Brooke; Adams-Huet, Beverley; Jaffery, Manall; Esposito, Phil; Dart, Lyn

    2016-12-01

    The effect of menu labels on food choices is unknown in Hispanics. This study evaluated the impact of menu labels on calories and macronutrients ordered in Hispanics. 372 Hispanics (18-65 years) were randomly assigned to menus with no labels (NL) (n=127), rank-ordered calorie labels plus a statement on energy needs per meal (CL) (n=123), or rank-ordered exercise labels showing minutes of brisk walking necessary to burn the food calories (EL) (n=122). The menus had identical food choices. Participants were instructed to select foods from the assigned menu as if having lunch in a fast food restaurant. One-way analysis of variance found no difference in calories ordered (median (25th and 75th centiles)) by menu condition (NL: 785.0 (465.0, 1010.0) kcal; CL: 790.0 (510.0, 1020.0) kcal; EL: 752.5 (520.0, 1033.8) kcal; p=0.75). Calories from specific foods and macronutrient intake were not different by menu condition. Menu label use was 26.8% in the CL and 25.4% in the EL condition. Calories ordered were not different between those who used and those who did not use the labels. Regression analysis showed that perception of being overweight (p=0.02), selecting foods based on health value (p<0.0001), and meeting exercise guidelines (p<0.0001) were associated with fewer calories ordered. Logistic regression showed that selecting foods based on health value (p=0.01) was associated with higher food label use. Menu labels did not affect food choices in Hispanic participants. Future studies should determine if nutrition, exercise, and weight perception counseling prior to menu labels intervention would result in better food choices. NCT02804503; post-results. Copyright © 2016 American Federation for Medical Research.

  15. Randomized Oversampling for Generalized Multiscale Finite Element Methods

    KAUST Repository

    Calo, Victor M.

    2016-03-23

    In this paper, we develop efficient multiscale methods for flows in heterogeneous media. We use the generalized multiscale finite element (GMsFEM) framework. GMsFEM approximates the solution space locally using a few multiscale basis functions. This approximation selects an appropriate snapshot space and a local spectral decomposition, e.g., the use of oversampled regions, in order to achieve an efficient model reduction. However, the successful construction of snapshot spaces may be costly if too many local problems need to be solved in order to obtain these spaces. We use a moderate quantity of local solutions (or snapshot vectors) with random boundary conditions on oversampled regions with zero forcing to deliver an efficient methodology. Motivated by the randomized algorithm presented in [P. G. Martinsson, V. Rokhlin, and M. Tygert, A Randomized Algorithm for the approximation of Matrices, YALEU/DCS/TR-1361, Yale University, 2006], we consider a snapshot space which consists of harmonic extensions of random boundary conditions defined in a domain larger than the target region. Furthermore, we perform an eigenvalue decomposition in this small space. We study the application of randomized sampling for GMsFEM in conjunction with adaptivity, where local multiscale spaces are adaptively enriched. Convergence analysis is provided. We present representative numerical results to validate the method proposed.

  16. Hydration of swelling clay and bacteria interaction. An experimental in situ reaction study

    International Nuclear Information System (INIS)

    Berger, J.

    2008-01-01

    This study reports on the physical-chemical behaviour of swelling di-octahedral clays (smectites) and their interaction with aqueous solutions and bacteria (Shewanella putrefaciens). Experimental results are presented for compacted clays, hydrated under confined volume conditions, using a new type of reaction-cell (the 'wet-cell' of Warr and Hoffman, 2004) that was designed for in situ X-ray diffraction (XRD) measurement. For comparison, dispersed clay systems were studied using standard batch solutions subjected to varying degrees of agitation. The combination of time-dependent in situ XRD measurements with gravimetric measurements and calculated diffraction patterns using the CALCMIX software (Plancon and Drits, 1999) allowed to successful quantification of the dynamics of water uptake and storage. This analytical procedure combined with published water vapour adsorption data enabled determination of the abundance of structured water layers, developed in the interlayer space, and the amount of water contained in different storage sites (interlayers, surfaces and pore spaces). Qualitative information on surface area and textural organization was also estimated based on calculated changes in the average particle thickness and the organization of water layer structures (ordering). Abiotic smectite hydration experiments, using a range of natural and industrial bentonites (SWy-2, IBECO, MX80, TIXOTON), focused on defining the role of the interlayer cation, variable clay packing densities and the ionic strength of the infiltrating solution. The rate of smectite hydration, as expected, was seen to be highly dependent on the type of interlayer cation (enhanced for Ca as opposed to Na) and the ionic strength of solution (enhanced uptake rates with saline solutions, particularly as they infiltrate Na-smectite). A range of dynamic changes in micro textural state occurred as a function of packing density. These changes explain the differences in hydration behaviour observed

  17. Hydration of swelling clay and bacteria interaction. An experimental in situ reaction study; Hydratation des argiles gonflantes et influence des bacteries. Etude experimentale de reaction in situ

    Energy Technology Data Exchange (ETDEWEB)

    Berger, J

    2008-01-15

    This study reports on the physical-chemical behaviour of swelling di-octahedral clays (smectites) and their interaction with aqueous solutions and bacteria (Shewanella putrefaciens). Experimental results are presented for compacted clays, hydrated under confined volume conditions, using a new type of reaction-cell (the 'wet-cell' of Warr and Hoffman, 2004) that was designed for in situ X-ray diffraction (XRD) measurement. For comparison, dispersed clay systems were studied using standard batch solutions subjected to varying degrees of agitation. The combination of time-dependent in situ XRD measurements with gravimetric measurements and calculated diffraction patterns using the CALCMIX software (Plancon and Drits, 1999) allowed to successful quantification of the dynamics of water uptake and storage. This analytical procedure combined with published water vapour adsorption data enabled determination of the abundance of structured water layers, developed in the interlayer space, and the amount of water contained in different storage sites (interlayers, surfaces and pore spaces). Qualitative information on surface area and textural organization was also estimated based on calculated changes in the average particle thickness and the organization of water layer structures (ordering). Abiotic smectite hydration experiments, using a range of natural and industrial bentonites (SWy-2, IBECO, MX80, TIXOTON), focused on defining the role of the interlayer cation, variable clay packing densities and the ionic strength of the infiltrating solution. The rate of smectite hydration, as expected, was seen to be highly dependent on the type of interlayer cation (enhanced for Ca as opposed to Na) and the ionic strength of solution (enhanced uptake rates with saline solutions, particularly as they infiltrate Na-smectite). A range of dynamic changes in micro textural state occurred as a function of packing density. These changes explain the differences in hydration behaviour

  18. The relationship of dynamical heterogeneity to the Adam-Gibbs and random first-order transition theories of glass formation.

    Science.gov (United States)

    Starr, Francis W; Douglas, Jack F; Sastry, Srikanth

    2013-03-28

    We carefully examine common measures of dynamical heterogeneity for a model polymer melt and test how these scales compare with those hypothesized by the Adam and Gibbs (AG) and random first-order transition (RFOT) theories of relaxation in glass-forming liquids. To this end, we first analyze clusters of highly mobile particles, the string-like collective motion of these mobile particles, and clusters of relative low mobility. We show that the time scale of the high-mobility clusters and strings is associated with a diffusive time scale, while the low-mobility particles' time scale relates to a structural relaxation time. The difference of the characteristic times for the high- and low-mobility particles naturally explains the well-known decoupling of diffusion and structural relaxation time scales. Despite the inherent difference of dynamics between high- and low-mobility particles, we find a high degree of similarity in the geometrical structure of these particle clusters. In particular, we show that the fractal dimensions of these clusters are consistent with those of swollen branched polymers or branched polymers with screened excluded-volume interactions, corresponding to lattice animals and percolation clusters, respectively. In contrast, the fractal dimension of the strings crosses over from that of self-avoiding walks for small strings, to simple random walks for longer, more strongly interacting, strings, corresponding to flexible polymers with screened excluded-volume interactions. We examine the appropriateness of identifying the size scales of either mobile particle clusters or strings with the size of cooperatively rearranging regions (CRR) in the AG and RFOT theories. We find that the string size appears to be the most consistent measure of CRR for both the AG and RFOT models. Identifying strings or clusters with the "mosaic" length of the RFOT model relaxes the conventional assumption that the "entropic droplets" are compact. We also confirm the

  19. First- and second-order processing in transient stereopsis.

    Science.gov (United States)

    Edwards, M; Pope, D R; Schor, C M

    2000-01-01

    Large-field stimuli were used to investigate the interaction of first- and second-order pathways in transient-stereo processing. Stimuli consisted of sinewave modulations in either the mean luminance (first-order stimulus) or the contrast (second-order stimulus) of a dynamic-random-dot field. The main results of the present study are that: (1) Depth could be extracted with both the first-order and second-order stimuli; (2) Depth could be extracted from dichoptically mixed first- and second-order stimuli, however, the same stimuli, when presented as a motion sequence, did not result in a motion percept. Based upon these findings we conclude that the transient-stereo system processes both first- and second-order signals, and that these two signals are pooled prior to the extraction of transient depth. This finding of interaction between first- and second-order stereoscopic processing is different from the independence that has been found with the motion system.

  20. Ferrimagnetic Properties of Bond Dilution Mixed Blume-Capel Model with Random Single-Ion Anisotropy

    International Nuclear Information System (INIS)

    Liu Lei; Yan Shilei

    2005-01-01

    We study the ferrimagnetic properties of spin 1/2 and spin-1 systems by means of the effective field theory. The system is considered in the framework of bond dilution mixed Blume-Capel model (BCM) with random single-ion anisotropy. The investigation of phase diagrams and magnetization curves indicates the existence of induced magnetic ordering and single or multi-compensation points. Special emphasis is placed on the influence of bond dilution and random single-ion anisotropy on normal or induced magnetic ordering states and single or multi-compensation points. Normal magnetic ordering states take on new phase diagrams with increasing randomness (bond and anisotropy), while anisotropy induced magnetic ordering states are always occurrence no matter whether concentration of anisotropy is large or small. Existence and disappearance of compensation points rely strongly on bond dilution and random single-ion anisotropy. Some results have not been revealed in previous papers and predicted by Neel theory of ferrimagnetism.

  1. Thermodynamic understanding on swelling pressure of bentonite buffer

    International Nuclear Information System (INIS)

    Sato, Haruo

    2007-01-01

    Smectite (montmorillonite) is a major clay mineral constituent of the bentonite buffer and backfilling materials to be used for the geological disposal of high-level radioactive waste. Swelling pressure of the bentonite buffer occurring in the permeation process of moisture was estimated based on thermodynamic theory and the thermodynamic data of interlayer water in smectite in this study. The relative partial molar Gibbs free energies (ΔG H2O ) of water on the smectite surface were measured as a function of water content (0-83%) in a dry density range of 0.6-0.9 Mg/m 3 . Purified Na-smectite of which interlayer cations were exchanged with Na + ions and soluble salts were completely removed, was used in this study. Obtained ΔG H2O decreased with an increase of water content in the range of water content lower than about 40%, and similar trends were obtained to data of Kunipia-F bentonite (Na-bentonite) of which smectite content was approximately 100 wt.%. From the specific surface area of smectite (ca. 800 m 2 /g) and the correlation between ΔG H2O and water content, water affected from the surface of smectite was estimated to be up to approximately 2 water layers. Swelling pressure versus smectite partial density (montmorillonite partial density) was estimated based on ΔG H2O from the chemical potential balance of water in equilibrium between the free water and moisturized smectite, and compared to data measured for various kinds of bentonites of which smectite contents were respectively different. The estimated swelling pressures were in good agreement with the measured data. (author)

  2. Birth order and post-traumatic stress disorder.

    Science.gov (United States)

    Green, Ben; Griffiths, Emily C

    2014-01-01

    To compare the birth order of patients with post-traumatic stress disorder (PTSD) and adjustment disorder (AD) with population norms. 83 PTSD patients and 104 AD control patients from a psychiatric trauma clinic were diagnosed according to DCR-10 guidelines. A family history was taken as to number of siblings, and their birth order. We compared the distribution of birth order for each patient group against birth order distributions expected by chance for the same years of birth using UK population-level birth order from the Office for National Statistics. Psychiatric patients with PTSD were more likely to be from a large family, specifically to be the fifth child or later (OR 4.78, p birth order between AD patients and the general population. People with PTSD are more likely to be the youngest children from large families than expected from a random sample of people born in the same years. This association with birth order was not found for another psychiatric diagnosis AD from the same clinic. We discuss possible psychosocial and biological causes, and implications for further research.

  3. Quality control and characterization of bentonite materials

    International Nuclear Information System (INIS)

    Kiviranta, L.; Kumpulainen, S.

    2011-12-01

    Before bentonite material is taken into use in performance testing, the quality of the material needs to be checked. Three high grade bentonite materials: two natural Nabentonites from Wyoming, and one natural Ca-bentonite from Milos, were characterized. Each material was characterized using duplicate or triplicate samples in order to study variability in material quality in batches. The procedure consisted of basic acceptance testing (water ratio, CEC, swelling index, liquid limit, and granule size distribution), advanced acceptance testing (exchangeable cations, chemical and mineralogical composition, density, swelling pressure and hydraulic conductivity) and complementary testing (herein surface area, water absorption capacity, montmorillonite composition, grain size distribution and plastic limit). All three materials qualified the requirements set for buffer bentonite for CEC, smectite content, swelling pressure, and hydraulic conductivity. Wyoming bentonites contained approximately 88 wt.% of smectite, and Milos bentonite 79 wt.% of smectite and 3 wt.% of illite. Precision of smectite analyses was ±2 %, and variances in composition of parallel samples within analytical errors, at least for Wyoming bentonites. Accuracy of quantitative analyses for trace minerals such as gypsum, pyrite or carbonates, was however low. As the concentrations of these trace minerals are important for Eh or pH buffering reactions or development of bentonite pore water composition, normative concentrations are recommended to be used instead of mineralogically determined concentrations. The swelling pressures and hydraulic conductivities of different materials were compared using EMDD. Swelling pressure was relatively higher for studied Cabentonite than for the studied Na-bentonites and the difference could not be explained with different smectite contents. Hydraulic conductivities seemed to be similar for all materials. The results of index tests correlated with the smectite content

  4. Random clustering ferns for multimodal object recognition

    OpenAIRE

    Villamizar Vergel, Michael Alejandro; Garrell Zulueta, Anais; Sanfeliu Cortés, Alberto; Moreno-Noguer, Francesc

    2017-01-01

    The final publication is available at link.springer.com We propose an efficient and robust method for the recognition of objects exhibiting multiple intra-class modes, where each one is associated with a particular object appearance. The proposed method, called random clustering ferns, combines synergically a single and real-time classifier, based on the boosted assembling of extremely randomized trees (ferns), with an unsupervised and probabilistic approach in order to recognize efficient...

  5. Random ordinary differential equations and their numerical solution

    CERN Document Server

    Han, Xiaoying

    2017-01-01

    This book is intended to make recent results on the derivation of higher order numerical schemes for random ordinary differential equations (RODEs) available to a broader readership, and to familiarize readers with RODEs themselves as well as the closely associated theory of random dynamical systems. In addition, it demonstrates how RODEs are being used in the biological sciences, where non-Gaussian and bounded noise are often more realistic than the Gaussian white noise in stochastic differential equations (SODEs).   RODEs are used in many important applications and play a fundamental role in the theory of random dynamical systems.  They can be analyzed pathwise with deterministic calculus, but require further treatment beyond that of classical ODE theory due to the lack of smoothness in their time variable. Although classical numerical schemes for ODEs can be used pathwise for RODEs, they rarely attain their traditional order since the solutions of RODEs do not have sufficient smoothness to have Taylor ...

  6. 2D gravity, random surfaces and all that

    International Nuclear Information System (INIS)

    Ambjoern, J.

    1990-11-01

    I review the recent progress in 2d gravity and discuss the new numerical simulations for 2d gravity and for random surfaces in d>2. The random surface theories of interest in d>2 have extrinsic curvature terms, and for a finite value of the extrinsic curvature coupling there seems to be a second order phase transition where the string tension scales. (orig.)

  7. Numerical Inversion for the Multiple Fractional Orders in the Multiterm TFDE

    OpenAIRE

    Sun, Chunlong; Li, Gongsheng; Jia, Xianzheng

    2017-01-01

    The fractional order in a fractional diffusion model is a key parameter which characterizes the anomalous diffusion behaviors. This paper deals with an inverse problem of determining the multiple fractional orders in the multiterm time-fractional diffusion equation (TFDE for short) from numerics. The homotopy regularization algorithm is applied to solve the inversion problem using the finite data at one interior point in the space domain. The inversion fractional orders with random noisy data...

  8. Order-disorder transition of vortex matter in Mg0.95B2

    International Nuclear Information System (INIS)

    Oliveira, A.A.M.; Sharma, P.A.; Hur, N.; Cheong, S-W.; Ortiz, W.A.

    2008-01-01

    Third-harmonic susceptibility has been employed to probe the order-disorder transition of vortex matter of a good-quality sample of MgB 2 with random disorder. In the major part of the temperature interval, the measured boundary line can be adjusted by a power-law function, in accordance with theoretical models for the melting of the ordered phase of a 3D vortex-glass. For larger temperatures, however, thermally-induced depinning anticipates disorder, which is also predictable for the vortex matter behavior of a clean system with small amounts of randomly distributed disorder, as is the case of the Mg 0.95 B 2 sample studied here

  9. Random unitary operations and quantum Darwinism

    International Nuclear Information System (INIS)

    Balaneskovic, Nenad

    2016-01-01

    We study the behavior of Quantum Darwinism (Zurek, Nature Physics 5, 181-188 (2009)) within the iterative, random unitary operations qubit-model of pure decoherence (Novotn'y et al, New Jour. Phys. 13, 053052 (2011)). We conclude that Quantum Darwinism, which describes the quantum mechanical evolution of an open system from the point of view of its environment, is not a generic phenomenon, but depends on the specific form of initial states and on the type of system-environment interactions. Furthermore, we show that within the random unitary model the concept of Quantum Darwinism enables one to explicitly construct and specify artificial initial states of environment that allow to store information about an open system of interest and its pointer-basis with maximal efficiency. Furthermore, we investigate the behavior of Quantum Darwinism after introducing dissipation into the iterative random unitary qubit model with pure decoherence in accord with V. Scarani et al (Phys. Rev. Lett. 88, 097905 (2002)) and reconstruct the corresponding dissipative attractor space. We conclude that in Zurek's qubit model Quantum Darwinism depends on the order in which pure decoherence and dissipation act upon an initial state of the entire system. We show explicitly that introducing dissipation into the random unitary evolution model in general suppresses Quantum Darwinism (regardless of the order in which decoherence and dissipation are applied) for all positive non-zero values of the dissipation strength parameter, even for those initial state configurations which, in Zurek's qubit model and in the random unitary model with pure decoherence, would lead to Quantum Darwinism. Finally, we discuss what happens with Quantum Darwinism after introducing into the iterative random unitary qubit model with pure decoherence (asymmetric) dissipation and dephasing, again in accord with V. Scarani et al (Phys. Rev. Lett. 88, 097905 (2002)), and reconstruct the corresponding

  10. A new simple technique for improving the random properties of chaos-based cryptosystems

    Science.gov (United States)

    Garcia-Bosque, M.; Pérez-Resa, A.; Sánchez-Azqueta, C.; Celma, S.

    2018-03-01

    A new technique for improving the security of chaos-based stream ciphers has been proposed and tested experimentally. This technique manages to improve the randomness properties of the generated keystream by preventing the system to fall into short period cycles due to digitation. In order to test this technique, a stream cipher based on a Skew Tent Map algorithm has been implemented on a Virtex 7 FPGA. The randomness of the keystream generated by this system has been compared to the randomness of the keystream generated by the same system with the proposed randomness-enhancement technique. By subjecting both keystreams to the National Institute of Standards and Technology (NIST) tests, we have proved that our method can considerably improve the randomness of the generated keystreams. In order to incorporate our randomness-enhancement technique, only 41 extra slices have been needed, proving that, apart from effective, this method is also efficient in terms of area and hardware resources.

  11. Quantum random walks using quantum accelerator modes

    International Nuclear Information System (INIS)

    Ma, Z.-Y.; Burnett, K.; D'Arcy, M. B.; Gardiner, S. A.

    2006-01-01

    We discuss the use of high-order quantum accelerator modes to achieve an atom optical realization of a biased quantum random walk. We first discuss how one can create coexistent quantum accelerator modes, and hence how momentum transfer that depends on the atoms' internal state can be achieved. When combined with microwave driving of the transition between the states, a different type of atomic beam splitter results. This permits the realization of a biased quantum random walk through quantum accelerator modes

  12. Random matrices and random difference equations

    International Nuclear Information System (INIS)

    Uppuluri, V.R.R.

    1975-01-01

    Mathematical models leading to products of random matrices and random difference equations are discussed. A one-compartment model with random behavior is introduced, and it is shown how the average concentration in the discrete time model converges to the exponential function. This is of relevance to understanding how radioactivity gets trapped in bone structure in blood--bone systems. The ideas are then generalized to two-compartment models and mammillary systems, where products of random matrices appear in a natural way. The appearance of products of random matrices in applications in demography and control theory is considered. Then random sequences motivated from the following problems are studied: constant pulsing and random decay models, random pulsing and constant decay models, and random pulsing and random decay models

  13. Climatic and palaeoceanographic changes during the Pliensbachian (Early Jurassic) inferred from clay mineralogy and stable isotope (C-O) geochemistry (NW Europe)

    DEFF Research Database (Denmark)

    Bougeault, Cédric; Pellenard, Pierre; Deconinck, Jean François

    2017-01-01

    -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...

  14. Nonparametric Bayesian predictive distributions for future order statistics

    Science.gov (United States)

    Richard A. Johnson; James W. Evans; David W. Green

    1999-01-01

    We derive the predictive distribution for a specified order statistic, determined from a future random sample, under a Dirichlet process prior. Two variants of the approach are treated and some limiting cases studied. A practical application to monitoring the strength of lumber is discussed including choices of prior expectation and comparisons made to a Bayesian...

  15. Considering clay rock heterogeneity in radionuclide retention

    International Nuclear Information System (INIS)

    Grambow, B.; Montavon, G.; Tournassat, C.; Giffaut, E.; Altmann, S.

    2010-01-01

    Document available in extended abstract form only. The Callovo-Oxfordian clay rock formation has a strong retention capacity for radionuclides, a favorable condition for the implementation of a nuclear waste repository. Principal retaining minerals are illite, and inter-stratified illite/smectite (I/S). Radionuclide retention has been studied on illite, illite/smectite and on clay rock obtained from different locations and data for retention on bentonite (80% smectite) are available. Sorption depends on the type of mineral, composition of mineralogical assemblages, individual mineral ion exchange capacities, ion distribution on exchange sites, specific surface areas, surface site types and densities for surface complexation as well as on water/rock ratios, temperature etc. As a consequence of mineralogical and textural variations, radionuclide retention properties are expected to vary with depth in the Callovo-Oxfordian formation. Using a simple additivity approach for the case of sorption of Cs and Ni it is shown that models and databases for illite and bentonite can be used to describe sorption in heterogeneous clay rock systems. A surface complexation/ion-exchange model as proposed by Bradbury and Baeyens without electrostatic contributions, was used directly as far as acid base properties are concerned but was modified with respect to sorption constants, in order to describe Na-, Ca, and Cs montmorillonite and bentonite MX-80 with a single set of surface complexation constants and also to account for carbonate and sulphate concentrations in groundwater. The model is integrated into the geochemical code PHREEQC considering dissolution/ precipitation/solubility constraints of accessory minerals (calcite, illite, celestite, quartz). Site densities for surface complexation and ion exchange are derived from the mass fractions of illite and of smectite in illite/smectite obtained from an overall fit of measured CEC data from all samples of the EST205 drill core

  16. Simulation of Higher-Order Electrical Circuits with Stochastic Parameters via SDEs

    Directory of Open Access Journals (Sweden)

    BRANCIK, L.

    2013-02-01

    Full Text Available The paper deals with a technique for the simulation of higher-order electrical circuits with parameters varying randomly. The principle consists in the utilization of the theory of stochastic differential equations (SDE, namely the vector form of the ordinary SDEs. Random changes of both excitation voltage and some parameters of passive circuit elements are considered, and circuit responses are analyzed. The voltage and/or current responses are computed and represented in the form of the sample means accompanied by their confidence intervals to provide reliable estimates. The method is applied to analyze responses of the circuit models of optional orders, specially those consisting of a cascade connection of the RLGC networks. To develop the model equations the state-variable method is used, afterwards a corresponding vector SDE is formulated and a stochastic Euler numerical method applied. To verify the results the deterministic responses are also computed by the help of the PSpice simulator or the numerical inverse Laplace transforms (NILT procedure in MATLAB, while removing random terms from the circuit model.

  17. Fractional Processes and Fractional-Order Signal Processing Techniques and Applications

    CERN Document Server

    Sheng, Hu; Qiu, TianShuang

    2012-01-01

    Fractional processes are widely found in science, technology and engineering systems. In Fractional Processes and Fractional-order Signal Processing, some complex random signals, characterized by the presence of a heavy-tailed distribution or non-negligible dependence between distant observations (local and long memory), are introduced and examined from the ‘fractional’ perspective using simulation, fractional-order modeling and filtering and realization of fractional-order systems. These fractional-order signal processing (FOSP) techniques are based on fractional calculus, the fractional Fourier transform and fractional lower-order moments. Fractional Processes and Fractional-order Signal Processing: • presents fractional processes of fixed, variable and distributed order studied as the output of fractional-order differential systems; • introduces FOSP techniques and the fractional signals and fractional systems point of view; • details real-world-application examples of FOSP techniques to demonstr...

  18. Factors affecting medication-order processing time.

    Science.gov (United States)

    Beaman, M A; Kotzan, J A

    1982-11-01

    The factors affecting medication-order processing time at one hospital were studied. The order processing time was determined by directly observing the time to process randomly selected new drug orders on all three work shifts during two one-week periods. An order could list more than one drug for an individual patient. The observer recorded the nature, location, and cost of the drugs ordered, as well as the time to process the order. The time and type of interruptions also were noted. The time to process a drug order was classified as six dependent variables: (1) total time, (2) work time, (3) check time, (4) waiting time I--time from arrival on the dumbwaiter until work was initiated, (5) waiting time II--time between completion of the work and initiation of checking, and (6) waiting time III--time after the check was completed until the order left on the dumbwaiter. The significant predictors of each of the six dependent variables were determined using stepwise multiple regression. The total time to process a prescription order was 58.33 +/- 48.72 minutes; the urgency status of the order was the only significant determinant of total time. Urgency status also significantly predicted the three waiting-time variables. Interruptions and the number of drugs on the order were significant determinants of work time and check time. Each telephone interruption increased the work time by 1.72 minutes. While the results of this study cannot be generalized to other institutions, pharmacy managers can use the method of determining factors that affect medication-order processing time to identify problem areas in their institutions.

  19. Fast physical random bit generation with chaotic semiconductor lasers

    Science.gov (United States)

    Uchida, Atsushi; Amano, Kazuya; Inoue, Masaki; Hirano, Kunihito; Naito, Sunao; Someya, Hiroyuki; Oowada, Isao; Kurashige, Takayuki; Shiki, Masaru; Yoshimori, Shigeru; Yoshimura, Kazuyuki; Davis, Peter

    2008-12-01

    Random number generators in digital information systems make use of physical entropy sources such as electronic and photonic noise to add unpredictability to deterministically generated pseudo-random sequences. However, there is a large gap between the generation rates achieved with existing physical sources and the high data rates of many computation and communication systems; this is a fundamental weakness of these systems. Here we show that good quality random bit sequences can be generated at very fast bit rates using physical chaos in semiconductor lasers. Streams of bits that pass standard statistical tests for randomness have been generated at rates of up to 1.7 Gbps by sampling the fluctuating optical output of two chaotic lasers. This rate is an order of magnitude faster than that of previously reported devices for physical random bit generators with verified randomness. This means that the performance of random number generators can be greatly improved by using chaotic laser devices as physical entropy sources.

  20. The potts chain in a random field: an exact solution

    International Nuclear Information System (INIS)

    Riera, R.; Chaves, C.M.G.F.; Santos, Raimundo R. dos.

    1984-01-01

    An exact solution is presented for the one-dimensional q-state Potts model in a quenched random field. The ferromagnetic phase is unstable against any small random field perturbation. The correlation function and the Edwards-Anderson order parameter Q are discussed. For finite q only the phase with Q ≠ 0 is present. (Author) [pt

  1. Chaos, complexity, and random matrices

    Science.gov (United States)

    Cotler, Jordan; Hunter-Jones, Nicholas; Liu, Junyu; Yoshida, Beni

    2017-11-01

    Chaos and complexity entail an entropic and computational obstruction to describing a system, and thus are intrinsically difficult to characterize. In this paper, we consider time evolution by Gaussian Unitary Ensemble (GUE) Hamiltonians and analytically compute out-of-time-ordered correlation functions (OTOCs) and frame potentials to quantify scrambling, Haar-randomness, and circuit complexity. While our random matrix analysis gives a qualitatively correct prediction of the late-time behavior of chaotic systems, we find unphysical behavior at early times including an O(1) scrambling time and the apparent breakdown of spatial and temporal locality. The salient feature of GUE Hamiltonians which gives us computational traction is the Haar-invariance of the ensemble, meaning that the ensemble-averaged dynamics look the same in any basis. Motivated by this property of the GUE, we introduce k-invariance as a precise definition of what it means for the dynamics of a quantum system to be described by random matrix theory. We envision that the dynamical onset of approximate k-invariance will be a useful tool for capturing the transition from early-time chaos, as seen by OTOCs, to late-time chaos, as seen by random matrix theory.

  2. Randomizer for High Data Rates

    Science.gov (United States)

    Garon, Howard; Sank, Victor J.

    2018-01-01

    NASA as well as a number of other space agencies now recognize that the current recommended CCSDS randomizer used for telemetry (TM) is too short. When multiple applications of the PN8 Maximal Length Sequence (MLS) are required in order to fully cover a channel access data unit (CADU), spectral problems in the form of elevated spurious discretes (spurs) appear. Originally the randomizer was called a bit transition generator (BTG) precisely because it was thought that its primary value was to insure sufficient bit transitions to allow the bit/symbol synchronizer to lock and remain locked. We, NASA, have shown that the old BTG concept is a limited view of the real value of the randomizer sequence and that the randomizer also aids in signal acquisition as well as minimizing the potential for false decoder lock. Under the guidelines we considered here there are multiple maximal length sequences under GF(2) which appear attractive in this application. Although there may be mitigating reasons why another MLS sequence could be selected, one sequence in particular possesses a combination of desired properties which offsets it from the others.

  3. Spatial serial order processing in schizophrenia.

    Science.gov (United States)

    Fraser, David; Park, Sohee; Clark, Gina; Yohanna, Daniel; Houk, James C

    2004-10-01

    The aim of this study was to examine serial order processing deficits in 21 schizophrenia patients and 16 age- and education-matched healthy controls. In a spatial serial order working memory task, one to four spatial targets were presented in a randomized sequence. Subjects were required to remember the locations and the order in which the targets were presented. Patients showed a marked deficit in ability to remember the sequences compared with controls. Increasing the number of targets within a sequence resulted in poorer memory performance for both control and schizophrenia subjects, but the effect was much more pronounced in the patients. Targets presented at the end of a long sequence were more vulnerable to memory error in schizophrenia patients. Performance deficits were not attributable to motor errors, but to errors in target choice. The results support the idea that the memory errors seen in schizophrenia patients may be due to saturating the working memory network at relatively low levels of memory load.

  4. Quantum Random Networks for Type 2 Quantum Computers

    National Research Council Canada - National Science Library

    Allara, David L; Hasslacher, Brosl

    2006-01-01

    Random boolean networks (RBNs) have been studied theoretically and computationally in order to be able to use their remarkable self-healing and large basins of altercation properties as quantum computing architectures, especially...

  5. Parallel random number generator for inexpensive configurable hardware cells

    Science.gov (United States)

    Ackermann, J.; Tangen, U.; Bödekker, B.; Breyer, J.; Stoll, E.; McCaskill, J. S.

    2001-11-01

    A new random number generator ( RNG) adapted to parallel processors has been created. This RNG can be implemented with inexpensive hardware cells. The correlation between neighboring cells is suppressed with smart connections. With such connection structures, sequences of pseudo-random numbers are produced. Numerical tests including a self-avoiding random walk test and the simulation of the order parameter and energy of the 2D Ising model give no evidence for correlation in the pseudo-random sequences. Because the new random number generator has suppressed the correlation between neighboring cells which is usually observed in cellular automaton implementations, it is applicable for extended time simulations. It gives an immense speed-up factor if implemented directly in configurable hardware, and has recently been used for long time simulations of spatially resolved molecular evolution.

  6. Recommendations and illustrations for the evaluation of photonic random number generators

    Science.gov (United States)

    Hart, Joseph D.; Terashima, Yuta; Uchida, Atsushi; Baumgartner, Gerald B.; Murphy, Thomas E.; Roy, Rajarshi

    2017-09-01

    The never-ending quest to improve the security of digital information combined with recent improvements in hardware technology has caused the field of random number generation to undergo a fundamental shift from relying solely on pseudo-random algorithms to employing optical entropy sources. Despite these significant advances on the hardware side, commonly used statistical measures and evaluation practices remain ill-suited to understand or quantify the optical entropy that underlies physical random number generation. We review the state of the art in the evaluation of optical random number generation and recommend a new paradigm: quantifying entropy generation and understanding the physical limits of the optical sources of randomness. In order to do this, we advocate for the separation of the physical entropy source from deterministic post-processing in the evaluation of random number generators and for the explicit consideration of the impact of the measurement and digitization process on the rate of entropy production. We present the Cohen-Procaccia estimate of the entropy rate h (𝜖 ,τ ) as one way to do this. In order to provide an illustration of our recommendations, we apply the Cohen-Procaccia estimate as well as the entropy estimates from the new NIST draft standards for physical random number generators to evaluate and compare three common optical entropy sources: single photon time-of-arrival detection, chaotic lasers, and amplified spontaneous emission.

  7. Recommendations and illustrations for the evaluation of photonic random number generators

    Directory of Open Access Journals (Sweden)

    Joseph D. Hart

    2017-09-01

    Full Text Available The never-ending quest to improve the security of digital information combined with recent improvements in hardware technology has caused the field of random number generation to undergo a fundamental shift from relying solely on pseudo-random algorithms to employing optical entropy sources. Despite these significant advances on the hardware side, commonly used statistical measures and evaluation practices remain ill-suited to understand or quantify the optical entropy that underlies physical random number generation. We review the state of the art in the evaluation of optical random number generation and recommend a new paradigm: quantifying entropy generation and understanding the physical limits of the optical sources of randomness. In order to do this, we advocate for the separation of the physical entropy source from deterministic post-processing in the evaluation of random number generators and for the explicit consideration of the impact of the measurement and digitization process on the rate of entropy production. We present the Cohen-Procaccia estimate of the entropy rate h(,τ as one way to do this. In order to provide an illustration of our recommendations, we apply the Cohen-Procaccia estimate as well as the entropy estimates from the new NIST draft standards for physical random number generators to evaluate and compare three common optical entropy sources: single photon time-of-arrival detection, chaotic lasers, and amplified spontaneous emission.

  8. Positioning of chromosomes in human spermatozoa is determined by ordered centromere arrangement.

    Directory of Open Access Journals (Sweden)

    Olga S Mudrak

    Full Text Available The intranuclear positioning of chromosomes (CHRs is a well-documented fact; however, mechanisms directing such ordering remain unclear. Unlike somatic cells, human spermatozoa contain distinct spatial markers and have asymmetric nuclei which make them a unique model for localizing CHR territories and matching peri-centromere domains. In this study, we established statistically preferential longitudinal and lateral positioning for eight CHRs. Both parameters demonstrated a correlation with the CHR gene densities but not with their sizes. Intranuclear non-random positioning of the CHRs was found to be driven by a specific linear order of centromeres physically interconnected in continuous arrays. In diploid spermatozoa, linear order of peri-centromeres was identical in two genome sets and essentially matched the arrangement established for haploid cells. We propose that the non-random longitudinal order of CHRs in human spermatozoa is generated during meiotic stages of spermatogenesis. The specific arrangement of sperm CHRs may serve as an epigenetic basis for differential transcription/replication and direct spatial CHR organization during early embryogenesis.

  9. Energy Contents of Frequently Ordered Restaurant Meals and Comparison with Human Energy Requirements and US Department of Agriculture Database Information: A Multisite Randomized Study

    Science.gov (United States)

    Urban, Lorien E.; Weber, Judith L.; Heyman, Melvin B.; Schichtl, Rachel L.; Verstraete, Sofia; Lowery, Nina S.; Das, Sai Krupa; Schleicher, Molly M.; Rogers, Gail; Economos, Christina; Masters, William A.; Roberts, Susan B.

    2017-01-01

    Background Excess energy intake from meals consumed away from home is implicated as a major contributor to obesity, and ~50% of US restaurants are individual or small-chain (non–chain) establishments that do not provide nutrition information. Objective To measure the energy content of frequently ordered meals in non–chain restaurants in three US locations, and compare with the energy content of meals from large-chain restaurants, energy requirements, and food database information. Design A multisite random-sampling protocol was used to measure the energy contents of the most frequently ordered meals from the most popular cuisines in non–chain restaurants, together with equivalent meals from large-chain restaurants. Setting Meals were obtained from restaurants in San Francisco, CA; Boston, MA; and Little Rock, AR, between 2011 and 2014. Main outcome measures Meal energy content determined by bomb calorimetry. Statistical analysis performed Regional and cuisine differences were assessed using a mixed model with restaurant nested within region×cuisine as the random factor. Paired t tests were used to evaluate differences between non–chain and chain meals, human energy requirements, and food database values. Results Meals from non–chain restaurants contained 1,205±465 kcal/meal, amounts that were not significantly different from equivalent meals from large-chain restaurants (+5.1%; P=0.41). There was a significant effect of cuisine on non–chain meal energy, and three of the four most popular cuisines (American, Italian, and Chinese) had the highest mean energy (1,495 kcal/meal). Ninety-two percent of meals exceeded typical energy requirements for a single eating occasion. Conclusions Non–chain restaurants lacking nutrition information serve amounts of energy that are typically far in excess of human energy requirements for single eating occasions, and are equivalent to amounts served by the large-chain restaurants that have previously been criticized

  10. Random walk on random walks

    NARCIS (Netherlands)

    Hilário, M.; Hollander, den W.Th.F.; Sidoravicius, V.; Soares dos Santos, R.; Teixeira, A.

    2014-01-01

    In this paper we study a random walk in a one-dimensional dynamic random environment consisting of a collection of independent particles performing simple symmetric random walks in a Poisson equilibrium with density ¿¿(0,8). At each step the random walk performs a nearest-neighbour jump, moving to

  11. First-principles studies of chromium line-ordered alloys in a molybdenum disulfide monolayer

    Science.gov (United States)

    Andriambelaza, N. F.; Mapasha, R. E.; Chetty, N.

    2017-08-01

    Density functional theory calculations have been performed to study the thermodynamic stability, structural and electronic properties of various chromium (Cr) line-ordered alloy configurations in a molybdenum disulfide (MoS2) hexagonal monolayer for band gap engineering. Only the molybdenum (Mo) sites were substituted at each concentration in this study. For comparison purposes, different Cr line-ordered alloy and random alloy configurations were studied and the most thermodynamically stable ones at each concentration were identified. The configurations formed by the nearest neighbor pair of Cr atoms are energetically most favorable. The line-ordered alloys are constantly lower in formation energy than the random alloys at each concentration. An increase in Cr concentration reduces the lattice constant of the MoS2 system following the Vegard’s law. From density of states analysis, we found that the MoS2 band gap is tunable by both the Cr line-ordered alloys and random alloys with the same magnitudes. The reduction of the band gap is mainly due to the hybridization of the Cr 3d and Mo 4d orbitals at the vicinity of the band edges. The band gap engineering and magnitudes (1.65 eV to 0.86 eV) suggest that the Cr alloys in a MoS2 monolayer are good candidates for nanotechnology devices.

  12. On grey levels in random CAPTCHA generation

    Science.gov (United States)

    Newton, Fraser; Kouritzin, Michael A.

    2011-06-01

    A CAPTCHA is an automatically generated test designed to distinguish between humans and computer programs; specifically, they are designed to be easy for humans but difficult for computer programs to pass in order to prevent the abuse of resources by automated bots. They are commonly seen guarding webmail registration forms, online auction sites, and preventing brute force attacks on passwords. In the following, we address the question: How does adding a grey level to random CAPTCHA generation affect the utility of the CAPTCHA? We treat the problem of generating the random CAPTCHA as one of random field simulation: An initial state of background noise is evolved over time using Gibbs sampling and an efficient algorithm for generating correlated random variables. This approach has already been found to yield highly-readable yet difficult-to-crack CAPTCHAs. We detail how the requisite parameters for introducing grey levels are estimated and how we generate the random CAPTCHA. The resulting CAPTCHA will be evaluated in terms of human readability as well as its resistance to automated attacks in the forms of character segmentation and optical character recognition.

  13. Numerical Inversion for the Multiple Fractional Orders in the Multiterm TFDE

    Directory of Open Access Journals (Sweden)

    Chunlong Sun

    2017-01-01

    Full Text Available The fractional order in a fractional diffusion model is a key parameter which characterizes the anomalous diffusion behaviors. This paper deals with an inverse problem of determining the multiple fractional orders in the multiterm time-fractional diffusion equation (TFDE for short from numerics. The homotopy regularization algorithm is applied to solve the inversion problem using the finite data at one interior point in the space domain. The inversion fractional orders with random noisy data give good approximations to the exact order demonstrating the efficiency of the inversion algorithm and numerical stability of the inversion problem.

  14. Vacuum instability in a random electric field

    International Nuclear Information System (INIS)

    Krive, I.V.; Pastur, L.A.

    1984-01-01

    The reaction of the vacuum on an intense spatially homogeneous random electric field is investigated. It is shown that a stochastic electric field always causes a breakdown of the boson vacuum, and the number of pairs of particles which are created by the electric field increases exponentially in time. For the choice of potential field in the form of a dichotomic random process we find in explicit form the dependence of the average number of pairs of particles on the time of the action of the source of the stochastic field. For the fermion vacuum the average number of pairs of particles which are created by the field in the lowest order of perturbation theory in the amplitude of the random field is independent of time

  15. Some Tests of Random Walk Hypothesis for Bulgarian Foreign Exchange Rates

    OpenAIRE

    Nikolai Gueorguiev

    1993-01-01

    The objective of this paper is to check if the exchange rate in newly emerged, relatively thin foreign exchange markets, follows a random walk pattern. The findings of the current study cast doubts on random walk presence in Bulgarian exchange rates against major international currencies. It turns out that the series of daily returns are stationary but correlated and therefore can be modelled better by higher-order ARIMA processes than by random walk.

  16. Random Walks on Homeo( S 1)

    Science.gov (United States)

    Malicet, Dominique

    2017-12-01

    In this paper, we study random walks {g_n=f_{n-1}\\ldots f_0} on the group Homeo ( S 1) of the homeomorphisms of the circle, where the homeomorphisms f k are chosen randomly, independently, with respect to a same probability measure {ν}. We prove that under the only condition that there is no probability measure invariant by {ν}-almost every homeomorphism, the random walk almost surely contracts small intervals. It generalizes what has been known on this subject until now, since various conditions on {ν} were imposed in order to get the phenomenon of contractions. Moreover, we obtain the surprising fact that the rate of contraction is exponential, even in the lack of assumptions of smoothness on the f k 's. We deduce various dynamical consequences on the random walk ( g n ): finiteness of ergodic stationary measures, distribution of the trajectories, asymptotic law of the evaluations, etc. The proof of the main result is based on a modification of the Ávila-Viana's invariance principle, working for continuous cocycles on a space fibred in circles.

  17. Warehouse Order-Picking Process. Review

    Directory of Open Access Journals (Sweden)

    E. V. Korobkov

    2015-01-01

    Full Text Available This article describes basic warehousing activities, namely: movement, information storage and transfer, as well as connections between typical warehouse operations (reception, transfer, assigning storage position and put-away, order-picking, hoarding and sorting, cross-docking, shipping. It presents a classification of the warehouse order-picking systems in terms of manual labor on offer as well as external (marketing channels, consumer’s demand structure, supplier’s replenishment structure and inventory level, total production demand, economic situation and internal (mechanization level, information accessibility, warehouse dimensionality, method of dispatch for shipping, zoning, batching, storage assignment method, routing method factors affecting the designing systems complexity. Basic optimization considerations are described. There is a literature review on the following sub-problems of planning and control of orderpicking processes.A layout design problem has been taken in account at two levels — external (facility layout problem and internal (aisle configuration problem. For a problem of distributing goods or stock keeping units the following methods are emphasized: random, nearest open storage position, and dedicated (COI-based, frequency-based distribution, as well as class-based and familygrouped (complimentary- and contact-based one. Batching problem can be solved by two main methods, i.e. proximity order batching (seed and saving algorithms and time-window order batching. There are two strategies for a zoning problem: progressive and synchronized, and also a special case of zoning — bucket brigades method. Hoarding/sorting problem is briefly reviewed. Order-picking routing problem will be thoroughly described in the next article of the cycle “Warehouse order-picking process”.

  18. RandomSpot: A web-based tool for systematic random sampling of virtual slides.

    Science.gov (United States)

    Wright, Alexander I; Grabsch, Heike I; Treanor, Darren E

    2015-01-01

    This paper describes work presented at the Nordic Symposium on Digital Pathology 2014, Linköping, Sweden. Systematic random sampling (SRS) is a stereological tool, which provides a framework to quickly build an accurate estimation of the distribution of objects or classes within an image, whilst minimizing the number of observations required. RandomSpot is a web-based tool for SRS in stereology, which systematically places equidistant points within a given region of interest on a virtual slide. Each point can then be visually inspected by a pathologist in order to generate an unbiased sample of the distribution of classes within the tissue. Further measurements can then be derived from the distribution, such as the ratio of tumor to stroma. RandomSpot replicates the fundamental principle of traditional light microscope grid-shaped graticules, with the added benefits associated with virtual slides, such as facilitated collaboration and automated navigation between points. Once the sample points have been added to the region(s) of interest, users can download the annotations and view them locally using their virtual slide viewing software. Since its introduction, RandomSpot has been used extensively for international collaborative projects, clinical trials and independent research projects. So far, the system has been used to generate over 21,000 sample sets, and has been used to generate data for use in multiple publications, identifying significant new prognostic markers in colorectal, upper gastro-intestinal and breast cancer. Data generated using RandomSpot also has significant value for training image analysis algorithms using sample point coordinates and pathologist classifications.

  19. Random model of two-level atoms interacting with electromagnetic field

    International Nuclear Information System (INIS)

    Kireev, A.N.; Meleshko, A.N.

    1983-12-01

    A phase transition has been studied in a random system of two-level atoms interacting with an electromagnetic field. It is shown that superradiation can arise when there is short-range order in a spin-subsystem. The existence of long-range order is irrelevant for this phase transition

  20. Pseudo-random bit generator based on lag time series

    Science.gov (United States)

    García-Martínez, M.; Campos-Cantón, E.

    2014-12-01

    In this paper, we present a pseudo-random bit generator (PRBG) based on two lag time series of the logistic map using positive and negative values in the bifurcation parameter. In order to hidden the map used to build the pseudo-random series we have used a delay in the generation of time series. These new series when they are mapped xn against xn+1 present a cloud of points unrelated to the logistic map. Finally, the pseudo-random sequences have been tested with the suite of NIST giving satisfactory results for use in stream ciphers.

  1. Spherically symmetric random walks. II. Dimensionally dependent critical behavior

    International Nuclear Information System (INIS)

    Bender, C.M.; Boettcher, S.; Meisinger, P.N.

    1996-01-01

    A recently developed model of random walks on a D-dimensional hyperspherical lattice, where D is not restricted to integer values, is extended to include the possibility of creating and annihilating random walkers. Steady-state distributions of random walkers are obtained for all dimensions D approx-gt 0 by solving a discrete eigenvalue problem. These distributions exhibit dimensionally dependent critical behavior as a function of the birth rate. This remarkably simple model exhibits a second-order phase transition with a universal, nontrivial critical exponent for all dimensions D approx-gt 0. copyright 1996 The American Physical Society

  2. Sampling large random knots in a confined space

    International Nuclear Information System (INIS)

    Arsuaga, J; Blackstone, T; Diao, Y; Hinson, K; Karadayi, E; Saito, M

    2007-01-01

    DNA knots formed under extreme conditions of condensation, as in bacteriophage P4, are difficult to analyze experimentally and theoretically. In this paper, we propose to use the uniform random polygon model as a supplementary method to the existing methods for generating random knots in confinement. The uniform random polygon model allows us to sample knots with large crossing numbers and also to generate large diagrammatically prime knot diagrams. We show numerically that uniform random polygons sample knots with large minimum crossing numbers and certain complicated knot invariants (as those observed experimentally). We do this in terms of the knot determinants or colorings. Our numerical results suggest that the average determinant of a uniform random polygon of n vertices grows faster than O(e n 2 )). We also investigate the complexity of prime knot diagrams. We show rigorously that the probability that a randomly selected 2D uniform random polygon of n vertices is almost diagrammatically prime goes to 1 as n goes to infinity. Furthermore, the average number of crossings in such a diagram is at the order of O(n 2 ). Therefore, the two-dimensional uniform random polygons offer an effective way in sampling large (prime) knots, which can be useful in various applications

  3. Sampling large random knots in a confined space

    Science.gov (United States)

    Arsuaga, J.; Blackstone, T.; Diao, Y.; Hinson, K.; Karadayi, E.; Saito, M.

    2007-09-01

    DNA knots formed under extreme conditions of condensation, as in bacteriophage P4, are difficult to analyze experimentally and theoretically. In this paper, we propose to use the uniform random polygon model as a supplementary method to the existing methods for generating random knots in confinement. The uniform random polygon model allows us to sample knots with large crossing numbers and also to generate large diagrammatically prime knot diagrams. We show numerically that uniform random polygons sample knots with large minimum crossing numbers and certain complicated knot invariants (as those observed experimentally). We do this in terms of the knot determinants or colorings. Our numerical results suggest that the average determinant of a uniform random polygon of n vertices grows faster than O(e^{n^2}) . We also investigate the complexity of prime knot diagrams. We show rigorously that the probability that a randomly selected 2D uniform random polygon of n vertices is almost diagrammatically prime goes to 1 as n goes to infinity. Furthermore, the average number of crossings in such a diagram is at the order of O(n2). Therefore, the two-dimensional uniform random polygons offer an effective way in sampling large (prime) knots, which can be useful in various applications.

  4. Sampling large random knots in a confined space

    Energy Technology Data Exchange (ETDEWEB)

    Arsuaga, J [Department of Mathematics, San Francisco State University, 1600 Holloway Ave, San Francisco, CA 94132 (United States); Blackstone, T [Department of Computer Science, San Francisco State University, 1600 Holloway Ave., San Francisco, CA 94132 (United States); Diao, Y [Department of Mathematics and Statistics, University of North Carolina at Charlotte, Charlotte, NC 28223 (United States); Hinson, K [Department of Mathematics and Statistics, University of North Carolina at Charlotte, Charlotte, NC 28223 (United States); Karadayi, E [Department of Mathematics, University of South Florida, 4202 E Fowler Avenue, Tampa, FL 33620 (United States); Saito, M [Department of Mathematics, University of South Florida, 4202 E Fowler Avenue, Tampa, FL 33620 (United States)

    2007-09-28

    DNA knots formed under extreme conditions of condensation, as in bacteriophage P4, are difficult to analyze experimentally and theoretically. In this paper, we propose to use the uniform random polygon model as a supplementary method to the existing methods for generating random knots in confinement. The uniform random polygon model allows us to sample knots with large crossing numbers and also to generate large diagrammatically prime knot diagrams. We show numerically that uniform random polygons sample knots with large minimum crossing numbers and certain complicated knot invariants (as those observed experimentally). We do this in terms of the knot determinants or colorings. Our numerical results suggest that the average determinant of a uniform random polygon of n vertices grows faster than O(e{sup n{sup 2}}). We also investigate the complexity of prime knot diagrams. We show rigorously that the probability that a randomly selected 2D uniform random polygon of n vertices is almost diagrammatically prime goes to 1 as n goes to infinity. Furthermore, the average number of crossings in such a diagram is at the order of O(n{sup 2}). Therefore, the two-dimensional uniform random polygons offer an effective way in sampling large (prime) knots, which can be useful in various applications.

  5. Emergent randomness in the Jaynes-Cummings model

    International Nuclear Information System (INIS)

    Garraway, B M; Stenholm, S

    2008-01-01

    We consider the well-known Jaynes-Cummings model and ask if it can display randomness. As a solvable Hamiltonian system, it does not display chaotic behaviour in the ordinary sense. Here, however, we look at the distribution of values taken up during the total time evolution. This evolution is determined by the eigenvalues distributed as the square roots of integers and leads to a seemingly erratic behaviour. That this may display a random Gaussian value distribution is suggested by an exactly provable result by Kac. In order to reach our conclusion we use the Kac model to develop tests for the emergence of a Gaussian. Even if the consequent double limits are difficult to evaluate numerically, we find definite indications that the Jaynes-Cummings case also produces a randomness in its value distributions. Numerical methods do not establish such a result beyond doubt, but our conclusions are definite enough to suggest strongly an unexpected randomness emerging in a dynamic time evolution

  6. A Randomization Procedure for "Trickle-Process" Evaluations

    Science.gov (United States)

    Goldman, Jerry

    1977-01-01

    This note suggests a solution to the problem of achieving randomization in experimental settings where units deemed eligible for treatment "trickle in," that is, appear at any time. The solution permits replication of the experiment in order to test for time-dependent effects. (Author/CTM)

  7. From Bloch to random lasing in ZnO self-assembled nanostructures

    DEFF Research Database (Denmark)

    Garcia-Fernandez, Pedro David; Cefe, López

    2013-01-01

    In this paper, we present measurements on UV lasing in ZnO ordered and disordered nanostructures. Bloch lasing is achieved in the ordered structures by exploiting very low group-velocity Bloch modes in ZnO photonic crystals. In the second case, random lasing is observed in ZnO photonic glasses. We...... study the lasing threshold in both cases and its dependence on the structural parameters. Finally, we present the transition from Bloch to random lasing by deliberately doping a ZnO inverse photonic crystal with a controlled amount of lattice vacancies effectively converting it into a translationally...

  8. Thermodynamic modelling of clay dehydration, stability and compositional evolution with temperature, pressure and H2O activity

    International Nuclear Information System (INIS)

    Vidal, O.; Dubacq, B.

    2010-01-01

    Document available in extended abstract form only. Full text of publication follows: The evaluation of the performance of clay-rich barrier considered for the disposal of radioactive waste and a reliable prediction of the impact of repository-induced disturbances upon the confinement properties of clay-rich geological formations requires reliable thermodynamic models for clay minerals. Such models have to take into account the variation of the hydration state of smectite as a function of temperature, pressure and water activity. We propose the first macroscopic thermodynamic model that account for the stepwise dehydration with increasing temperature or decreasing H 2 O activity of K, Na, Ca and Mg-smectite. The model relies on the relative stability of the different solid-solutions that describe the hydration of di- or tri-octahedral-smectites containing 0, 1, 2 or 3 interlayer water layers. The inclusion of anhydrous mica end-members makes it possible to cover, with the same solid-solution model, the entire range of composition from low-charge to high-charge smectite, through illite to mica. Non-ideal Margules parameters were used to describe the non-ideality of the solid solutions between the hydrated and dehydrated smectite end-members. Standard state properties of all smectite end-members as well as Ca- and Mg-muscovite and -phlogopite were initially estimated by oxide summation. These values were then refined and the other non-ideal interactions were estimated on the basis of different experimental data. The stepwise dehydration of smectite, and its stability and compatibility relations were calculated by Gibbs free energy minimizing. Our results account for the progressive evolution of smectite to inter-layered illite/smectite and then to mica, as observed in nature and experiments, and our model provides an explanation for the thermodynamic stability of smectite and illite/ smectite compared to mica + kaolinite or pyrophyllite assemblages. The results

  9. Continuous-time quantum random walks require discrete space

    International Nuclear Information System (INIS)

    Manouchehri, K; Wang, J B

    2007-01-01

    Quantum random walks are shown to have non-intuitive dynamics which makes them an attractive area of study for devising quantum algorithms for long-standing open problems as well as those arising in the field of quantum computing. In the case of continuous-time quantum random walks, such peculiar dynamics can arise from simple evolution operators closely resembling the quantum free-wave propagator. We investigate the divergence of quantum walk dynamics from the free-wave evolution and show that, in order for continuous-time quantum walks to display their characteristic propagation, the state space must be discrete. This behavior rules out many continuous quantum systems as possible candidates for implementing continuous-time quantum random walks

  10. Continuous-time quantum random walks require discrete space

    Science.gov (United States)

    Manouchehri, K.; Wang, J. B.

    2007-11-01

    Quantum random walks are shown to have non-intuitive dynamics which makes them an attractive area of study for devising quantum algorithms for long-standing open problems as well as those arising in the field of quantum computing. In the case of continuous-time quantum random walks, such peculiar dynamics can arise from simple evolution operators closely resembling the quantum free-wave propagator. We investigate the divergence of quantum walk dynamics from the free-wave evolution and show that, in order for continuous-time quantum walks to display their characteristic propagation, the state space must be discrete. This behavior rules out many continuous quantum systems as possible candidates for implementing continuous-time quantum random walks.

  11. Stability of a nonlinear second order equation under parametric bounded noise excitation

    International Nuclear Information System (INIS)

    Wiebe, Richard; Xie, Wei-Chau

    2016-01-01

    The motivation for the following work is a structural column under dynamic axial loads with both deterministic (harmonic transmitted forces from the surrounding structure) and random (wind and/or earthquake) loading components. The bounded noise used herein is a sinusoid with an argument composed of a random (Wiener) process deviation about a mean frequency. By this approach, a noise parameter may be used to investigate the behavior through the spectrum from simple harmonic forcing, to a bounded random process with very little harmonic content. The stability of both the trivial and non-trivial stationary solutions of an axially-loaded column (which is modeled as a second order nonlinear equation) under parametric bounded noise excitation is investigated by use of Lyapunov exponents. Specifically the effect of noise magnitude, amplitude of the forcing, and damping on stability of a column is investigated. First order averaging is employed to obtain analytical approximations of the Lyapunov exponents of the trivial solution. For the non-trivial stationary solution however, the Lyapunov exponents are obtained via Monte Carlo simulation as the stability equations become analytically intractable. (paper)

  12. Heavy-traffic limits for polling models with exhaustive service and non-FCFS service orders

    NARCIS (Netherlands)

    P. Vis (Petra); R. Bekker (Rene); R.D. van der Mei (Rob)

    2015-01-01

    htmlabstractWe study cyclic polling models with exhaustive service at each queue under a variety of non-FCFS (first-come-first-served) local service orders, namely last-come-first-served with and without preemption, random-order-of-service, processor sharing, the multi-class priority scheduling with

  13. Extinction order and altered community structure rapidly disrupt ecosystem functioning.

    Science.gov (United States)

    Larsen, Trond H; Williams, Neal M; Kremen, Claire

    2005-05-01

    By causing extinctions and altering community structure, anthropogenic disturbances can disrupt processes that maintain ecosystem integrity. However, the relationship between community structure and ecosystem functioning in natural systems is poorly understood. Here we show that habitat loss appeared to disrupt ecosystem functioning by affecting extinction order, species richness and abundance. We studied pollination by bees in a mosaic of agricultural and natural habitats in California and dung burial by dung beetles on recently created islands in Venezuela. We found that large-bodied bee and beetle species tended to be both most extinction-prone and most functionally efficient, contributing to rapid functional loss. Simulations confirmed that extinction order led to greater disruption of function than predicted by random species loss. Total abundance declined with richness and also appeared to contribute to loss of function. We demonstrate conceptually and empirically how the non-random response of communities to disturbance can have unexpectedly large functional consequences.

  14. Partially ordered sets, transfinite topology and the dimension of Cantorian-fractal spacetime

    Energy Technology Data Exchange (ETDEWEB)

    Marek-Crnjac, L. [Institute of Mathematics and Physics, University of Maribor (Slovenia)], E-mail: leila.marek@guest.arnes.si

    2009-11-15

    We introduce partially ordered sets and relate them to random Cantor sets of E-infinity theory. Subsequently we derive the dimensionality of Cantorian-fractal spacetime using posets and E-infinity transfinite Cantor sets.

  15. Energy Contents of Frequently Ordered Restaurant Meals and Comparison with Human Energy Requirements and U.S. Department of Agriculture Database Information: A Multisite Randomized Study.

    Science.gov (United States)

    Urban, Lorien E; Weber, Judith L; Heyman, Melvin B; Schichtl, Rachel L; Verstraete, Sofia; Lowery, Nina S; Das, Sai Krupa; Schleicher, Molly M; Rogers, Gail; Economos, Christina; Masters, William A; Roberts, Susan B

    2016-04-01

    Excess energy intake from meals consumed away from home is implicated as a major contributor to obesity, and ∼50% of US restaurants are individual or small-chain (non-chain) establishments that do not provide nutrition information. To measure the energy content of frequently ordered meals in non-chain restaurants in three US locations, and compare with the energy content of meals from large-chain restaurants, energy requirements, and food database information. A multisite random-sampling protocol was used to measure the energy contents of the most frequently ordered meals from the most popular cuisines in non-chain restaurants, together with equivalent meals from large-chain restaurants. Meals were obtained from restaurants in San Francisco, CA; Boston, MA; and Little Rock, AR, between 2011 and 2014. Meal energy content determined by bomb calorimetry. Regional and cuisine differences were assessed using a mixed model with restaurant nested within region×cuisine as the random factor. Paired t tests were used to evaluate differences between non-chain and chain meals, human energy requirements, and food database values. Meals from non-chain restaurants contained 1,205±465 kcal/meal, amounts that were not significantly different from equivalent meals from large-chain restaurants (+5.1%; P=0.41). There was a significant effect of cuisine on non-chain meal energy, and three of the four most popular cuisines (American, Italian, and Chinese) had the highest mean energy (1,495 kcal/meal). Ninety-two percent of meals exceeded typical energy requirements for a single eating occasion. Non-chain restaurants lacking nutrition information serve amounts of energy that are typically far in excess of human energy requirements for single eating occasions, and are equivalent to amounts served by the large-chain restaurants that have previously been criticized for providing excess energy. Restaurants in general, rather than specific categories of restaurant, expose patrons to

  16. Magnetic ordering in arrays of one-dimensional nanoparticle chains

    International Nuclear Information System (INIS)

    Serantes, D; Baldomir, D; Pereiro, M; Hernando, B; Prida, V M; Sanchez Llamazares, J L; Zhukov, A; Ilyn, M; Gonzalez, J

    2009-01-01

    The magnetic order in parallel-aligned one-dimensional (1D) chains of magnetic nanoparticles is studied using a Monte Carlo technique. If the easy anisotropy axes are collinear along the chains a macroscopic mean-field approach indicates antiferromagnetic (AFM) order even when no interparticle interactions are taken into account, which evidences that a mean-field treatment is inadequate for the study of the magnetic order in these highly anisotropic systems. From the direct microscopic analysis of the evolution of the magnetic moments, we observe spontaneous intra-chain ferromagnetic (FM)-type and inter-chain AFM-type ordering at low temperatures (although not completely regular) for the easy-axes collinear case, whereas a random distribution of the anisotropy axes leads to a sort of intra-chain AFM arrangement with no inter-chain regular order. When the magnetic anisotropy is neglected a perfectly regular intra-chain FM-like order is attained. Therefore it is shown that the magnetic anisotropy, and particularly the spatial distribution of the easy axes, is a key parameter governing the magnetic ordering type of 1D-nanoparticle chains.

  17. Generating equilateral random polygons in confinement II

    International Nuclear Information System (INIS)

    Diao, Y; Ernst, C; Montemayor, A; Ziegler, U

    2012-01-01

    In this paper we continue an earlier study (Diao et al 2011 J. Phys. A: Math. Theor. 44 405202) on the generation algorithms of random equilateral polygons confined in a sphere. Here, the equilateral random polygons are rooted at the center of the confining sphere and the confining sphere behaves like an absorbing boundary. One way to generate such a random polygon is the accept/reject method in which an unconditioned equilateral random polygon rooted at origin is generated. The polygon is accepted if it is within the confining sphere, otherwise it is rejected and the process is repeated. The algorithm proposed in this paper offers an alternative to the accept/reject method, yielding a faster generation process when the confining sphere is small. In order to use this algorithm effectively, a large, reusable data set needs to be pre-computed only once. We derive the theoretical distribution of the given random polygon model and demonstrate, with strong numerical evidence, that our implementation of the algorithm follows this distribution. A run time analysis and a numerical error estimate are given at the end of the paper. (paper)

  18. Convergence to equilibrium under a random Hamiltonian

    Science.gov (United States)

    Brandão, Fernando G. S. L.; Ćwikliński, Piotr; Horodecki, Michał; Horodecki, Paweł; Korbicz, Jarosław K.; Mozrzymas, Marek

    2012-09-01

    We analyze equilibration times of subsystems of a larger system under a random total Hamiltonian, in which the basis of the Hamiltonian is drawn from the Haar measure. We obtain that the time of equilibration is of the order of the inverse of the arithmetic average of the Bohr frequencies. To compute the average over a random basis, we compute the inverse of a matrix of overlaps of operators which permute four systems. We first obtain results on such a matrix for a representation of an arbitrary finite group and then apply it to the particular representation of the permutation group under consideration.

  19. How random is a random vector?

    International Nuclear Information System (INIS)

    Eliazar, Iddo

    2015-01-01

    Over 80 years ago Samuel Wilks proposed that the “generalized variance” of a random vector is the determinant of its covariance matrix. To date, the notion and use of the generalized variance is confined only to very specific niches in statistics. In this paper we establish that the “Wilks standard deviation” –the square root of the generalized variance–is indeed the standard deviation of a random vector. We further establish that the “uncorrelation index” –a derivative of the Wilks standard deviation–is a measure of the overall correlation between the components of a random vector. Both the Wilks standard deviation and the uncorrelation index are, respectively, special cases of two general notions that we introduce: “randomness measures” and “independence indices” of random vectors. In turn, these general notions give rise to “randomness diagrams”—tangible planar visualizations that answer the question: How random is a random vector? The notion of “independence indices” yields a novel measure of correlation for Lévy laws. In general, the concepts and results presented in this paper are applicable to any field of science and engineering with random-vectors empirical data.

  20. How random is a random vector?

    Science.gov (United States)

    Eliazar, Iddo

    2015-12-01

    Over 80 years ago Samuel Wilks proposed that the "generalized variance" of a random vector is the determinant of its covariance matrix. To date, the notion and use of the generalized variance is confined only to very specific niches in statistics. In this paper we establish that the "Wilks standard deviation" -the square root of the generalized variance-is indeed the standard deviation of a random vector. We further establish that the "uncorrelation index" -a derivative of the Wilks standard deviation-is a measure of the overall correlation between the components of a random vector. Both the Wilks standard deviation and the uncorrelation index are, respectively, special cases of two general notions that we introduce: "randomness measures" and "independence indices" of random vectors. In turn, these general notions give rise to "randomness diagrams"-tangible planar visualizations that answer the question: How random is a random vector? The notion of "independence indices" yields a novel measure of correlation for Lévy laws. In general, the concepts and results presented in this paper are applicable to any field of science and engineering with random-vectors empirical data.