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.

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.)

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

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.

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

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

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.

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

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.

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.

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

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.

Clay membrane made of natural high plasticity clay

DEFF Research Database (Denmark)

Foged, Niels; Baumann, Jens

1998-01-01

Leachate containment in Denmark has through years been regulated by the DIF Recommendation for Sanitary Landfill Liners (DS/R 466). It states natural clay deposits may be used for membrane material provided the membrane and drainage system may contain at least 95% of all leachate created throughout...... ion transport as well as diffusion.Clay prospection for clays rich in smectite has revealed large deposits of Tertiary clay of very high plasticity in the area around Rødbyhavn on the Danish island Lolland. The natural clay contains 60 to 75% smectite, dominantly as a sodium-type. The clay material...... has been evaluated using standardised methods related to mineralogy, classification, compaction and permeability, and initial studies of diffusion properties have been carried out. Furthermore, at a test site the construction methods for establishing a 0.15 to 0.3m thick clay membrane have been tested...

Clay membrane made of natural high plasticity clay:

DEFF Research Database (Denmark)

Foged, Niels; Baumann, Jens

1999-01-01

Leachate containment in Denmark has throughout the years been regulated by the DIF Recommendation for Sanitary Landfill Liners (DS/R4669. It states that natural clay deposits may be used as membrane material provided the membrane and drainage system contains at least 95% of all leachate created...... into account advective ion transport as well as diffusion. Clay prospecting for clays rich in smectite has revealed large deposits of Tertiary clay of very high plasticity in the area around Rødbyhavn on the Danish island of Lolland. The natural clay contains 60-75% smectite, dominantly as a sodium......-type. The clay material has been evaluated using the standardized methods related to mineralogy, classification, compaction and permeability, and initial studies of diffusion properties have been carried out. Furthermore, at a test site the construction methods for establishing a 0.15-0.3 m thick clay membrane...

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.

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.

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.

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

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.

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)

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.

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.

Choice of french clays as engineered barrier components for waste disposal

International Nuclear Information System (INIS)

Coulon, H.; Lajudie, A.; Debrabant, P.; Atabek, R.; Jorda, M.; Andre-Jehan, R.

1987-01-01

Results are presented of physical measurements on candidate buffer materials for use in nuclear fuel waste disposal. The materials being considered as constituent elements of engineered barriers are essentially calcium smectite clays, in other terms swelling clays, coming from fourteen french deposits. The criteria for good candidates are mainly: smectite content in the clay materials, carbonate and organic material content and bulk density of the material, compacted under a pressure of 100 MPa. 14 references, 4 figures, 6 tables

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)

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.

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...

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.

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.

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

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.

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)

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

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

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

Comprehensive review of geosynthetic clay liner and compacted clay liner

Science.gov (United States)

Shankar, M. Uma; Muthukumar, M.

2017-11-01

Human activity inevitably produces waste materials that must be managed. Some waste can be reused. However many wastes that cannot be used beneficially must be disposed of ensuring environmental safety. One of the common methods of disposal is landfilling. The most common problems of the landfill site are environmental degradation and groundwater contamination caused by leachate produced during the decomposition process of organic material and rainfall. Liner in a landfill is an important component which prevent leachate migration and prevent groundwater contamination. Earthen liners have been widely used to contain waste materials in landfill. Liners and covers for municipal and hazardous waste containment facilities are often constructed with the use of fine-grained, low plasticity soils. Because of low permeability geosynthetic clay liners and compacted clay liners are the main materials used in waste disposal landfills. This paper summaries the important geotechnical characteristics such as hydraulic conductivity, liquid limit and free swell index of geosynthetic clay liner and compacted clay liner based on research findings. This paper also compares geosynthetic clay liner and compacted clay liner based on certain criteria such as thickness, availability of materials, vulnerability to damage etc.

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.

Recovery of Porosity and Permeability for High Plasticity Clays

DEFF Research Database (Denmark)

Krogsbøll, Anette; Foged, Niels Nielsen

to be the case for high plasticity clays that are uncemented, and with a high content of clay minerals, especially smectite. Oedometer tests on samples from the Paleogene period show that 80% or more of the compaction will recover when unloaded, and if unloaded to a stress lower than in situ stress level...

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)

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 ...

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.

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.

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.)

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.

Effects of biochar on hydraulic conductivity of compacted kaolin clay.

Science.gov (United States)

Wong, James Tsz Fung; Chen, Zhongkui; Wong, Annie Yan Yan; Ng, Charles Wang Wai; Wong, Ming Hung

2018-03-01

Compacted clay is widely used as capillary barriers in landfill final cover system. Recently, biochar amended clay (BAC) has been proposed as a sustainable alternative cover material. However, the effects of biochar on saturated hydraulic conductivity (k sat ) of clay with high degree of compaction is not yet understood. The present study aims to investigate the effects of biochar on k sat of compacted kaolin clay. Soil specimens were prepared by amending kaolin clay with biochar derived from peanut-shell at 0, 5 and 20% (w/w). The k sat of soil specimens was measured using a flexible water permeameter. The effects of biochar on the microstructure of the compacted clay was also investigated using MIP. Adding 5% and 20% of biochar increased the k sat of compacted kaolin clay from 1.2 × 10 -9 to 2.1 × 10 -9 and 1.3 × 10 -8 ms -1 , respectively. The increase in k sat of clay was due to the shift in pore size distribution of compacted biochar-amended clay (BAC). MIP results revealed that adding 20% of biochar shifted the dominant pore diameter of clay from 0.01-0.1 μm (meso- and macropores) to 0.1-4 μm (macropores). Results reported in this communication revealed that biochar application increased the k sat of compacted clay, and the increment was positively correlated to the biochar percentage. Copyright © 2017 Elsevier Ltd. All rights reserved.

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)

Permeability response of oil-contaminated compacted clays

International Nuclear Information System (INIS)

Silvestri, V.; Mikhail, N.; Soulie, M.

1997-01-01

This paper presents the results of a laboratory investigation on the behavior of motor oil-contaminated, partially saturated compacted clays. For the study, both a natural clay and an artificially purified kaolinite, contaminated with 0 to 8% of motor oil, were firstly compacted following the ASTM standard procedure. Secondly, permeability tests were carried out in a triaxial cell on 10 cm-diameter compacted clay specimens. The results of the investigation indicate that increasing percentages of motor oil decrease both the optimum water content and the optimum dry density of the two clays. However, whereas the optimum water content on the average decreases by about 6% when the percentage contamination increases from 0 to 8%, the corresponding decrease in the optimum dry density is less than 3%. Even though the optimum dry density decreases as the percentage of oil increases from 0 to 8%, there is, however, a range in oil content varying between 2 and 4% for which the optimum dry density is slightly greater than that of the untreated soils. As far as the permeability tests are concerned, the results indicate that as the percentage of oil increases, the coefficient of permeability decreases substantially, especially for clay specimens which were initially compacted on the dry side of optimum

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)

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)

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.

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

Effect of Compaction on Compressive Strength of Unfired Clay Blocks

International Nuclear Information System (INIS)

Lakho, N.A.; Zardari, M.A.; Pathan, A.A.

2016-01-01

This study investigates the possible use of unfired compacted clay blocks as a substitute of CSEB (Compressed Stabilized Earth Blocks) for the construction of economical houses. Cubes of 150 mm size were cut from the clay blocks which were compacted at various intensities of pressure during the casting. The results show that the compressive strength of the clay cubes increased with the compacting pressure to which the blocks were subjected during casting. The average crushing strength of the cubes, sawed from clay blocks that were subjected to compacting pressure of 7.2 MPa, was found to be 4.4 MPa. This value of compressive strength is about 50 percent more than that of normal CSEB. This study shows that the compacted clay blocks could be used as economical walling material as replacement of CSEB. (author)

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.

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.

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.

The effect of freeze-thaw cycles on the hydraulic conductivity of compacted clay

International Nuclear Information System (INIS)

Waite, D.; Anderson, L.; Caliendo, J.; McFarland, M.

1994-01-01

A study was conducted to investigate the detrimental effects of freeze-thaw on the hydraulic conductivity of compacted clay. The purpose of this study was to determine the effect that molding water content has on the hydraulic conductivity of a compacted clay soil that is subjected to freeze-thaw cycles, and to determine the relationship between the number of freeze-thaw cycles and the hydraulic conductivity of the compacted clay soil. Clay soils compacted and frozen wet of optimum experienced an increase in hydraulic conductivity of approximately 140 fold. The hydraulic conductivity of clay compacted dry of optimum increased ten fold. These results are consistent with recent research which suggests that clay compacted wet of optimum experiences large increases in hydraulic conductivity while the hydraulic conductivity of clay compacted dry of optimum increases to a lesser extent. 12 refs., 9 figs

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

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

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

Diffusion through statically compacted clay

International Nuclear Information System (INIS)

Ho, C.L.; Shebl, M.A.A.

1994-01-01

This paper presents experimental work on the effect of compaction on contaminant flow through clay liners. The experimental program included evaluation of soil properties, compaction, permeability and solute diffusion. A permeameter was built of non reactive materials to test samples compacted at different water contents and compactive efforts. The flow of a permeating solute, LiCl, was monitored. Effluent samples were collected for solute concentration measurements. The concentrations were measured by performing atomic adsorption tests. The analyzed results showed different diffusion characteristics when compaction conditions changed. At each compactive effort, permeability decreased as molding water content increased. Consequently, transit time (measured at relative concentration 50%) increased and diffusivity decreased. As compactive effort increased for soils compacted dry of optimum, permeability and diffusion decreased. On the other hand, as compactive effort increased for soils compacted wet of optimum, permeability and diffusivity increased. Tortuosity factor was indirectly measured from the diffusion and retardation rate. Tortuosity factor also decreased as placement water content was increased from dry of optimum to wet of optimum. Then decreases were more pronounced for low compactive effort tests. 27 refs., 7 figs., 5 tabs

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.

Compressive Strength of Compacted Clay-Sand Mixes

Directory of Open Access Journals (Sweden)

Faseel Suleman Khan

2014-01-01

Full Text Available The use of sand to improve the strength of natural clays provides a viable alternative for civil infrastructure construction involving earthwork. The main objective of this note was to investigate the compressive strength of compacted clay-sand mixes. A natural clay of high plasticity was mixed with 20% and 40% sand (SP and their compaction and strength properties were determined. Results indicated that the investigated materials exhibited a brittle behaviour on the dry side of optimum and a ductile behaviour on the wet side of optimum. For each material, the compressive strength increased with an increase in density following a power law function. Conversely, the compressive strength increased with decreasing water content of the material following a similar function. Finally, the compressive strength decreased with an increase in sand content because of increased material heterogeneity and loss of sand grains from the sides during shearing.

Compaction of microfossil and clay-rich chalk sediments

DEFF Research Database (Denmark)

Fabricius, Ida Lykke

2001-01-01

The aim of this study was to evaluate the role of microfossils and clay in the compaction of chalk facies sediments. To meet this aim, chalk sediments with varying micro texture were studied. The sediments have been tested uniaxially confined in a stainless-steel compaction cell. The sediments are......: 1) Pure carbonate chalk with mudstone texture from Stevns Klint (Denmark), 2) Relatively pure chalk sediments with varying content of microfossils from the Ontong Java Plateau (Western Pacific), 3) Clay-rich chalk and mixed sediments from the Caribbean. The tested samples were characterised...

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)

Gas breakthrough and emission through unsaturated compacted clay in landfill final cover

International Nuclear Information System (INIS)

Ng, C.W.W.; Chen, Z.K.; Coo, J.L.; Chen, R.; Zhou, C.

2015-01-01

Highlights: • Explore feasibility of unsaturated clay as a gas barrier in landfill cover. • Gas breakthrough pressure increases with clay thickness and degree of saturation. • Gas emission rate decreases with clay thickness and degree of saturation. • A 0.6 m-thick clay layer may be sufficient to meet gas emission rate limit. - Abstract: Determination of gas transport parameters in compacted clay plays a vital role for evaluating the effectiveness of soil barriers. The gas breakthrough pressure has been widely studied for saturated swelling clay buffer commonly used in high-level radioactive waste disposal facility where the generated gas pressure is very high (in the order of MPa). However, compacted clay in landfill cover is usually unsaturated and the generated landfill gas pressure is normally low (typically less than 10 kPa). Furthermore, effects of clay thickness and degree of saturation on gas breakthrough and emission rate in the context of unsaturated landfill cover has not been quantitatively investigated in previous studies. The feasibility of using unsaturated compacted clay as gas barrier in landfill covers is thus worthwhile to be explored over a wide range of landfill gas pressures under various degrees of saturation and clay thicknesses. In this study, to evaluate the effectiveness of unsaturated compacted clay to minimize gas emission, one-dimensional soil column tests were carried out on unsaturated compacted clay to determine gas breakthrough pressures at ultimate limit state (high pressure range) and gas emission rates at serviceability limit state (low pressure range). Various degrees of saturation and thicknesses of unsaturated clay sample were considered. Moreover, numerical simulations were carried out using a coupled gas–water flow finite element program (CODE-BRIGHT) to better understand the experimental results by extending the clay thickness and varying the degree of saturation to a broader range that is typical at different

Gas breakthrough and emission through unsaturated compacted clay in landfill final cover

Energy Technology Data Exchange (ETDEWEB)

Ng, C.W.W.; Chen, Z.K.; Coo, J.L. [Department of Civil and Environmental Engineering, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon (Hong Kong); Chen, R., E-mail: chenrui1005@hotmail.com [Shenzhen Key Laboratory of Urban and Civil Engineering for Disaster Prevention and Mitigation, Harbin Institute of Technology Shenzhen Graduate School, Shenzhen 518055 (China); Zhou, C. [Department of Civil and Environmental Engineering, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon (Hong Kong)

2015-10-15

Highlights: • Explore feasibility of unsaturated clay as a gas barrier in landfill cover. • Gas breakthrough pressure increases with clay thickness and degree of saturation. • Gas emission rate decreases with clay thickness and degree of saturation. • A 0.6 m-thick clay layer may be sufficient to meet gas emission rate limit. - Abstract: Determination of gas transport parameters in compacted clay plays a vital role for evaluating the effectiveness of soil barriers. The gas breakthrough pressure has been widely studied for saturated swelling clay buffer commonly used in high-level radioactive waste disposal facility where the generated gas pressure is very high (in the order of MPa). However, compacted clay in landfill cover is usually unsaturated and the generated landfill gas pressure is normally low (typically less than 10 kPa). Furthermore, effects of clay thickness and degree of saturation on gas breakthrough and emission rate in the context of unsaturated landfill cover has not been quantitatively investigated in previous studies. The feasibility of using unsaturated compacted clay as gas barrier in landfill covers is thus worthwhile to be explored over a wide range of landfill gas pressures under various degrees of saturation and clay thicknesses. In this study, to evaluate the effectiveness of unsaturated compacted clay to minimize gas emission, one-dimensional soil column tests were carried out on unsaturated compacted clay to determine gas breakthrough pressures at ultimate limit state (high pressure range) and gas emission rates at serviceability limit state (low pressure range). Various degrees of saturation and thicknesses of unsaturated clay sample were considered. Moreover, numerical simulations were carried out using a coupled gas–water flow finite element program (CODE-BRIGHT) to better understand the experimental results by extending the clay thickness and varying the degree of saturation to a broader range that is typical at different

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

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)

Uniaxial backfill block compaction

International Nuclear Information System (INIS)

Koskinen, V.

2012-05-01

The main parts of the project were: to make a literature survey of the previous uniaxial compaction experiments; do uniaxial compaction tests in laboratory scale; and do industrial scale production tests. Object of the project was to sort out the different factors affecting the quality assurance chain of the backfill block uniaxial production and solve a material sticking to mould problem which appeared during manufacturing the blocks of bentonite and cruched rock mixture. The effect of mineralogical and chemical composition on the long term functionality of the backfill was excluded from the project. However, the used smectite-rich clays have been tested for mineralogical consistency. These tests were done in B and Tech OY according their SOPs. The objective of the Laboratory scale tests was to find right material- and compaction parameters for the industrial scale tests. Direct comparison between the laboratory scale tests and industrial scale tests is not possible because the mould geometry and compaction speed has a big influence for the compaction process. For this reason the selected material parameters were also affected by the previous compaction experiments. The industrial scale tests were done in summer of 2010 in southern Sweden. Blocks were done with uniaxial compaction. A 40 tons of the mixture of bentonite and crushed rock blocks and almost 50 tons of Friedland-clay blocks were compacted. (orig.)

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 Csclay minerals. Copyright © 2012 Elsevier Inc. All rights reserved.

Investigation of alteration behaviour of compacted bentonite contracted with carbon steel for 10 years

International Nuclear Information System (INIS)

Suyama, Tadahiro; Ueno, Kenichi; Sasamoto, Hiroshi

2008-03-01

To evaluate long term behavior of corrosion for carbon steel in compacted bentonite, and to evaluate long term stability of bentonite, corrosion experiments were conducted using synthetic sea water and synthetic groundwater at 50 and 80degC for 10 years under anaerobic atmosphere. In the present study, the samples of compacted bentonite after experiments were investigated to understand the alteration behavior of bentonite by iron-bentonite interactions. Results were summarized below. Iron generated by corrosion of carbon steel was migrated into compacted bentonite further in the synthetic seawater case than in the synthetic groundwater case. Result of TEM observation for the sample of synthetic sea water case at 80degC showed that the original layer structure for clay minerals was maintained and the layer distance was about 12[A] which was similar to the layer distance of normal 2:1 smectite. Thus, it was suggested that there was no change in smectite before and after experiments. Iron generated by corrosion of carbon steel was migrated into compacted bentonite in anaerobic condition case but scarcely migrated in aerobic condition case. Results of EPMA analysis indicated that the maximum migration depth of iron in compacted bentonite was about 0.2 mm for sample in synthetic sea water at 80degC under anaerobic condition. Results of XRD analysis for the sample in which iron migration in compacted bentonite was observed showed that there was no corrosion product in compacted bentonite and the structure of clay mineral in bentonite was di-octahedral. Furthermore, the result of XRD analysis under relative humidity controlled condition suggested that the swelling property of sample after experiment was similar to that of initial Na-type smectite. Therefore, it was supposed that the initial Na-type smectite did not change during the experiment. Batch type experiments with different temperature, solutions and duration have been conducted to understand the alteration

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.

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.

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)

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)

Clastic compaction unit classification based on clay content and integrated compaction recovery using well and seismic data

Directory of Open Access Journals (Sweden)

Zhong Hong

2016-11-01

Full Text Available Abstract Compaction correction is a key part of paleo-geomorphic recovery methods. Yet, the influence of lithology on the porosity evolution is not usually taken into account. Present methods merely classify the lithologies as sandstone and mudstone to undertake separate porosity-depth compaction modeling. However, using just two lithologies is an oversimplification that cannot represent the compaction history. In such schemes, the precision of the compaction recovery is inadequate. To improve the precision of compaction recovery, a depth compaction model has been proposed that involves both porosity and clay content. A clastic lithological compaction unit classification method, based on clay content, has been designed to identify lithological boundaries and establish sets of compaction units. Also, on the basis of the clastic compaction unit classification, two methods of compaction recovery that integrate well and seismic data are employed to extrapolate well-based compaction information outward along seismic lines and recover the paleo-topography of the clastic strata in the region. The examples presented here show that a better understanding of paleo-geomorphology can be gained by applying the proposed compaction recovery technology.

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.

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.

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

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

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.

Factors that influence the design of modified clays - or how knowing your clay can save your day

International Nuclear Information System (INIS)

Gates, W.P.; Slade, P.G.

1998-01-01

Full text: Smectites vary greatly in their permanent layer charge characteristics, including total charge, distribution of charge between tetrahedral and octahedral sheets and heterogeneity of charge from flake to flake. Smectites and vermiculites are different from the micaceous layer silicates in their ability to swell by the uptake of cations and polar and non polar solvents. Vermiculites differ from the smectites predominantly in the large contribution of tetrahedrally located charge relative to their total layer charge density. Understanding of the complex relations between layer charge and interlayer space of clay mineral surfaces can be applied toward the design of optimal organically modified clays suitable for environmental and industrial uses. In general, it is known that smectite charge density dictates the total amount of modifying organic cation that can be added to a particular clay, the orientation that the organic cation adopts within the interlayer spaces with respect to the siloxane surfaces of the clay and ultimately, the capacity of specific, organically modified clay to imbibe contaminants or other compounds. These same properties are dependent on the size and configuration of the modifying organic cation(s) as well as the percentage of the exchange capacity utilised, and thus, the amount of specific surface of the clay that is covered by the modifying organic cation. All these factors must be kept in mind in the design of inexpensive and useful modified clays. This paper reports on the application of polarised FT-IR and X-ray diffraction methods to the observation that layer charge density governs the orientation of trimethylphenylammonium (TMPA) cations in the interlayer space of smectites and vermiculites. The TMPA exchanged forms of several smectites and vermiculites were studied, whose layer charges ranged between X=0.37 and X=0.95 e - per formula unit and in which the location of charge varied with respect to the octahedral and

Procedures and apparatus for measuring diffusion and distribution coefficients in compacted clays

Energy Technology Data Exchange (ETDEWEB)

Hume, H B

1993-12-01

Diffusion and distribution coefficients are needed to assess the migration of radionuclides through the compacted clay-based buffer and backfill materials proposed for use in a nuclear fuel waste disposal vault. This report describes the techniques used to measure these coefficients. Both steady-state and transient diffusion experiments are discussed. The procedures used to prepare the clay plug, assemble the cell, conduct the experiment and calculate the results are described. In addition, methods for obtaining distribution coefficients for radionuclides on both loose and compacted clays are discussed. (author). 18 refs., 3 tabs., 16 figs.

Procedures and apparatus for measuring diffusion and distribution coefficients in compacted clays

International Nuclear Information System (INIS)

Hume, H.B.

1993-12-01

Diffusion and distribution coefficients are needed to assess the migration of radionuclides through the compacted clay-based buffer and backfill materials proposed for use in a nuclear fuel waste disposal vault. This report describes the techniques used to measure these coefficients. Both steady-state and transient diffusion experiments are discussed. The procedures used to prepare the clay plug, assemble the cell, conduct the experiment and calculate the results are described. In addition, methods for obtaining distribution coefficients for radionuclides on both loose and compacted clays are discussed. (author). 18 refs., 3 tabs., 16 figs

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.

Development of clay characterization methods for use in repository design with application to a natural Ca bentonite clay containing a redox front

International Nuclear Information System (INIS)

Karnland, O.; Pusch, R.

1990-12-01

Natural smectite clays in the form of 'true' bentonites formed from volcanic ash, or resulting from in-situ weathering of rock, are suitable for a number of sealing options in repositories, both as tightening component of sand/clay backfills and as highly efficient buffer for embedment of canisters, as well as for fracture sealing. The price and quality, in terms of smectite content and type of smectite, vary considerably and an optimum choice of clay for use in repositories has to be based on quantitative quality data. This requires characterization of the clay material for which a test scheme has been worked out. It comprises determination of the granulometrical, chemical, and mineralogical compositions, as well as of certain physical properties. Recent research shows the importance of the type of smectite for the longevity of buffers in repository environment, beidellite being less favourable and saponite superior to montmorillonite, which is the most common smectite species. The test scheme hence includes means of distinguishing between various smectite minerals. The influence of accessory minerals on the chemical integrity of both the smectite and the canister material requires identification also of such minerals, for which the scheme is useful as well. The report summarizes the various test procedures and gives data from application of the scheme to samples from a natural Ca bentonite containing a redox front. This study suggests that a significant part of the iron in the clay fraction is in the form of Fe 2+ in octahedral positions of the montmorillonite of unoxidized natural clay and that it is converted to Fe 3+ on oxidation. Part of the iron is probably in the form of the Fe 2+ Fe 3+ hydroxy compounds that give the unoxidized clay its bluish colour, while they can be assumed to be transformed to yellowish FeOOH forms on oxidation. (author)

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)

Synthesis and characterization of organophilic clay from Cuban Chiqui Gomez bentonite

International Nuclear Information System (INIS)

Cortes, Guillermo R. Martin; Hennies, Wildor T.; Valera, Ticiane S.; Esper, Fabio J.; Diaz, Francisco R. Valenzuela

2009-01-01

Smectite are clay minerals with a layered structure and nanometric thickness, high specific area and a huge variety of uses. Consisting on stacked layers of about 1nm thickness, including two silica tetrahedral and one octahedral sheet. Properties of natural Smectite can be enhanced by organic modification, due to the substitution of the exchangeable cations in the interlayer area. In fact, the properties of the modified smectite (organophilic clay) are related to its modified chemical composition and structural parameters. The interaction of smectite clays with surfactants has an important interest in the fields of drilling fluids, paints, cosmetic, ceramic industries and others. Recent applications are: remediation of contaminated areas and polymer/clay nanocomposites. The aim of this paper is to obtain organophilic clays using a bentonite from the Chiqui Gomez deposit in Central Cuba. The raw and organophilic clays were analyzed by DRX, SEM, swelling capacity in organic solvents and others. (author)

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.

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.

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

Methylene blue adsorption in clay mineral dealt with organic cation

International Nuclear Information System (INIS)

Silva, T.L.; Lemos, V.P.

2011-01-01

The interaction among organic cations, as the methylene blue (AM) and benzyltrimethylammonium (BTMA), and clay minerals of the group of the smectite they result in the formation of applied materials in the adsorption of organic pollutant presents in waters, soils and you cultivate. In this work they were prepared the adsorbents (organic-clays) smectite - AM and smectite-BTMA. The precursory sample of smectite was collected in Rio Branco-Acre. We were also used an smectite sample collected in Sena Madureira (SM)-Acre already characterized in previous work and a sample of standard smectite Swy-2-Na-Montmorillonite (SWy-2) of Wymong - USA. The organic agents selected for this study they were: Blue of Methylene, denominated AM and Benzyltrimethylammonium, denominated BTMA. They were appraised the capacities adsorptive of the treated samples with BTMA being used AM as adsorbate. The results of these evaluations detected that ran total adsorption of AM (concentrations varying from 1 to 10 ppm) for the treated samples with BTMA. The organic cation, BTMA, interacting with the surfaces of the natural clay was more efficient in the adsorption of AM than the clay without the previous treatment with this salt. (author)

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

clay is highly compacted. In developing the dynamic force balance model for colloidal expansion, it is acknowledged that accurate description of the viscous drag force, or equivalently the permeability, is very important to describe the swelling process of compacted bentonite as it expands and eventually turns from a gel into a sol in low ionic strength waters. For this reason, a Kozeny-Carman-like equation is elaborated in order to satisfactorily predict the permeability of the purified and fully Na-exchanged bentonite in dilute homo-ionic solutions, based on a set of permeability measurements. We present the measured versus predicted values of the permeabilities for Na-bentonites in different NaCl solutions. It is seen that the measured values are aligned in a narrow band along the predicted ones, falling well in the range of 1/2 and 2 times the predicted permeabilities. For usual laboratory results of the permeability test, this is definitely within the expected margin of variations. The force balance model, together with a friction model derived from the permeability, is then validated against accurate observations of the expansion process of the Na-exchanged bentonite in a water filled vertical test tube. The expansion is followed in detail over a month, by use of the magnetic resonance imaging technique with a spatial resolution of 0.2 mm, as an initially compacted tablet of Na-bentonite expands in water. The model accurately predicts not only the expansion rate, the general features of the expansion but also the basic behaviour at the expanding gel/sol interface, as exemplified for the case of expansion of a purified and fully Na-exchanged bentonite (WyNa) in an initially 0.5 mM CaCl 2 solution. The agreements demonstrate in turn that the Kozeny-Carman-like equation is successful in predicting the permeability of the Na-bentonite in dilute homo-ionic solutions. The model will be used to quantify the release of colloidal particles from an expanding buffer around

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)

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.

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.

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.

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)

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.

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.

Water diffusion through compacted clays analyzed by neutron scattering and tracer experiments

Energy Technology Data Exchange (ETDEWEB)

Gonzalez Sanchez, F

2007-11-15

Clay minerals are aluminium phyllosilicates, mostly products of the chemical alteration and mechanical breakdown of igneous and metamorphic rocks. Their physical and chemical properties can be directly related to their layered, fine-grained (large surface area) structure. These properties such as large water retention, low hydraulic conductivity, heat resistance and ionic exchange capacities, make clays ideal for many different applications, e.g. as sealing material for the underground disposal of radioactive waste. The long-term disposal of radioactive waste in an underground geological repository is based on a multibarrier concept. In the barrier of highly compacted clay, water is intercalated and confined between the clay layers. The narrow pores are responsible that under natural hydraulic gradients, molecular diffusion through water is the dominant transport mechanism for released radionuclides. The properties of water at the water-clay interface differ from that of bulk water. Therefore, a good and deep understanding of the water structure and dynamics in compacted clay systems is fundamental. This knowledge is the base for the progressing research about transport of pollutants through the compacted clays and argillaceous rock of radioactive waste barriers. This study focusses on four different types of pure clays, two of them charged, namely montmorillonite and illite (both in a Na and Ca form), and two uncharged, namely kaolinite and pyrophyllite. Their structural differences result in a significantly different behaviour in contact with water. In case of montmorillonite, water is located in between particles and in the interlayer space. In illite, water is found only in between particles, because the interlayer surfaces are tightly linked by potassium cations. The layers of kaolinite and pyrophyllite are uncharged and, consequently, water is located only in between particles. The clay powders were compacted to reach a high bulk dry density of about 1.9 g

Water diffusion through compacted clays analyzed by neutron scattering and tracer experiments

International Nuclear Information System (INIS)

Gonzalez Sanchez, F.

2007-11-01

Clay minerals are aluminium phyllosilicates, mostly products of the chemical alteration and mechanical breakdown of igneous and metamorphic rocks. Their physical and chemical properties can be directly related to their layered, fine-grained (large surface area) structure. These properties such as large water retention, low hydraulic conductivity, heat resistance and ionic exchange capacities, make clays ideal for many different applications, e.g. as sealing material for the underground disposal of radioactive waste. The long-term disposal of radioactive waste in an underground geological repository is based on a multibarrier concept. In the barrier of highly compacted clay, water is intercalated and confined between the clay layers. The narrow pores are responsible that under natural hydraulic gradients, molecular diffusion through water is the dominant transport mechanism for released radionuclides. The properties of water at the water-clay interface differ from that of bulk water. Therefore, a good and deep understanding of the water structure and dynamics in compacted clay systems is fundamental. This knowledge is the base for the progressing research about transport of pollutants through the compacted clays and argillaceous rock of radioactive waste barriers. This study focusses on four different types of pure clays, two of them charged, namely montmorillonite and illite (both in a Na and Ca form), and two uncharged, namely kaolinite and pyrophyllite. Their structural differences result in a significantly different behaviour in contact with water. In case of montmorillonite, water is located in between particles and in the interlayer space. In illite, water is found only in between particles, because the interlayer surfaces are tightly linked by potassium cations. The layers of kaolinite and pyrophyllite are uncharged and, consequently, water is located only in between particles. The clay powders were compacted to reach a high bulk dry density of about 1.9 g

EFFECTS OF INORGANIC SALT SOLUTION ON SOME PROPERTIES OF COMPACTED CLAY LINERS

Directory of Open Access Journals (Sweden)

KHALID R. MAHMOOD AL-JANABI

2017-12-01

Full Text Available Processed and natural clays are widely used to create impermeable liners in solid waste disposal landfills. The engineering properties of clay liners can be significantly affected by the leachate from the waste mass. In this study, the effect of inorganic salt solutions will be investigated. These solutions used at different concentrations. Two type of inorganic salt MnSO4 and FeCl3 are used at different concentration 2%,5%, 10%. Clay used in this study was the CL- clay (kaolinite. The results show that the consistency limits and unconfined compressive strength increased as the concentration of salts increased. While the permeability tends to decrease as salt concentration increased. Also, the compression index decreases as the concentration increased from 2% to 5%. The swelling index tends to increase slightly as the concentration of MnSO4 increased, while its decrease as the concentration of FeCl3. In this paper, it is aimed to investigate the performance of compacted clay liner exposed to the certain chemicals generated by the leachate and their effects on the geotechnical properties of compacted clay liner such consistency limits, permeability coefficient, compressibility characteristics and unconfined compressive strength.

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.

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

Electric Resistance Tests on Compacted Clay Material under Dynamic Load Coupled with Dry-Wet Cycling

Directory of Open Access Journals (Sweden)

Zheng Lu

2018-01-01

Full Text Available The study of compacted clay material under dynamic load coupled with dry-wet cycling is one of the most important areas in the field of transportation. In this paper, experiments in terms of compacted clay under dynamic load coupled with dry-wet cycling are performed, and synchronous resistivity tests are also conducted. According to the test results, the influences of cumulative plastic strain, dry-wet cycles, and amplitudes on the soil resistivity are analyzed. Then a new damage factor based on resistivity is proposed to evaluate the long-term performance of compacted clay material. The result of research shows that the evolution of the soil resistivity can be divided into two stages, which has a contrary tendency with that of cumulative plastic strain. The dry-wet cycles and amplitudes have a significant effect on the damage of the compacted soil, which indicates that the dry-wet cycling of compacted soil materials should not be ignored in road engineering, especially in rainy and humid areas.

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.

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.

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

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.

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

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

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

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.

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

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

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.

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.

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.

Permeability Characteristics of Compacted and Stabilized Clay with Cement, Peat Ash and Silica Sand

OpenAIRE

Seyed Esmaeil Mousavi; Leong Sing Wong

2016-01-01

The present paper investigates the influence of stabilization with cement, peat ash, and silica sand on permeability coefficient (kv) of compacted clay, using a novel approach to stabilize the clay with peat ash as a supplementary material of cement in the compacted and stabilized soil. In order to assess the mentioned influence, test specimens of both untreated and stabilized soil have been tested in the laboratory so that their permeability could be evaluated. Falling head and one dimension...

Consistency in the description of diffusion in compacted bentonite

International Nuclear Information System (INIS)

Lehikoinen, J.; Muurinen, A.

2009-01-01

A macro-level diffusion model, which aims to provide a unifying framework for explaining the experimentally observed co-ion exclusion and greatly controversial counter-ion surface diffusion in a consistent fashion, is presented. It is explained in detail why a term accounting for the non-zero mobility of the counter-ion surface excess is required in the mathematical form of the macroscopic diffusion flux. The prerequisites for the consistency of the model and the problems associated with the interpretation of diffusion in such complex pore geometries as in compacted smectite clays are discussed. (author)

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.

X-ray diffraction analysis of clay stones, Muglad Sedimentary Basin, Sudan

International Nuclear Information System (INIS)

Ali, A. E.

1997-01-01

This study deals with the theoretical and experimental aspects of X-ray diffraction (XRD) technique. Moreover the XRD technique has been used to investigate the clay mineral types and their distribution for samples obtained from exploration wells in the Mugald Sedimentary Basin in Western Sudan. The studied samples range in depth from 1524 m to 4572 m. The XRD analysis of samples shows that they consist of kaolinite, smectite, illite, chlorite and the mixed-layer smectite/illite. Kaolinite has higher abundance (15 - 72 %) followed by illite (7 - 34 %), smectite (11 - 76 %) and the less abundance of chlorite and the mixed-layer smectite/illite. Non-clay minerals found include quartz and cristabolite. The clay mineral types and their vertical distribution reflect various controls such as environmental, burial diagenesis, source rocks and climatic influences in the Muglad Sedimentary Basin. (author). 19 refs., 11 figs., 3 tabs

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.

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')

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

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

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

Hydrothermal field test with french candidate clay embedding steel heater in the Stripa mine

International Nuclear Information System (INIS)

Pusch, R.; Karnland, O.; Lajudie, A.; Lechelle, J.; Bouchet, A.

1992-12-01

Field experiments with French kaolinite/smectite clay heated up to 170 degrees C in boreholes in granite were conducted for 8 months and 4 years. The clay heated for 8 months has a considerably higher water content and it had undergone much less changes in mineralogy and physical properties than the clay exposed to heating for 4 years. The drying of the latter clay was probably caused by hydrogen gas from corrosion of the heater. The clay next to the heater turned into clay-stone despite conversion of the kaolinite component to smectite. (42 refs)

Geotechnical and geochemical assessments of shales in Anambra basin, SE-Nigeria as compacted clay liner in landfill system

International Nuclear Information System (INIS)

Tijani, Moshood N.; Adesina, Rasheed B.; Wagner, Jean-Frank

2012-01-01

density irrespective of the compaction level to be utilized in the field. In addition, the permeability of 2.14 - 9.12 x 10 -5 cm/s is higher than 1 x 10 -7 cm/s recommended for typical isolation barriers, which implies negative impacts in respect of possible attendant contamination of the surrounding soil and groundwater by the leachates. The geochemical analyses of the samples reflect relatively high SiO 2 values of 52.1-55.8% compared to Al 2 O 3 of 16.96-27.45% and Fe 2 O 3 of 3.10 -7 .19%, which suggest the dominance of kaolinite as confirmed by the XRD. Nonetheless, the occurrence of illite in Enugu and Nkporo shales and smectite in Imo shale is a confirmation of the relatively high plasticity indices mentioned earlier and indication of good sorption properties. The CEC of the samples have relatively low value of 2.6 - 5.1 cmol/kg, which is less than the recommended minimum of 10 meq/100 g. The sorption capacity of the samples with respect to Zn, Cu, Pb, Cd and Ni ranges from 24.4 to 34.7 ppm with metal sorption in the order of Zn >Cu > Pb > Cd > Ni. The overall assessment revealed that the metal uptake, CEC and plasticity index of the shale samples are positively correlated suggesting strong influence of the clay mineralogy on the sorption characteristics of the samples. In spite of the observed relatively high permeability and swelling potential as well as moderate good sorption properties, the study shale units could be enhanced to the required specification through appropriate amendment technology. Though the shale units do not generally satisfy the requirements of compacted clay liners, however, based on the sorption characteristics, Enugu, Nkporo and Imo shales can be adequately employed for attenuation of contaminant leachates in double, composite or and multiple lining systems

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.

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.

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

Microbial incidence on copper and titanium embedded in compacted bentonite clay

Energy Technology Data Exchange (ETDEWEB)

Persson, Joergen; Lydmark, Sara; Edlund, Johanna; Paeaejaervi, Anna; Pedersen, Karsten (Microbial Analytics Sweden AB (Sweden))

2011-10-15

The incidence of bacteria on metal surfaces was examined in an experimental setting simulating conditions of the proposed Swedish concept for disposal of spent nuclear fuel. Titanium and copper rods were embedded in compacted bentonite clay saturated with groundwater collected at a depth of 450 m. Bentonite blocks were exposed to an external flux of groundwater with or without added lactate or H{sub 2} for up to 203 days. Bacterial accumulation on metal rods and in the surrounding bentonite was analyzed using real-time quantitative PCR (qPCR), with genetic markers for overall bacterial presence (16S rDNA) as well as specific for sulfate-reducing bacteria (apsA). Clay species composition was analyzed by cloning and sequencing 16S rDNA extracted from the clay. Results suggest limited bacterial accumulation on metal surfaces, amounting to a maximum of approximately 106 apsA copies cm-2, corresponding to a 3.7% coverage of metal surfaces. Bacterial species composition appeared to be a mix of species originating from the bentonite clay and from the added groundwater, including an apparently high proportion of sulfate-reducing bacteria. While titanium surfaces exhibited higher bacterial presence than did copper surfaces, neither the degree of bentonite compaction nor the addition of lactate or H{sub 2} appeared to have any effect on the bacterial incidence on metal surfaces

Microbial incidence on copper and titanium embedded in compacted bentonite clay

International Nuclear Information System (INIS)

Persson, Joergen; Lydmark, Sara; Edlund, Johanna; Paeaejaervi, Anna; Pedersen, Karsten

2011-10-01

The incidence of bacteria on metal surfaces was examined in an experimental setting simulating conditions of the proposed Swedish concept for disposal of spent nuclear fuel. Titanium and copper rods were embedded in compacted bentonite clay saturated with groundwater collected at a depth of 450 m. Bentonite blocks were exposed to an external flux of groundwater with or without added lactate or H 2 for up to 203 days. Bacterial accumulation on metal rods and in the surrounding bentonite was analyzed using real-time quantitative PCR (qPCR), with genetic markers for overall bacterial presence (16S rDNA) as well as specific for sulfate-reducing bacteria (apsA). Clay species composition was analyzed by cloning and sequencing 16S rDNA extracted from the clay. Results suggest limited bacterial accumulation on metal surfaces, amounting to a maximum of approximately 10 6 apsA copies cm -2 , corresponding to a 3.7% coverage of metal surfaces. Bacterial species composition appeared to be a mix of species originating from the bentonite clay and from the added groundwater, including an apparently high proportion of sulfate-reducing bacteria. While titanium surfaces exhibited higher bacterial presence than did copper surfaces, neither the degree of bentonite compaction nor the addition of lactate or H 2 appeared to have any effect on the bacterial incidence on metal surfaces

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.

Comparing uranyl sorption complexes on soil and reference clays

International Nuclear Information System (INIS)

Chisholm-Brause, C.J.; Berg, J.M.; Conradson, S.D.; Morris, D.E.; McKinley, J.P.; Zachara, J.M.

1993-01-01

Clay minerals and other components in natural soils may play a key role in limiting the mobility of uranium in the environment through the formation of sorption complexes. Reference clays are frequently used as models to study sorption processes because they have well-known chemical and physical properties, but they may differ chemically and morphologically from clays derived from natural soils. Therefore, inferences based on reference clay data have been questioned. The authors have used luminescence and x-ray absorption spectroscopies to characterize the sorption complexes of aqueous uranyl (UO 2 2+ ) species on two soil smectites from the Kenoma and Ringold formations, and compared these results to those obtained on reference smectite clays. The pH dependence of uptake suggests that the ratio of sorption on amphoteric edge sites is greater for the soil smectites than for reference clays such as Wyoming montmorillonite (SWy-1). The luminescence spectra for uranyl sorbed to the soil clays are very similar to those for uranyl sorbed principally to the edge sites of SWy-1. This observation supports the solution data suggesting that adsorption to amphoteric sites is a more important mechanism for soil clays. However, the spectral data indicate that the sorption complexes on natural and reference clays are quite similar. Furthermore, as with the reference clays, the authors have found that the chemistry of the solution plays a greater role in defining the sorption complex than does the clay matrix. Thus, if differences in surface properties are adequately taken into account, the reference clays may serve as useful analogs for soil clays in investigations of metal-ion sorption

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

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

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

Induced polarization of clay-sand mixtures: experiments and modeling

International Nuclear Information System (INIS)

Okay, G.; Leroy, P.; Tournassat, C.; Ghorbani, A.; Jougnot, D.; Cosenza, P.; Camerlynck, C.; Cabrera, J.; Florsch, N.; Revil, A.

2012-01-01

Document available in extended abstract form only. Frequency-domain induced polarization (IP) measurements consist of imposing an alternative sinusoidal electrical current (AC) at a given frequency and measuring the resulting electrical potential difference between two other non-polarizing electrodes. The magnitude of the conductivity and the phase lag between the current and the difference of potential can be expressed into a complex conductivity with the in-phase representing electro-migration and a quadrature conductivity representing the reversible storage of electrical charges (capacitive effect) of the porous material. Induced polarization has become an increasingly popular geophysical method for hydrogeological and environmental applications. These applications include for instance the characterization of clay materials used as permeability barriers in landfills or to contain various types of contaminants including radioactive wastes. The goal of our study is to get a better understanding of the influence of the clay content, clay mineralogy, and pore water salinity upon complex conductivity measurements of saturated clay-sand mixtures in the frequency range ∼1 mHz-12 kHz. The complex conductivity of saturated unconsolidated sand-clay mixtures was experimentally investigated using two types of clay minerals, kaolinite and smectite in the frequency range 1.4 mHz - 12 kHz. Four different types of samples were used, two containing mainly kaolinite (80% of the mass, the remaining containing 15% of smectite and 5% of illite/muscovite; 95% of kaolinite and 5% of illite/muscovite), and the two others containing mainly Na-smectite or Na-Ca-smectite (95% of the mass; bentonite). The experiments were performed with various clay contents (1, 5, 20, and 100% in volume of the sand-clay mixture) and salinities (distilled water, 0.1 g/L, 1 g/L, and 10 g/L NaCl solution). In total, 44 saturated clay or clay-sand mixtures were prepared. Induced polarization measurements

Preferred Orientation and Anisotropy of Clay minerals and Pores in Posidonia Shales

Science.gov (United States)

Kanitpanyacharoen, W.; Chen, K.; Wenk, H.

2010-12-01

Shales compose a large part of sedimentary basins and form the seal and source rocks for hydrocarbon reservoirs. They are also of great interest in context of repositories for nuclear waste and carbon sequestration. A comprehensive study of shale properties is thus crucial for seismic prospecting, particularly due to high elastic anisotropy that is contributed by the alignment of constituent clay minerals during compaction and diagenesis. In this study, we quantitatively analyze composition, crystal preferred orientation (or texture), and the 3D porosity structure in four Posidonia shales from Germany using high energy synchrotron x-rays. We can infer texture information from x-ray diffraction images relying on the Rietveld method, as well as determine the 3D porosity structure from tomography images. We observed that quartz and calcite are dominating phases while illite-smectite, illite-mica and kaolinite are the major clay minerals. The texture strength of clays range from 4.22 to 6.12 m.r.d. A comparison of shallow Posidonia shales with deep shales from the North Sea, Saudi Arabia, and the Gulf of Mexico documents that P-wave anisotropy increases with increasing phyllosilicate content (mainly illite-smectite and kaolinite) and increasing burial. Low absorption features in microtomography images indicate porosity (including kerogen and fractures), which is estimated at 1 vol% and observed to be anisotropic, mainly organized parallel to bedding with little connectivity of flat pores in direction perpendicular to the bedding plane.

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)

The Buffer and Backfill Handbook. Part 2: Materials and techniques

International Nuclear Information System (INIS)

Pusch, Roland

2001-12-01

of commercially smectite-rich clays. Chapter 4 deals with the non-clay mineral components of mixtures of such material, termed 'ballast' here, and smectitic clay. Mixtures of this sort can primarily be used for backfilling shafts and tunnels with less tight soil material than the buffer clay but sufficiently low-conductive and expansive to prevent deposition tunnels from serving as effective hydraulic conductors. The chapter also describes major sources, primarily glacial deposits and crushed rock. Chapter 5 deals with the granulometric composition of mixtures of smectitic clay and ballast for achieving good compactability and effective filling of clay in the voids between ballast grains. Focus is on the gradation of the ballast and the density of the clay component since it controls the hydraulic conductivity of the mixtures. Chapter 6 deals with chemical composition and properties of smectitic clays and ballast materials. It is a very comprehensive issue and we will confine ourselves to describe the chemical composition of clays tested by SKB and provide a basis for estimating their chemical stability and physical performance. This latter issue is under investigation and is further treated in Part 3. Chapter 7 gives the basis of selection of suitable buffers and clay/ballast mixtures with respect to their desired performance in a repository. Major physical properties of common commercial smectite-rich clays and clay/ballast mixtures are described in detail and can serve as reference in designing buffers and backfills. Chapter 8 deals with methods for preparing buffer materials, primarily blocks of highly compacted smectite-rich clay materials. Also, major physical properties of compacted blocks are given as a basis of determining the performance of the system of blocks applied in deposition holes before hydration, swelling and homogenisation has started. Chapter 9 describes methods for preparing, applying and compacting clay/ballast mixtures. Examples are given

The Buffer and Backfill Handbook. Part 2: Materials and techniques

Energy Technology Data Exchange (ETDEWEB)

Pusch, Roland [Geodevelopment AB, Lund (Sweden)

2001-12-01

of commercially smectite-rich clays. Chapter 4 deals with the non-clay mineral components of mixtures of such material, termed 'ballast' here, and smectitic clay. Mixtures of this sort can primarily be used for backfilling shafts and tunnels with less tight soil material than the buffer clay but sufficiently low-conductive and expansive to prevent deposition tunnels from serving as effective hydraulic conductors. The chapter also describes major sources, primarily glacial deposits and crushed rock. Chapter 5 deals with the granulometric composition of mixtures of smectitic clay and ballast for achieving good compactability and effective filling of clay in the voids between ballast grains. Focus is on the gradation of the ballast and the density of the clay component since it controls the hydraulic conductivity of the mixtures. Chapter 6 deals with chemical composition and properties of smectitic clays and ballast materials. It is a very comprehensive issue and we will confine ourselves to describe the chemical composition of clays tested by SKB and provide a basis for estimating their chemical stability and physical performance. This latter issue is under investigation and is further treated in Part 3. Chapter 7 gives the basis of selection of suitable buffers and clay/ballast mixtures with respect to their desired performance in a repository. Major physical properties of common commercial smectite-rich clays and clay/ballast mixtures are described in detail and can serve as reference in designing buffers and backfills. Chapter 8 deals with methods for preparing buffer materials, primarily blocks of highly compacted smectite-rich clay materials. Also, major physical properties of compacted blocks are given as a basis of determining the performance of the system of blocks applied in deposition holes before hydration, swelling and homogenisation has started. Chapter 9 describes methods for preparing, applying and compacting clay/ballast mixtures. Examples are

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

Science.gov (United States)

Bourg, Ian C; Ajo-Franklin, Jonathan B

2017-09-19

The ability to predict the permeability of fine-grained soils, sediments, and sedimentary rocks is a fundamental challenge in the geosciences with potentially transformative implications in subsurface hydrology. In particular, fine-grained sedimentary rocks (shale, mudstone) constitute about two-thirds of the sedimentary rock mass and play important roles in three energy technologies: petroleum geology, geologic carbon sequestration, and radioactive waste management. The problem is a challenging one that requires understanding the properties of complex natural porous media on several length scales. One inherent length scale, referred to hereafter as the mesoscale, is associated with the assemblages of large grains of quartz, feldspar, and carbonates over distances of tens of micrometers. Its importance is highlighted by the existence of a threshold in the core scale mechanical properties and regional scale energy uses of shale formations at a clay content X clay ≈ 1/3, as predicted by an ideal packing model where a fine-grained clay matrix fills the gaps between the larger grains. A second important length scale, referred to hereafter as the nanoscale, is associated with the aggregation and swelling of clay particles (in particular, smectite clay minerals) over distances of tens of nanometers. Mesoscale phenomena that influence permeability are primarily mechanical and include, for example, the ability of contacts between large grains to prevent the compaction of the clay matrix. Nanoscale phenomena that influence permeability tend to be chemomechanical in nature, because they involve strong impacts of aqueous chemistry on clay swelling. The second length scale remains much less well characterized than the first, because of the inherent challenges associated with the study of strongly coupled nanoscale phenomena. Advanced models of the nanoscale properties of fine-grained media rely predominantly on the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, a mean field

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.

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

Multifaceted role of clay minerals in pharmaceuticals

OpenAIRE

Khurana, Inderpreet Singh; Kaur, Satvinder; Kaur, Harpreet; Khurana, Rajneet Kaur

2015-01-01

The desirable physical and physiochemical properties of clay minerals have led them to play a substantial role in pharmaceutical formulations. Clay minerals like kaolin, smectite and palygorskite-sepiolite are among the world's most valuable industrial minerals and of considerable importance. The elemental features of clay minerals which caused them to be used in pharmaceutical formulations are high specific area, sorption capacity, favorable rheological properties, chemical inertness, swelli...

Effects of natural heating on a clay formation

International Nuclear Information System (INIS)

Polizzano, C.; Sensi, L.; Leoni, L.; Sartori, F.

1985-01-01

As a contribution to the characterization of clay deposits as possible sites for nuclear waste disposal, the metamorphic effects induced on Pliocene argillaceous sediments by the small subvolcanic body of Orciatico (Tuscany, Italy) were investigated. In areas close to marginal facies of the magmatic body, where temperatures were presumably ranging from 100 to 500 0 C, the thermo-metamorphic aureole thickness doesn't exceed 2 meters. In this zone the clay fraction (45-69% of the bulk rock) changes from an illite+illite/smectite interstratified+vermiculite+chloritic intergrades assemblage to a paragenesis characterized only by illite+smectite, the later being the most stable phase among the clay minerals. Within such zone alkalis (Na,K, and Rb) and alkaline-earths (Ca and Sr) result to be the most highly mobilized elements

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.

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

Science.gov (United States)

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

Methylene blue adsorption in clay mineral dealt with organic cation; Sorcao de azul de metileno em argila esmectitica tratada com cation organico

Energy Technology Data Exchange (ETDEWEB)

Silva, T.L. [Universidade Federal do Para (UFPA), Maraba, PA (Brazil). Faculdade de Engenharia de Materiais; Lemos, V.P., E-mail: tls1981@hotmail.com [Universidade Federal do Para (UFPA), Belem, PA (Brazil). Centro de Geociencias

2011-07-01

The interaction among organic cations, as the methylene blue (AM) and benzyltrimethylammonium (BTMA), and clay minerals of the group of the smectite they result in the formation of applied materials in the adsorption of organic pollutant presents in waters, soils and you cultivate. In this work they were prepared the adsorbents (organic-clays) smectite - AM and smectite-BTMA. The precursory sample of smectite was collected in Rio Branco-Acre. We were also used an smectite sample collected in Sena Madureira (SM)-Acre already characterized in previous work and a sample of standard smectite Swy-2-Na-Montmorillonite (SWy-2) of Wymong - USA. The organic agents selected for this study they were: Blue of Methylene, denominated AM and Benzyltrimethylammonium, denominated BTMA. They were appraised the capacities adsorptive of the treated samples with BTMA being used AM as adsorbate. The results of these evaluations detected that ran total adsorption of AM (concentrations varying from 1 to 10 ppm) for the treated samples with BTMA. The organic cation, BTMA, interacting with the surfaces of the natural clay was more efficient in the adsorption of AM than the clay without the previous treatment with this salt. (author)

Thermal Analysis: A Complementary Method to Study the Shurijeh Clay Minerals

Directory of Open Access Journals (Sweden)

Golnaz Jozanikohan

2015-06-01

Full Text Available Clay minerals are considered the most important components of clastic reservoir rock evaluation studies. The Shurijeh gas reservoir Formation, represented by shaly sandstones of the Late Jurassic-Early Cretaceous age, is the main reservoir rock in the Eastern Kopet-Dagh sedimentary Basin, NE Iran. In this study, X-ray diffraction (XRD, X-ray fluorescence (XRF, scanning electron microscopic (SEM studies, and thermal analysis including differential thermal analysis (DTA, and thermogravimetric analysis (TGA techniques were utilized in the characterization of the Shurijeh clay minerals in ten representative samples. The XRF studies showed that silica and aluminum oxides are present quantities. The XRD test was then used to determine the mineralogical composition of bulk components, as well as the clay fraction. The XRD patterns indicated the presence of dominant amount of quartz and plagioclase, with moderate to minor amounts of alkali feldspar, anhydrite, carbonates (calcite and dolomite, hematite and clay minerals. The most common clays in the Shurijeh Formation were illite, chlorite, and kaolinite. However, in very few samples, glauconite, smectite, and mixed layer clay minerals of both illite-smectite and chlorite-smectite types were also recognized. The XRD results were quantified, using the elemental information from the XRF test, showing that each Shurijeh exhibited low to moderate amounts of clay minerals, typically up to 21%. The amount of illite, the most dominant clay mineral, reached maximum of 13.5%, while the other clay types were significantly smaller. Based on the use of SEM and thermal data, the results of the identification of clay minerals, corresponded with the powder X-ray diffraction analysis, which can be taken into account as an evidence of the effectiveness of the thermal analysis technique in clay typing, as a complementary method besides the XRD.

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

Mobility and survival of sulphate-reducing bacteria in compacted and fully water saturated bentonite - microstructural aspects

Energy Technology Data Exchange (ETDEWEB)

Pusch, R. [Geodevelopment AB, Lund (Sweden)

1999-12-01

Sulphate-reducing bacteria will not be able to enter MX-80 buffer clay with the intended bulk density, i.e. 1900-2100 kg/m{sup 3}. Nor will they be able to survive and migrate in such environment. The only circumstances under which sulphate-reducing bacteria can enter, survive and migrate in engineered soil barriers in a KBS-3-type repository are those prevailing in backfills with lower MX-80 contents than about 10 % or in more smectite-rich, poorly compacted backfills saturated with electrolyte-rich pore water with Ca as dominating cation. In the phase of hydration and expansion of canister-embedding buffer, bacteria can enter the initially very soft clay gel at the rock/buffer contact to a depth of about a centimeter.

Mobility and survival of sulphate-reducing bacteria in compacted and fully water saturated bentonite - microstructural aspects

International Nuclear Information System (INIS)

Pusch, R.

1999-12-01

Sulphate-reducing bacteria will not be able to enter MX-80 buffer clay with the intended bulk density, i.e. 1900-2100 kg/m 3 . Nor will they be able to survive and migrate in such environment. The only circumstances under which sulphate-reducing bacteria can enter, survive and migrate in engineered soil barriers in a KBS-3-type repository are those prevailing in backfills with lower MX-80 contents than about 10 % or in more smectite-rich, poorly compacted backfills saturated with electrolyte-rich pore water with Ca as dominating cation. In the phase of hydration and expansion of canister-embedding buffer, bacteria can enter the initially very soft clay gel at the rock/buffer contact to a depth of about a centimeter

Clay Mineralogy of AN Alluvial Aquifer in a Mountainous, Semiarid Terrain, AN Example from Rifle, Colorado

Science.gov (United States)

Elliott, W. C.; Lim, D.; Zaunbrecher, L. K.; Pickering, R. A.; Williams, K. H.; Navarre-Sitchler, A.; Long, P. E.; Noel, V.; Bargar, J.; Qafoku, N. P.

2015-12-01

Alluvial sediments deposited along the Colorado River corridor in the semi-arid regions of central to western Colorado can be important hosts for legacy contamination including U, V, As and Se. These alluvial sediments host aquifers which are thought to provide important "hot spots" and "hot moments" for microbiological activity controlling organic carbon processing and fluxes in the subsurface. Relatively little is known about the clay mineralogy of these alluvial aquifers and the parent alluvial sediments in spite of the fact that they commonly include lenses of silt-clay materials. These lenses are typically more reduced than coarser grained materials, but zones of reduced and more oxidized materials are present in these alluvial aquifer sediments. The clay mineralogy of the non-reduced parent alluvial sediments of the alluvial aquifer located in Rifle, CO (USA) is composed of chlorite, smectite, illite, kaolinite and quartz. The clay mineralogy of non-reduced fine-grained materials at Rifle are composed of the same suite of minerals found in the sediments plus a vermiculite-smectite intergrade that occurs near the bottom of the aquifer near the top of the Wasatch Formation. The clay mineral assemblages of the system reflect the mineralogically immature character of the source sediments. These assemblages are consistent with sediments and soils that formed in a moderately low rainfall climate and suggestive of minimal transport of the alluvial sediments from their source areas. Chlorite, smectite, smectite-vermiculite intergrade, and illite are the likely phases involved in the sorption of organic carbon and related microbial redox transformations of metals in these sediments. Both the occurrence and abundance of chlorite, smectite-vermiculite, illite and smectite can therefore exert an important control on the contaminant fluxes and are important determinants of biogeofacies in mountainous, semiarid terrains.

Production of smectite organophylic clays from three commercial sodium bentonite

International Nuclear Information System (INIS)

Valenzuela Diaz, Francisco R.; Souza Santos, Persio de

1995-01-01

Laboratory cationic exchange procedures using Brazilian's commercial quaternary ammonium salt and three samples of commercial sodium bentonites (two Brazilian's and one from Wyoming (US) are described. Swelling values in some liquid organic media are shown for the organophilic clays and for a Brazilian's commercial organophilic clay. Organophilic clays with larger swelling values than the commercial organophilic clay in kerosene, Varsol, toluene and soya bean oil were obtained. (author)

Effect of by-product steel slag on the engineering properties of clay soils

Directory of Open Access Journals (Sweden)

Faisal I. Shalabi

2017-10-01

Full Text Available Clay soils, mainly if they contain swelling minerals such as smectite or illite, may cause severe damage to structures, especially when these soils are subjected to wetting and drying conditions. High expansion and reduction in shear strength and foundation bearing capacity will take place due to the increase in water content of these soils. The engineering properties of these kinds of soils can be improved by using additives and chemical stabilizers. In this work, by-product steel slag was used to improve the engineering properties of clay soils. Lab and field experimental programs were developed to investigate the effect of adding different percentages of steel slag on plasticity, swelling, compressibility, shear strength, compaction, and California bearing ratio (CBR of the treated materials. The results of tests on the clay soil showed that as steel slag content increased, the soil dry density, plasticity, swelling potential, and cohesion intercept decreased and the angle of internal friction increased. For the CBR, the results of the tests showed an increase in the CBR value with the increase in slag content.

Detailed mineralogical characterization of the Bullfrog and Tram members USW-G1, with emphasis on clay mineralogy

International Nuclear Information System (INIS)

Bish, D.L.

1981-10-01

The detailed mineralogy of the Bullfrog and Tram Members of the Crater Flat Tuff from drill hole USW-G1 has been examined, primarily to characterize fully the amounts and types of clay minerals in the tuffs and the possible effects clay minerals have on rock properties. Results of bulk sample x-ray diffraction analyses agree closely with previous determinations, although slightly higher clay mineral contents were found in this study. X-ray diffraction analysis of fine fractions revealed that the clay minerals in the tuffs are sodium-saturated montmorillonite-beidellites with typical layer charges and no high-charge layers. These smectites are found in virtually all samples of the Bullfrog and Tram, and there is no correlation between the amounts of smectites and the amounts of zeolite, quartz, and feldspar. Smectites are present in both welded and nonwelded horizons and are scarce in some zones with slight-to-absent welding

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

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

Water uptake, migration and swelling characteristics of unsaturated and saturated, highly compacted bentonite

International Nuclear Information System (INIS)

Pusch, R.

1980-09-01

The report presents the results of a number of laboratory tests and field observations to form the basis of a physical and mathematical model that can be used for predicting water uptake and swelling in highly compacted bentonite components of an actual deposition plant. The clay buffer masses have been suggested as barriers in the Swedish KBS concepts. Two commercially available bentonites were used for the production of samples. The rate of water uptake suggests a mathematical model based on a simple diffusion equation. The rate is determined by the access of water and thousands of years may pass before saturation is obtained. The rate of swelling is governed by the negative pore pressure and the permeability. There is reasonable agreement with field observations. The observed swelling potential of old smectite-rich clays has offered the evidence. (G.B.)

Elastic deformation behaviour of Palaeogene clay from Fehmarn Belt area

DEFF Research Database (Denmark)

Awadalkarim, Ahmed; Foged, Niels Nielsen; Fabricius, Ida Lykke

2014-01-01

Palaeogene clay samples were obtained by high quality boring and sampling techniques (Geobore S-system), during the extensive site investigations for building a bridge in the Fehmarn Belt area to link between Rødbyhavn in Denmark and Puttgarden in Germany. The Palaeogene clay is rich in smectite...

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

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.

Influence of Polymer-Clay Interfacial Interactions on the Ignition Time of Polymer/Clay Nanocomposites.

Science.gov (United States)

Zope, Indraneel S; Dasari, Aravind; Yu, Zhong-Zhen

2017-08-11

Metal ions present on smectite clay (montmorillonite) platelets have preferential reactivity towards peroxy/alkoxy groups during polyamide 6 (PA6) thermal decomposition. This changes the decomposition pathway and negatively affects the ignition response of PA6. To restrict these interfacial interactions, high-temperature-resistant polymers such as polyetherimide (PEI) and polyimide (PI) were used to coat clay layers. PEI was deposited on clay by solution-precipitation, whereas PI was deposited through a solution-imidization-precipitation technique before melt blending with PA6. The absence of polymer-clay interfacial interactions has resulted in a similar time-to-ignition of PA6/PEI-clay (133 s) and PA6/PI-clay (139 s) composites as neat PA6 (140 s). On the contrary, PA6 with conventional ammonium-based surfactant modified clay has showed a huge drop in time-to-ignition (81 s), as expected. The experimental evidences provided herein reveal the role of the catalytic activity of clay during the early stages of polymer decomposition.

Clay mineralogy of selected borehole sediments from the Lawrence Livermore National Laboratory and Sandia National Laboratories, Livermore, California

International Nuclear Information System (INIS)

Smith, D.K.; Peifer, D.W.; Rood, C.K.

1992-04-01

Smectite, 90 to 100% interstratified illite-smectite, chlorate, and kaolinite are identified in boreholes drilled in fluvial and alluvial fan deposits of the Plio-Pleistocene Livermore Formation in the vicinity of Lawrence Livermore National Laboratory (LLNL) and Sandia National Laboratories (SNL), Livermore. X-ray diffraction, scanning electron microscopy, and electron microprobe studies indicate the clays persist through 150 ft of gravels, sands, silts, and mudstones of the vadose zone to total drilling depths of 200 ft in the saturated zone. Scanning electron microscopy indicates that true clays (layer silicate only) comprise between 2 and 15 modal percent of the Livermore Formation. Authigenic and detrital smectite, 90% interlayered illite-smectite, and chlorate persist throughout the stratigraphic section; kaolinite occurs only in the upper 100 ft of the section and is absent below. Smectite comprises between 60 to 90% of the true (layer silicate only) clay fraction. Illite and kaolinite±chlorite abundances fluctuate between 10 to 30% and 10 to 20% of this fraction, respectively. Authigenic smectite, illite, and chlorate crystallize together with detrital phases; the authigenic component increases with depth. The relative percentages of clay minerals define unique mineralogical intervals, which can be correlated between boreholes. Pervasive microfractures and interconnected porosity are inherent in the finer sediments; the microfractures typically are 1 mm or less in width and are variably spaced. Voids and microfractures are conspicuously lined by clays. Porosity for the argillaceous sediments ranges between 23 and 40%; Brunauer, Emmett, and Teller (BET) specific surface area decreases variably from 40 m 2 /g near the surface to 15 m 2 /g at the 115-ft depth. Within the pelitic matrix, iron, iron-titanium, chromium, and manganese oxides are pervasive

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.

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

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.)

Clay-based materials for engineered barriers: a review

International Nuclear Information System (INIS)

Lajudie, A.; Raynal, J.; Petit, J.C.; Toulhoat, P.

1994-01-01

The potential importance of backfilling and plugging in underground radioactive waste repositories has led different research institutions to carry out extensive studies of swelling clay materials for the development of engineered barriers in underground conditions. These materials should combine a variety of hydro-thermo-mechanical and geochemical properties: impermeability, swelling ability in order to fill all void space, heat transfer and retention capacity for the most noxious radionuclides. Smectite clays best exhibit these properties and most of the research effort has been devoted to this type of materials. In this paper, mineralogical composition, sodium or calcium content, thermo-hydro-mechanical properties, swelling pressure, hydraulic and thermal conductivity, and chemical properties of five smectite clays selected by five major nuclear countries are reviewed: Avonseal montmorillonite (Canada), MX 80 montmorillonite (Sweden), Montigel montmorillonite (Switzerland), S-2 montmorillonite (Spain), and Fo-Ca inter stratified kaolinite/beidellite (France). (J.S.). 29 refs., 5 figs., 3 tabs

Organic Synthesis using Clay Catalysts

Indian Academy of Sciences (India)

cept, though not new, has received enormous attention in recent times. The desire to make ... which they are divided into four main groups such as, illite, smectite .... acid or driving out NH3 by heating the NH4 + ion treated clay. It is clear from ...

R7T7 nuclear waste glass behavior in moist clay: role of the clay mass/glass surface area ratio

International Nuclear Information System (INIS)

Godon, N.; Vernaz, E.

1989-01-01

R7T7 glass alteration was investigated in the presence of various moist clays. In contact with smectite 4a, selected in France as a potential engineered barrier material, the glass was significantly corroded: after 6 months the glass corrosion rate was practically the same as the initial alteration rate in double-distilled water. Substantially lower alteration was observed in contact with bentonite 6 activated by sodium carbonate. Smectite 4a consumes silicon released by glass corrosion, and thus retards the rise to high silicon concentrations in solution at which the glass corrosion rate diminishes. Glass can therefore in some cases be altered as much in moist clay as in water with high renewal rates. Other experiments with smaller quantities of smectite 4a showed that the phenomenon becomes less important in time: its duration is proportional to the ratio between the clay mass (C) and the glass surface area (SA). Comparing the results of studies at different C/SA ratios indicates that low glass corrosion rates are obtained more slowly at higher C/SA ratios. Tests with 239 Pu-doped R7T7 glass also showed that the radionuclide retention factor in the alteration film at the glass surface is only 6, compared with a factor of nearly 50 in double-distilled water

Investigating the swelling pressure of compacted crushed-Callovo-Oxfordian clay-stone

International Nuclear Information System (INIS)

Tang, C. S.; Tang, A. M.; Cui, Y. J.; Delage, P.; Schroeder, C.; De Laure, E.

2011-01-01

This paper presents an experimental study on the swelling pressure of heavily compacted crushed Callovo-Oxfordian (COx) clay-stone at a dry unit mass ρ d =2.0 Mg/m 3 using four different methods: constant-volume, swell-reload, zero-swell and adjusted constant-volume method. Results show that the swelling pressure varies in the range of 1-5 MPa and depends significantly on the test method. From the constant-volume tests, it is observed that the swelling behavior during wetting is a function of the suction and depends on both the hydration paths and wetting conditions (e.g. vapor-wetting or liquid-wetting). The swelling pressure decreases significantly with saturation time. To identify the microstructure changes of specimens before and after wetting, mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM) tests were performed. It is observed that, after wetting, the large inter-aggregate pores observed in the as-compacted specimen are no longer apparent; the whole pattern is characterized by a general swell of hydrated clay particles, rendering the soil more homogenous. Results from MIP indicated that wetting caused a significant reduction of the entrance diameter of the dominant inter-aggregate pores from 2.1 to 0.5μm whereas intra-aggregate pores were not significantly influenced. (authors)

Influence of coupling phenomena on the transport through compacted clays

Energy Technology Data Exchange (ETDEWEB)

Rosanne, M.; Koudina, N.; Adler, P.M. [IPGP, Paris (France); Tevissen, E. [ANDRA, Dept. Etude-Experimentation et Calcul, Chatenay Malabry (France)

2001-07-01

Our principal motivation was to study the influence of the coupling phenomena on transport through compacted clays. Coupled transports may occur when a pressure gradient {nabla}P, and electrical field E and a concentration gradient {nabla}C interact. These three gradients induce three fluxes. A flow is generated characterized by the seepage velocity U; a solute flux J{sub L} and a current density I are generated. Close to equilibrium, when the gradients are not to large, the problem is linear and the fluxes are linear functions of the gradients. A first series of experiments was performed with argillite to determine the diagonal properties, i.e., permeability, conductivity, and diffusion coefficient. In a second series of experiments, the voltage resulting from an imposed concentration gradient between two reservoirs separated by a clay sample was systematically measured; this corresponds to the coefficient L{sub 13}. (orig.)

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

Science.gov (United States)

Jaynes, William F.; Zartman, Richard E.

2011-01-01

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

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.

Evaluation of natural clay Brasgel as adsorbent in removal of lead in synthetic waste water

International Nuclear Information System (INIS)

Lima, W.S.; Rodrigues, M.G.F.; Mota, M.F.; Patricio, A.C.L.; Silva, M.M.

2012-01-01

The smectite clays have high adsorption capacity and cation exchange. Due to its chemical and physical characteristics, they can be effectively used as adsorbent of pollutants (such as metal ions). The initial objective of this study was to characterize the clay Brasgel through the techniques of X-Ray Diffraction (XRD), X-Ray Spectrometry by Energy Dispersive (EDX) and nitrogen adsorption (BET method), seeking its use in removing lead (Pb 2+ ) from synthetic effluents. System was used in finite bath to assess the potential removal of lead (Pb 2+ ), following a 2 2 factorial experimental design with three center point experiments, taking as input variables: pH and initial concentrations of lead (Pb 2+ ). The clay has Brasgel clay in its composition that characterize it as a smectite clay. By having a large surface area, this clay showed great potential on the adsorption of metal ions. (author)

Effect of temperature on volume change behaviour of statically compacted kaolin clay

Directory of Open Access Journals (Sweden)

Ileme Ogechi

2016-01-01

Full Text Available Several soils are subjected to high temperature due to the environment where they are located or activities around them. For instance, upper layer of soils in tropical regions, soils around geothermal structures, clay barriers around nuclear waste repository systems. Numerous studies have pointed out that high temperature affects the hydro-mechanical properties of soils. Notwithstanding already existing studies, the influence of temperature on soils is still a challenge, as most of these studies are soil specific and cannot be inferred as the behaviour of all soils. This paper presents an experimental study on the influence of temperature on the volume change behaviour of statically compacted kaolin clay. Compacted samples were tested at varying temperatures using a suction controlled oedometer cell. The influence of temperature on the magnitude of volumetric strain occurring during mechanical and thermal loading was investigated. The study showed that an increase in temperature increased the magnitude of volumetric strain of the soil on loading. Additionally, the results presented in the light of LC curve showed that an increase in temperature resulted in the contraction and a change in the position of the LC curve.

Surface modification of synthetic clay aimed at biomolecule adsorption: synthesis and characterization

Directory of Open Access Journals (Sweden)

Angela de Mello Ferreira Guimarães

2007-03-01

Full Text Available This work describes the process for functionalization of laponite through the grafting of 3-mercaptopropyltrimethoxysilane (MPTS. Laponite is synthetic smectite clay with surface area of 350 m²/g. The samples, prior to and after functionalization, were characterized by chemical analyses, thermogravimetric analysis (TGA, x ray diffraction (XRD, diffuse reflectance infrared Fourier transform spectroscopy (DRIFT, scanning electron microscopy and energy dispersive spectrometry (MEV/EDS. Infrared spectroscopy and elemental analyses confirmed the presence of organic chains and thiol groups in the modified clay. The immobilized and available thiol group, measured according to the Volhard method, totaled 1.4 meq/g of clay, with approximately 90% accessible for Ag+ trapping. These results represent an improvement as compared to other works concerning the functionalization of smectite-type clays in which the effect produced by functional group blockage limits the access of species to less than 10% of the complexing sites.

High-pressure gas-breakthrough apparatus and a procedure for determining the gas-breakthrough pressure of compacted clay

International Nuclear Information System (INIS)

Hume, H.B.

1997-08-01

Gas may be produced in a nuclear fuel waste disposal vault. Given that the vault will be sealed with clay-based materials, the fate of the gas is uncertain. Therefore, an instrument was previously built to measure the pressure required to pass gas through compacted clay materials (a gas-breakthrough apparatus). However, the 10 MPa pressure limit of the apparatus was insufficient to test compacted buffer material at the density proposed in the Canadian concept for nuclear fuel waste disposal. Therefore, a high-pressure (50 Wa) gas-breakthrough apparatus was designed, constructed and installed. This report describes the components of the apparatus and the materials and procedures that are used for the gas-breakthrough tests. (author)

Mean electrostatic and Poisson-Boltzmann models for multicomponent transport through compacted clay

International Nuclear Information System (INIS)

Steefel, C.I.; Galindez, J.M.

2012-01-01

Document available in extended abstract form only. Electrical double layer effects in the pore space of clays become increasingly important as the level of compaction increases and intergrain and interlayer spacings shift towards the range of nano-meters. At such scales, solute transport can no longer be explained by concentration gradients alone and it becomes necessary to include the electrostatic effects on chemical potentials. In fact, the electrical double layer (EDL) that develops in the neighborhood of the negatively charged clay surfaces can extend well into the aqueous phase, effectively constraining the space available to anions (known as anion exclusion), thus distorting the spatial distribution of ionic species in solution. In this study, we make use of two approaches for addressing the accumulation and transport of charged ionic species in the electrical double layers of compacted bentonite: 1) a mean electrostatic approach based on the assumption of Donnan equilibrium, and 2) a 2D numerical approach based on the multicomponent Poisson-Nernst-Planck (NPP) set of equations. For the mean electrostatic or Donnan approach to the electrical double layer [1], two options are considered: 1) a model in which surface complexation in the Stern layer may partly balance the fixed charge of the montmorillonite making up the bentonite buffer, and 2) a model in which the fixed mineral charge is balanced completely by the diffuse layer. In the mean electrostatic approach, one additional equation that balances the charge between the Stern layer and the diffuse layer is added to the multicomponent reactive transport code CrunchFlow. The only additional unknown that is required is the mean electrostatic potential, although it may be necessary in certain cases to consider the volume (or width) of the electrical double layer as an additional implicit unknown. Both ions and neutral species may diffuse within the diffuse layer according to their gradients and species

Characterization of clay (bentonite)/crushed granite mixtures to build barriers against the migration of radionuclides: diffusion studies and physical properties

International Nuclear Information System (INIS)

Mingarro, E.; Rivas, P.; Villar, L.P. del; Cruz, B. de la; Gomez, P.; Hernandez, A.; Turrero, M.J.; Villar, M.V.; Campos, R.; Cozar, J.

1991-01-01

In Spain, the possibility is being considered of storage of radioactive waste in granitic rocks, using Spanish clays as backfill and sealing materials. The study and selection of these materials is the objective of the project, accomplished with Community financial support under CEC contract No Fl1W-0191-E (TT). With the aim of minimizing the chemical-mineralogical disequilibrium between the granitic rock and the artificial barrier, the possibility has been studied of using molten granite as an additive and illite as clayish material, instead of the normal use of smectite (montmorillonite). The studies have been carried out on 30 commercial Spanish clays and two kinds of granite and have been orientated to the selection of materials and the optimization of the clay-granite mixtures, chemical characterization, mechanics and physics of the mixtures and compacted blocks, determination of their behaviour in the gradient fields of temperature, pressure and chemical potentials and to the determination of the migration parameters. 59 Figs.; 6 Micrograph; 52 Tabs.; 30 Refs

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

Science.gov (United States)

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

1993-01-01

Orographic precipitation on the southern flank of the southeastern Koolau Mountains produces a pronounced precipitation gradient. The corresponding gradient in the intensity of the chemical weathering environment provides an opportunity to address the effects of varying chemical weathering intensity on the composition of clay-size weathering products in soils developed on basalt. In addition, little-modified remnants of the constructional surface of the Koolau Volcano, isolated by stream dissection, remain as facets on the southern ends of the parallel ridges of the study area. By comparing clay mineralogy of soils developed on these older geomorphic surfaces with those developed on the younger sharp-crested ridges and steep side slopes, the effects of weathering duration on clay mineralogy can also be addressed.Soil clays in this part of the Koolau Mountains are mineralogically complex; principal phases include smectite, kaolinite, and halloysite, but pure end member phases are uncommon. Rather, most phases contain some amount of mixed layering. Smectite may contain small (Volcano are markedly more leached than those from younger landscapes in the same precipitation regime. Although smectite may be present, kaolinite is the dominant phase, and accumulations of Fe and Ti occur in the uppermost soil levels. Enrichment of Zr and Ti in these soils, as compared to concentrations in the original basaltic parent material, indicates that as much as 75% of the parent material has been lost. Thus weathering duration may affect soil clay composition in the same way as weathering intensity.Because smectite and halloysite are expandable clay minerals, their presence in soils may decrease slope stability and influence the nature of slope processes. Soil avalanches occur on steep slopes throughout the study area, whereas slow-moving landslides appear to be restricted to gentler slopes in drier parts of the study area where smectite is abundant. The clay mineralogy of soils thus

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)

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)

Transport and leaching of technetium and uranium from spent UO2 fuel in compacted bentonite clay

International Nuclear Information System (INIS)

Ramebaeck, H.; Albinsson, Y.; Skaalberg, M.; Eklund, U.B.; Kjellberg, L.; Werme, L.

2000-01-01

The transport properties of Tc and U in compacted bentonite clay and the leaching behaviour of these elements from spent nuclear fuel in the same system were investigated. Pieces of spent UO 2 fuel were embedded in bentonite clay (ρ d =2100 kg/m 3 ). A low saline synthetic groundwater was used as the aqueous phase. After certain experimental times, the bentonite clay was cut into 0.1 mm thick slices, which were analysed for their content of Tc and U. Measurements were made using inductively coupled plasma mass spectrometry. Tc analysis comprised chemical separation. The analysis of U was done by means of detecting 236 U, since the natural content of U in bentonite clay made it impossible to distinguish between U originating from the fuel and the clay. The influence of different additives mixed into the clay was studied. The results showed an influence on both transport and leaching behaviour when metallic Fe was mixed into the clay. This indicates that Tc and U are reduced to their lower oxidation states as a result of this additive

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.

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

Science.gov (United States)

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

2018-03-01

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

A mechanistic study of the uniform corrosion of copper in compacted clay-sand soil

International Nuclear Information System (INIS)

Litke, C.D.; Ryan, S.R.; King, F.

1992-08-01

The results of a study of the mechanism of uniform corrosion of copper under simulated nuclear fuel waste disposal conditions are presented. Evidence is given that suggests that the rate-controlling process is the transport of copper corrosion products away from the corroding surface. In the experiments described here, the copper diffused through a column of compacted clay-sand buffer. The properties of the buffer material, especially its ability to sorb copper species, are significant in determining the rate of uniform corrosion of copper. The evidence that copper diffusion is rate-controlling stems from the effect of γ-radiation on the tests. In the presence of γ-radiation, copper diffused farther along the column of compacted buffer material than in the unirradiated tests, but the corrosion rate was lower. These two effects can be best explained in terms of a slow copper-diffusion process. Irradiation is thought to reduce the extent of sorption of copper by the clay component of the buffer. This results in a more mobile copper species and a smaller interfacial flux of copper (i.e., a lower corrosion rate)

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.

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

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.

Review of Studies of Clay Minerals as Significant Component of Potential Host Rocks or Engineering Barriers for Radioactive Waste Disposals Performed at Comenius University in Bratislava

International Nuclear Information System (INIS)

Peter, Uhlik; Vladimir, Sucha; Maria, Caplovicova; Igor, Stricek

2013-01-01

About 50 % of electric power is produced by nuclear power plants in Slovakia. In spite of the significant production of nuclear waste, Slovakia has not defined basic strategy of radioactive-waste isolation. However, some pilot projects and studies have been carried out. Five areas were determined as prospective sites for construction of deep geological repository (DGR). Two of them are situated in the south of Slovakia. Szecseny schlier (mixture of siltstones and Clay-stones) of Lucenec Formation (Egerian) is one of the most prospective host rocks from lithological, structural and spatial perspective. Besides the investigation of potential host rock for DGR the studies of bentonite properties as important part of engineering barriers for radioactive waste disposals were performed. Detailed mineral and structural analyses of smectites from the bentonitic material exposed to laboratory Mock-Up test were realised. Particular interest has been focused on interaction between Fe and smectites. Other field of interest is investigation of sorption of Cs and Sr on natural and modified bentonites, including irradiation. Purpose of this work is to present a short review of other studies done by our group with partial focusing to interaction of organic dye (Rhoda-mine 6G) with smectite that is connected with changes of layer charge after treatment; possibilities to measure preferential orientation of clays after compaction by TEM and to effort to use X-ray micro-tomography for inner structure of sediments. (authors)

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)

Poro-elasto-plastic behaviour of dry compacted Fo-Ca clay: experiment and modelling. Application to the re-saturation of an engineered clay barrier

International Nuclear Information System (INIS)

Lassabatere, Th.; Imbert, Ch.; Etile, M.A.

1999-01-01

Many projects of underground repositories for high level radioactive waste involve an engineered clay barrier, placed between the waste canister and the surrounding rock. When hydrated, this barrier seals the gap and provides a good watertightness. The natural clay powder, dried and compacted, exhibits hydro-mechanical couplings during the hydration. Such a coupled behaviour, interesting for the industrial application, has been clearly demonstrated by many studies and laboratory experiments. But the modelling of this behaviour, in order to predict the hydration of the clay barrier, is difficult. A coupled modelling, based, at a macroscopic scale, on the thermodynamics of unsaturated porous media, is proposed. This thermodynamical model founds a general framework for non linear poro-elastic and poro-elasto-plastic coupled behaviours. The symmetries of this coupling, induced by this thermodynamical framework, let us take into account the often neglected influence of the mechanical state on the hydraulic problem of the re-saturation of the clay. The complete resolution of the flow problem, coupled with the mechanical behaviour, leads us to study the influence of the rheological behaviour chosen for the clay (elastic - linear or no linear -, or elastoplastic) on the evaluation of the duration of the re-saturation of the clay barrier). (authors)

The redox properties of the natural iron-bearing clay mineral ferruginous smectite SWA-1: a combined electrochemical and spectroscopic study

International Nuclear Information System (INIS)

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

2012-01-01

Document available in extended abstract form only. Iron-bearing clay minerals are ubiquitous in the environment and clay-mineral-based materials have been proposed to be part of backfill material in nuclear waste repositories. Laboratory and field studies have confirmed that structural iron (Fe) in clay minerals participates in redox reactions with organic pollutants, metals, and radionuclides, thus influencing their transport and reactivity. Knowledge of the redox properties of Fe-bearing clay minerals is therefore essential for understanding and predicting the fate, mobility, and bioavailability subsurface contaminants. A quantitative understanding of clay mineral redox behavior remains lacking, however, due to constraints in previous experimental approaches and the complex structural changes that accompany changes in the Fe oxidation state. This work provides a quantitative means for measuring the redox properties of Fe-bearing clay minerals, which can be applied to both field and laboratory studies tracking radionuclide-clay mineral redox reactions. Here we use mediated electrochemical reduction and oxidation to determine the electron accepting and donating capacities of several natural Fe-bearing clay minerals with different structural Fe content (2.3 to 21 wt-%) and varied redox histories. Results indicate that the fraction of redox-active Fe in clay minerals is mineral-dependent, and is linked to the thermodynamics of reduction and oxidation as well as to the ability of clay minerals to conduct electrons and facilitate structural re-arrangements required to maintain charge balance. The reduction potential (E H ) characteristics of a natural ferruginous smectite (SWa-1) were further characterized as a function of solution conditions and repeated Fe reduction and oxidation cycles. SWa-1 samples were analyzed with Moessbauer spectroscopy (MS) and X-ray absorption spectroscopy (XAS) to link observed redox potential behavior to structural properties and changes

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

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

Hydraulic conductivity study of compacted clay soils used as landfill liners for an acidic waste

International Nuclear Information System (INIS)

Hamdi, Noureddine; Srasra, Ezzeddine

2013-01-01

Highlights: ► Examined the hydraulic conductivity evolution as function of dry density of Tunisian clay soil. ► Follow the hydraulic conductivity evolution at long-term of three clay materials using the waste solution (pH=2.7). ► Determined how compaction affects the hydraulic conductivity of clay soils. ► Analyzed the concentration of F and P and examined the retention of each soil. - Abstract: Three natural clayey soils from Tunisia were studied to assess their suitability for use as a liner for an acid waste disposal site. An investigation of the effect of the mineral composition and mechanical compaction on the hydraulic conductivity and fluoride and phosphate removal of three different soils is presented. The hydraulic conductivity of these three natural soils are 8.5 × 10 −10 , 2.08 × 10 −9 and 6.8 × 10 −10 m/s for soil-1, soil-2 and soil-3, respectively. Soil specimens were compacted under various compaction strains in order to obtain three wet densities (1850, 1950 and 2050 kg/m 3 ). In this condition, the hydraulic conductivity (k) was reduced with increasing density of sample for all soils. The test results of hydraulic conductivity at long-term (>200 days) using acidic waste solution (pH = 2.7, charged with fluoride and phosphate ions) shows a decrease in k with time only for natural soil-1 and soil-2. However, the specimens of soil-2 compressed to the two highest densities (1950 and 2050 kg/m 3 ) are cracked after 60 and 20 days, respectively, of hydraulic conductivity testing. This damage is the result of a continued increase in the internal stress due to the swelling and to the effect of aggressive wastewater. The analysis of anions shows that the retention of fluoride is higher compared to phosphate and soil-1 has the highest sorption capacity.

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.

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

Science.gov (United States)

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

2018-03-01

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

Evaluation of the mineralogical characterization of several smectite clay deposits of the state of Paraiba, Brazil using statistical analysis of variance; Avaliacao da caracterizacao mineralogica de diversos depositos de argilas esmectiticas do estado da Paraiba utilizando analise estatistica de variancia

Energy Technology Data Exchange (ETDEWEB)

Gama, A.J.A.; Menezes, R.R.; Neves, G.A.; Brito, A.L.F. de, E-mail: agama@reitoria.ufcg.edu.br [Universidade Federal de Campina Grande (UFCG), PB (Brazil)

2015-07-01

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)

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.

Lightweight self-compacting concrete with light expanded clay aggregate (LECA

Directory of Open Access Journals (Sweden)

Heiza Khaled

2018-01-01

Full Text Available Lightweight concretes have been successfully applied in building constructions for many years due to their favorable material properties, particularly their low specific weight in connection with a high strength, a high capability of thermal insulation and a high durability. The development leading to lightweight self-compacting concrete (LWSCC represents an important advanced step within the recent years. This concrete combines the favorable properties of a lightweight concrete with those of a self-compacting concrete. Research work is aimed on development of (LWSCC with the use of light aggregates “Light expanded clay aggregate (LECA”. In this research, first by specific gravity factor method, twenty different mix designs of (LWSCC were cast and tested to find out the values of slump flow, J-ring , V-funnel and 28 day compressive strength. Based on the results obtained, the best mix design was selected for further investigation. This paper also focuses on studying the effect of changing the reinforcement ratio on reinforced two way slabs when the dimensions were kept constant.

Experimental evaluation of the hydraulic resistance of compacted bentonite/boom clay interface

International Nuclear Information System (INIS)

Tang, Anh-Minh; Cui, Yu-Jun; Delage, Pierre; Munoz, Juan Jorge; Li, Xiang-Ling

2008-01-01

In the framework of the in-situ PRACLAY Heater experiment to be performed in the HADES URF in Mol (Belgium), the feasibility of a hydraulic cut-off of the Excavation Damaged Zone (EDZ) and the Repository Components (RC) of the disposal galleries by using a horizontal seal will be examined. It has been planned to install an annular seal composed of compacted bentonite between the heated zone and the access gallery (PRACLAY seal test), so that to avoid any hydraulic shortcut towards the access gallery. According to numerical scoping calculations, heating until 80 deg C will induce a pore pressure of the order of 3.0 MPa. In order to verify the effects of this water pressure on the performance of the annular seal system and more specifically on the hydraulic resistance of the interface between the compacted bentonite and the host rock (Boom clay), laboratory percolation tests at 20 and 80 deg C were performed. The results confirm the performance of the compacted bentonite seal to avoid the hydraulic shortcut to the access gallery under the foreseen hydraulic and thermal conditions. (author)

Clay Mineralogy of Basaltic Hillsides Soils in the Western State of Santa Catarina

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Jaime Antonio de Almeida

2018-02-01

Full Text Available ABSTRACT A commonly accepted concept holds that highly fertile, shallow soils are predominant in the Basaltic Hillsides of Santa Catarina State, in southern Brazil, but their agricultural use is restricted, either by excessive stoniness, low effective depth or steep slopes. Information about soil properties and distribution along the slopes in this region is, however, scarce, especially regarding genesis and clay fraction mineralogy. The objective of this study was to evaluate soil properties of 12 profiles distributed in three toposequences (T of the Basaltic Hillsides in the State of Santa Catarina, two located in the valley of the Peixe River (Luzerna - T1 and Ipira - T2 and one in Descanso, in the far West of the state (T3. The main focus was the mineralogical composition of the clay fraction, identified by X-ray diffractometry (XRD, and its relations with the soil chemical properties. The morphological, chemical, and mineralogical properties of the soils of the toposequences differed from each other. In most soils, the position of the most intense XRD reflections indicated predominance of kaolinite (K however, for being broad and asymmetric, a participation of interstratified kaolinite-smectite (K-S was assumed. Soils of T2 and T3, located in regions with higher temperatures, lower water surplus, and lower altitude than those of T1, were more fertile, mostly redder, and contained higher proportions of smectites (S and interstratified K-S mineral, accounting for a higher activity of the clay fraction of most soils. The T1 soils were generally less fertile, with lower clay activity and, aside from kaolinite, contained smectites with interlayered hydroxy-Al polymers (HIS. The low estimated smectite contents of the most fertile soils of all toposequences disagree with the high values of cation exchange capacity (CEC and clay activity related to pure kaolinite soils. The broad and asymmetric reflections of most of the supposed kaolinites

Surface modification of montmorillonite on surface Acid-base characteristics of clay and thermal stability of epoxy/clay nanocomposites.

Science.gov (United States)

Park, Soo-Jin; Seo, Dong-Il; Lee, Jae-Rock

2002-07-01

In this work, the effect of surface treatments on smectitic clay was investigated in surface energetics and thermal behaviors of epoxy/clay nanocomposites. The pH values, X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR) were used to analyze the effect of cation exchange on clay surface and the exfoliation phenomenon of clay interlayer. The surface energetics of clay and thermal properties of epoxy/clay nanocomposites were investigated in contact angles and thermogravimetric analysis (TGA), respectively. From the experimental results, the surface modification of clay by dodecylammonium chloride led to the increases in both distance between silicate layers of about 8 A and surface acid values, as well as in the electron acceptor component (gamma(+)(s)) of surface free energy, resulting in improved interfacial adhesion between basic (or electron donor) epoxy resins and acidic (electron acceptor) clay interlayers. Also, the thermal stability of nanocomposites was highly superior to pure epoxy resin due to the presence of the well-dispersed clay nanolayer, which has a barrier property in a composite system.

Clay mineral association in the salt formation of the Transylvanian Basin and its paleoenvironmental significance

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Nicoleta Bican-Bris̡an

2006-04-01

Full Text Available The investigated clay fraction was separated from salt samples recovered from three boreholes located in the Praid salt deposit area. For comparison, samples collected from Turda deposit (Franz Josef adit, the Rudolf and Ghizele chambers and from the salt massif from Sărăţel were also analyzed. The qualitative investigations evidenced a clay minerals association dominated by illite and chlorite accompanied by subordinate amounts of kaolinite, smectite, fibrous clays (sepiolite, palygorskite, and in minor amounts, by 14/14 chlorite/vermiculite and chlorite/smectite interstratifications. A quantitative evaluation (% including a standard graphical representation was performed only for the borehole samples (Praid, according to the vertical distribution. The genetical interpretation of the identified clay minerals association took into account the influence of the sedimentation mechanisms and the climate control on the mineral phases. The environment of formation for the salt in the Transylvanian Basin was defined by the presence of specific climatic factors, also suggested by the palynological investigations.

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

Permeability Characteristics of Compacted and Stabilized Clay with Cement, Peat Ash and Silica Sand

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Seyed Esmaeil Mousavi

2016-06-01

Full Text Available The present paper investigates the influence of stabilization with cement, peat ash, and silica sand on permeability coefficient (kv of compacted clay, using a novel approach to stabilize the clay with peat ash as a supplementary material of cement in the compacted and stabilized soil. In order to assess the mentioned influence, test specimens of both untreated and stabilized soil have been tested in the laboratory so that their permeability could be evaluated. Falling head and one dimensional consolidation tests of laboratory permeability were performed on the clay specimens and the chemical compositions of the materials as well as microstructure of the stabilized soil with 18% cement, 2% peat ash, and 5% silica sand were investigated, using X-ray fluorescence and scanning electron microscopy respectively. Results show that for soil stabilization with up to 8% cement content (of the dry weight of the soil, the average value of coefficient of permeability (kv is very close to that of untreated soil, whereas the kv value decreases drastically for 18% cement under identical void ratio conditions. It is further revealed that addition of 18% cement, 2% peat ash, and 5% silica sand had decreased the coefficient of permeability by almost 2.2 folds after 24 h, while about 1.7 folds increase was observed in coefficient of permeability once 13.5% of cement, 1.5% of peat ash, and 20% of silica sand were added. The partial replacement of cement with the 2% peat ash can reduce the consumption of cement for soil stabilization.

Radiocesium sorption in relation to clay mineralogy of paddy soils in Fukushima, Japan

Energy Technology Data Exchange (ETDEWEB)

Nakao, Atsushi, E-mail: na_4_ka_triplochiton@kpu.ac.jp [Graduate School of Life and Environmental Sciences, Kyoto Prefectural University, Hangi-cho 1-5, Shimogamo, Sakyo-ku, Kyoto 606-8522 (Japan); Ogasawara, Sho [Graduate School of Life and Environmental Sciences, Kyoto Prefectural University, Hangi-cho 1-5, Shimogamo, Sakyo-ku, Kyoto 606-8522 (Japan); Sano, Oki; Ito, Toyoaki [Field Science Center, Graduate School of Agricultural Science, Tohoku University, Naruko-Onsen 232-3, Osaki, Miyagi 989-6711 (Japan); Yanai, Junta [Graduate School of Life and Environmental Sciences, Kyoto Prefectural University, Hangi-cho 1-5, Shimogamo, Sakyo-ku, Kyoto 606-8522 (Japan)

2014-01-01

Relationships between Radiocesium Interception Potential (RIP) and mineralogical characteristics of the clay fraction isolated from 97 paddy soils (Hama-dori, n = 25; Naka-dori, n = 36; Aizu, n = 36) in Fukushima Prefecture, Japan were investigated to clarify the mineralogical factors controlling the {sup 137}Cs retention ability of soils (half-life 30.1 y). Of all the fission products released by the Fukushima accident, {sup 137}Cs is the most important long-term contributor to the environmental contamination. The RIP, a quantitative index of the {sup 137}Cs retention ability, was determined for the soil clays. The composition of clay minerals in the soil clays was estimated from peak areas obtained using X-ray diffraction (XRD) analyses. The predominant clay mineral was smectite in soils from Hama-dori and Aizu, while this was variable for those from Naka-dori. Native K content of the soil clays was found to be an indicator of the amount of micaceous minerals. The average RIP for the 97 soil clays was 7.8 mol kg{sup −1}, and ranged from 2.4 mol kg{sup −1} to 19.4 mol kg{sup −1}. The RIP was significantly and positively correlated with native K content for each of the geographical regions, Hama-dori (r = 0.76, p < 0.001), Naka-dori (r = 0.43, p < 0.05), and Aizu (r = 0.76, P < 0.001), while it was not related to the relative abundance of smectite. The linear relationship between RIP and native K content not only indicate a large contribution of micaceous minerals to the {sup 137}Cs retention ability of the soil clays, but also could be used to predict the {sup 137}Cs retention ability of soil clays for other paddy fields in Fukushima and other areas. - Highlights: • RIP was measured for 97 paddy soils from Fukushima to assess {sup 137}Cs retention ability. • The dominant clay mineral was smectite, but this did not control RIP. • RIP was positively correlated with native K content. • Micaceous minerals were found to control the {sup 137}Cs retention

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)

Clay Mineralogy of Soils on Quaternary Sediment in Northeast of Urmia

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Parisa Farzamnia

2017-03-01

10.83 °C respectively and the soil moisture and temperature regimes are dry xeric and mesic respectively. In this study, eight soil profiles in quaternary sediments were dug and sampled and the morphological, physical, chemical and mineralogical properties were determined using standard methods. Results and Discussion: According to the results, Illite, smectite, Kaolinite, chlorite, vermiculite and hydroxy interlayer vermiculite (HIV were the dominant clay minerals in these soils. The origin of illite, chlorite and kaolinite were related to inheritance from parent material. Regarding to the present of some smectite in the parent material of these soils, some of smectites have been inherited from parent material. Nevertheless it seems that, the most of smectites in these soils have pedogenic origin. Based on mineralogical results and trends variation of smectite and illite along studied profiles, we concluded that some of smectites in these soils have been formed from illite transformation. In profiles 4 and 6, regarding to low depth water table and consequently poor drainage, high pH and high values of calcium and magnesium cations, provide suitable conditions for the neoformation of smectit and so, some of smectites have been formed via neoformation from soil solution. In these soils, vermiculites were pedogenic and have been formed during transformation of illite to smectite. Small amounts of hydroxy interlayer vermiculites were present in buried horizons and regarding that they were not present in parent material, it might be because these minerals are pedogenic and have been formed in a past wetter climate. The transformation of illite to smectite in lower horizons needs high moisture and regarding to recent semiarid climate of study area, the suitable amount of moisture for this transformation, especially in lower depths and also in buried horizons, is not present. Thus, it seems the transformation of illite to smectite in lower depths and buried horizons has

Influence of leachate on the Oligocene-Miocene clays of the İstanbul area, Turkey

OpenAIRE

ÖZTOPRAK, SADIK; LAÇİN, DAVUT

2018-01-01

Oligo-Miocene clay outcrops on the European side (west and northwest part) of İstanbul were analysed. Formerly, a landfill and sanitary landfill were built on the clay. Mineral liners of the current and extending parts of the İstanbul landfill consist of these clays, since they include a considerable amount of smectite, illite, and kaolinite. With this feature, these clays are also an important candidate for the buffer material of repositories for nuclear wastes of newly planned nuclear power...

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...

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)

Hydrothermal behaviour of sedimentary saponitic clays from Madrid Basin

International Nuclear Information System (INIS)

Cuevas Rodriguez, J.

1993-01-01

The hydrothermal behavior of sedimentary saponitic clays from Madrid Basin has been investigated to assess their potential use as a buffer material in high level radioactive waste repositories. This paper deals with a review of several aspects that has been studied: the adsorption and irreversible fixation of K'+, the alteration in absence of potassium and the effects of heat and steam on textural properties of the smectitic clay. Experiments have covered temperatures up to 175 degree centigree with an excess of liquid water except on the last subject. Chemical and XRD analyses of final clay products and solutions indicates minor alteration of the saponite in the hydrothermal experiments either in the presence or absence of potassium. No illitization or chloritization processes seems to affect the smectite. Sepiolite was found to be largely dissolved at 175 degree centigree, a process that inhibited recrystallization or formation of illite observed when illite was present in significant amounts in starting materials. Accessory minerals (illite and sepiolite) accompanying as traces the saponitic material underwent and intense degradation at 175 degree centigree in absence of potassium. On the other hand, clay steamed at 200 degree centigree showed significant textural changes forming highly stable silt size aggregates which hindered the swelling abilities of the saponitic material, a fact that was previously observed in montmorillonites. (Author) 25 refs

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

Science.gov (United States)

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

2008-12-01

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

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.

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

Geological and technological characterization of the Late Jurassic-Early Cretaceous clay deposits (Jebel Ammar, northeastern Tunisia) for ceramic industry

Science.gov (United States)

Ben M'barek-Jemaï, Moufida; Sdiri, Ali; Ben Salah, Imed; Ben Aissa, Lassaad; Bouaziz, Samir; Duplay, Joelle

2017-05-01

Late Jurassic-Lower Cretaceous clays of the Jebel Ammar study site were used as raw materials for potential applications in ceramic industry. Physico-chemical characterization of the collected samples was performed using atomic absorption spectroscopy, X-ray diffraction, thermogravimetry and dilatometry (Bugot's curve). Geotechnical study was also undertaken by the assessment of plasticity and liquidity limits. It was found that high concentrations of silica, alumina with SiO2/Al2O3 ratio characterized the studied clays; its high amounts of CaO and Fe2O3 in the Late Jurassic clays indicated their calcareous nature. In addition, technological tests indicated moderate to low plasticity values for the Late Jurassic and Lower Cretaceous clays, respectively. Clay fraction (<2 μm) reached 50% of the natural clay in some cases. Mineralogical analysis showed that Jurassic clays were dominated by smectite, illite and kaolinite, as clay mineral species; calcite was the main associated mineral. Lower Cretaceous clays were mainly composed of abundant illite accompanied by well-crystallized smectite and kaolinite. Kaolinite gradually increased upwards, reaching 70% of the total clay fraction (i.e. <2 μm). Quartz, calcite and feldspar were the main non-clay minerals. Based on these analyses, the clays meet technological requirements that would allow their use in the ceramic industry and for the manufacturing of ceramic tiles.

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

Science.gov (United States)

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

2011-01-01

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

Influence of clay and silica on permeability and capillary entry pressure of chalk reservoirs in the North Sea

DEFF Research Database (Denmark)

Røgen, Birte; Fabricius, Ida Lykke

2002-01-01

specific surface area. Fifty-nine Tor and Ekofisk Formation chalk samples from five North Sea chalk reservoirs were investigated. All contain quartz and clay minerals, most commonly kaolinite and smectite, with trace amounts of illite. The contents of calcite and quartz are inversely correlated and both......)): calcite between 0.5 and 3.5, quartz about 5, kaolinite about 15, and smectite about 60....

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

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

Fe(0)-clays interactions at 90°C under anoxic conditions: a comparative study between clay fraction of Callovo-Oxfordian and other purified clays

International Nuclear Information System (INIS)

Rivard, C.; Pelletier, M.; Villieras, F.; Barres, O.; Galmiche, M.; Ghanbaja, J.; Kohler, A.; Michau, N.

2010-01-01

Document available in extended abstract form only. In the context of the geological disposal of high-level radioactive waste it is of prime importance to understand the interactions between the saturated clay formation and steel containers. This can be achieved through an in-depth analysis of iron-clay interactions. Previous studies on the subject investigated the influence of solid/liquid ratio, iron/clay ratio, temperature and reaction time. The aim of the present study is to explain Callovo-Oxfordian-Fe(0) interactions by determining the role of each mineral phases present in the Callovo-Oxfordian (clay minerals, quartz, carbonates and pyrite) on the mechanisms of interaction between metal iron and clay particles. In that context, it is especially important to understand in detail the influence of clay nature and to obtain some insight about the relationships between interaction mechanisms at the molecular scale and crystallographic properties (particle size, TO or TOT layers, amount of edge faces...). The influence of the combination of different clays and the addition of other minerals must also be studied. In a first step, the Callovo-Oxfordian argillite from the Andra's underground research laboratory was purified to extract the clay fraction (illite, illite-smectite, kaolinite and chlorite). Batch experiments were carried out in anoxic conditions at 90 deg. C in the presence of background electrolyte (NaCl 0.02 M.L -1 , CaCl 2 0.04 M.L -1 ) for durations of one, three or nine months in the presence of metallic iron powder. Experiments without iron were used as control. The iron/clay ratio was fixed at 1/3 with a solid/liquid ratio of 1/20. The above mentioned experiments were also carried out in parallel on other purified clays: two smectites (Georgia bentonite and SWy2 from the Clay Minerals Society), one illite (illite du Puy) and one kaolinite (KGa2, from the Clay Minerals society). At the end of the experiments, solid and liquid phases were

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.

Retention of radiocaesium traces in clay: a dynamic semi-empirical modelling

International Nuclear Information System (INIS)

Lewyckyi, N.

2001-01-01

The contribution consists of an abstract of a PhD thesis. After deposition, Cs + bioavailability in soil is a key parameter with regard to public exposure after a severe nuclear accident.The objective of the PhD thesis was to understand and model the interaction of Cs + and 2:1 clay minerals. This interaction was characterised through Cs + sorption-desorption experiments carried out on seven 2:1 clay minerals (four smectite types, illite, biotite and vermiculite)

Heterogeneous photo-Fenton oxidation with natural clays for phenol and tyrosol remediation

Directory of Open Access Journals (Sweden)

Djeffal L.

2013-09-01

Full Text Available Due to their excellent properties, clays have been widely used in several applications, particularly in catalysis. In this paper, three clays were used as heterogeneous photo-Fenton catalysts for phenol and tyrosol oxidations. Particular attention was given to the effect of the main operating conditions on the process performance. A total conversion was obtained for both organic pollutants with studied catalysts in 20 minutes reaction. For phenol, a total organic carbon (TOC conversion of 93% was obtained using sieved and calcined smectite clay. The TOC conversion was 60% for tyrosol with the same catalyst. Clays were characterized by chemical analysis, BET, XRD, TPR and SEM.

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.

Acid activation of natural clays aiming their application in adsorption

International Nuclear Information System (INIS)

Silva, M.M. da; Sousa, A.K.F. de; Lima, W.S.; Vasconcelos, P.N.M. de; Rodrigues, M. G.F.

2012-01-01

Clays of smectite type have wide application in industrial, mainly due to their adsorption properties. However, it is necessary to subject them to chemical treatments to optimize their potential. This study aimed to analyze the effects of acid activation on the clay Brasgel fresh. In the acid activation was used concentrated hydrochloric acid at different concentrations (3M, 4.5 M and 6 M) at a temperature of 70 ° C for 30 minutes. The samples fresh and activated technique were characterized by X-ray Diffraction (XRD). The results show that the properties of clay after activation are improved, it could be used as adsorbents in the treatment of wastewater. (author)

Clay mineralogy, grain size distribution and their correlations with trace metals in the salt marsh sediments of the Skallingen barrier spit, Danish Wadden Sea

DEFF Research Database (Denmark)

He, Changling; Bartholdy, Jesper; Christiansen, Christian

2012-01-01

metals. The clay assembly of the sediment consists of illite, kaolinite and much less chlorite and smectite. The major clay minerals of illite, kaolinite as well as chlorite correlate very poorly with all the trace metals investigated, due probably to the weak competing strength of these clays compared...

Planning of experimental removal of cadmium in finite bath system using the chocolate clay B as adsorbent

International Nuclear Information System (INIS)

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

2012-01-01

The smectite clays are characterized by having a high cation exchange capacity and ability to remove metal ions. They have great industrial importance, for its abundance and low cost. The first part of this work was to characterize the clay called Chocolate B through the techniques of X-Ray Diffraction, X-Ray Spectroscopy and Energy Dispersive Physical Adsorption of Nitrogen. The second part of the work aims to evaluate the significance of the variables: pH and initial concentration on removal of cadmium in a batch system. In the experimental design used was a 2 2 factorial analysis with the addition at the central point, and evaluated the percentage of removal (Rem%) and removal capacity (EQF). XRD results corroborating the chemical analysis (EDX), characterized as a B Chocolate smectite clays. Statistical analysis showed a strong influence of variable pH on the removal of cadmium. (author)

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

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

This paper is an extension of a previous paper where the natural and purified clay in the homoionic Na form were physico-chemically characterized (doi:10.1016/j.clay.2008.04.014). In this study, the adsorption behavior of U (VI) on a purified Na-smectite suspension is studied using batch adsorption experiments and surface complexation modeling (double layer model). The sorption of uranium was investigated as a function of pH, uranium concentration, solid to liquid ratio, effect of natural organic matter (NOM) and NaNO(3) background electrolyte concentration. Using the MINTEQA2 program, the speciation of uranium was calculated as a function of pH and uranium concentration. Model predicted U (VI) aqueous speciation suggests that important aqueous species in the [U (VI)]=1mg/L and pH range 3-7 including UO(2)(2+), UO(2)OH(+), and (UO(2))(3)(OH)(5)(+). The concentration of UO(2)(2+) decreased and that of (UO(2))(3)(OH)(5)(+) increased with increasing pH. The potentiometric titration values and uptake of uranium in the sodium smectite suspension were simulated by FITEQL 4.0 program using a two sites model, which is composed of silicate and aluminum reaction sites. We compare the acidity constants values obtained by potentiometric titration from the purified sodium smectite with those obtained from single oxides (quartz and alpha-alumina), taking into account the surface heterogeneity and the complex nature of natural colloids. We investigate the uranium sorption onto purified Na-smectite assuming low, intermediate and high edge site surfaces which are estimated from specific surface area percentage. The sorption data is interpreted and modeled as a function of edge site surfaces. A relationship between uranium sorption and total site concentration was confirmed and explained through variation in estimated edge site surface value. The modeling study shows that, the convergence during DLM modeling is related to the best estimation of the edge site surface from the N(2

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...

Crystal chemistry and Moessbauer spectroscopic analysis of clays around Riyadh for brick industry

Energy Technology Data Exchange (ETDEWEB)

Khalil, Mutasim I., E-mail: mkhalil@ksu.edu.sa [King Saud University, Department of Chemistry, College of Science (Saudi Arabia)

2013-04-15

A total of 30 clay samples were collected from the area around Riyadh city, Saudi Arabia. A complete chemical analysis was carried out using different techniques. X-ray diffraction studies showed that the clay samples were mainly of the smectite group with traces of the kaolinite one. The samples studied were classified as nontronite clay minerals. One of the clay fraction has been studied by Moessbauer spectroscopy as raw clay fraction and after being fired at 950-1,000 Degree-Sign C. The Moessbauer spectra showed accessory iron compounds in the form of hematite and goethite. The structural iron contents disintegrate on firing transforming into magnetic iron oxide and a paramagnetic small particles iron oxide.

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

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.

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

Clay minerals assemblage in the Neogene fluvial succession of the Pishin Belt, Pakistan

DEFF Research Database (Denmark)

Kasi, Aimal Khan; Kassi, Akhtar Muhammad; Friis, Henrik

2014-01-01

indicate derivation of material from the Pre-Miocene sedimentary and meta-sedimentary terrains of the Pishin Belt. X-ray diffraction (XRD) analyses indicate that clay minerals in various mudstones and sandstone samples are identical and detrital in nature and include smectite, chlorite, illite, serpentine...... and kaolinite. Smectite and chlorite are most probably derived from the metavolcanic and mafic volcanic rocks, respectively. Presence of serpentine in samples of the Bostan Formation indicates altered ultramafic rocks as one of the source terrains. Illite is probably recycled from the older sedimentary...

Clay components in soil dictate environmental stability and bioavailability of cervid prions in mice

Directory of Open Access Journals (Sweden)

A. Christy Wyckoff

2016-11-01

Full Text Available Chronic wasting disease affects cervids and is the only known prion disease to affect free-ranging wildlife populations. CWD spread continues unabated, and exact mechanisms of its seemingly facile spread among deer and elk across landscapes in North America remain elusive. Here we confirm that naturally contaminated soil contains infectious CWD prions that can be transmitted to susceptible model organisms. We show that smectite clay content of soil potentiates prion binding capacity of different soil types from CWD endemic and non-endemic areas, likely contributing to environmental stability of bound prions. The smectite clay montmorillonite (Mte increased prion retention and bioavailability in vivo. Trafficking experiments in live animals fed bound and unbound prions showed that mice retained significantly more Mte-bound than unbound prions. Mte promoted rapid uptake of prions from the stomach to the intestines via enterocytes and M cells, and then to macrophages and eventually CD21+ B cells in Peyer’s patches and spleens. These results confirm clay components in soil as an important vector in CWD transmission at both environmental and organismal levels.□

Clay minerals in sandstone uranium deposits: radwaste applications

International Nuclear Information System (INIS)

Brookins, D.G.

1990-01-01

Clay minerals play an important role in the genesis of uranium deposits in sandstones. They incorporate the rate earths (REE), U, Sb, Th, Cs, Rb, Sr, Y, Ba, and even small amounts of chalcophiles. These minerals possess analog elements for many of the radwaste fission products as well as actinides and some actinide daughters. In sandstone uranium deposits, clay minerals are also associated with sulfide minerals, usually pyrite, and organic carbonaceous matter. The primary clay minerals are usually smectites, illites, chlorites and mixed layer varieties. The integrity of these clay minerals is demonstrated by their retention of formational-mineralization ages determined by Rb-Sr geochronologic investigation of the Grants Mineral Belt of the United States. The importance of the clay minerals as analog for parts of the multi-barrier concept in radwaste disposal is their ability to impede water penetration into - and movement of key elements out of uranium rich zones. The clay minerals further sorb and in other ways incorporate into their structures many fission products and actinide analogs from man-made nuclear wastes. 22 refs., 1 fig., 3 tabs

Influence of microorganisms on swelling behavior of smectites

International Nuclear Information System (INIS)

Viefhaus, Hanna; Schanz, Tom

2012-01-01

Document available in extended abstract form only. Considerable interaction of smectitic clay minerals and water leads to the pronounced seal effect needed for barrier materials in the toxic and nuclear waste storage. Nano-structural processes on the molecular level cause macroscopic material properties such as fluid/ion permeability and volume change/swelling pressure development, that are taken into account when characterizing the barrier material. In situ behavior results from a combination of specific influence factors (e.g. electrolyte concentration, temperature, pH-value) due to the great dependence on the environmental conditions of clay water interaction. Considering this aspect, the origin of change in chemical and physical variables become relevant. Particularly in terms of naturally existing and rapid changing factors such as microbial activity. Due to the biodiversity of microorganisms and their individual diversity of metabolism processes, many species have been studied with respect to the influence on the different soil properties. In this study, the effects created by microbial biocenose have been the object of investigation. This corresponds to natural conditions rather than the isolated species. The present study concerns the swelling behavior of smectitic clay with respect to the influence of induced microbial accumulation. Two types of smectites were studied, Calcigel (Ca 2+ -ions embedded between the silicate layers) and MX80 (Na + -ions embedded). A natural silt was mixed at a ratio of 70:30 for the dry mass with smectites, this provided an amount of microbial portfolio. Using the mixtures, samples were created (20 mm height, 70 mm diameter) with two types of water contents. They exhibited the same dry densities of 1.495 g/cm 3 (Calcigel) and 1.386 g/cm 3 (MX80). Water adsorption was permitted through the contact of the sample with the liquid phase and also unhindered volume change in one dimension. The addition of nutrients to the liquid phase

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

Science.gov (United States)

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

2015-12-01

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

Deformation and Fabric in Compacted Clay Soils

Science.gov (United States)

Wensrich, C. M.; Pineda, J.; Luzin, V.; Suwal, L.; Kisi, E. H.; Allameh-Haery, H.

2018-05-01

Hydromechanical anisotropy of clay soils in response to deformation or deposition history is related to the micromechanics of platelike clay particles and their orientations. In this article, we examine the relationship between microstructure, deformation, and moisture content in kaolin clay using a technique based on neutron scattering. This technique allows for the direct characterization of microstructure within representative samples using traditional measures such as orientation density and soil fabric tensor. From this information, evidence for a simple relationship between components of the deviatoric strain tensor and the deviatoric fabric tensor emerge. This relationship may provide a physical basis for future anisotropic constitutive models based on the micromechanics of these materials.

Evaluation of natural clay Brasgel as adsorbent in removal of lead in synthetic waste water; Avaliacao da argila Brasgel natural como adsorvente na remocao de chumbo de efluentes sinteticos

Energy Technology Data Exchange (ETDEWEB)

Lima, W.S.; Rodrigues, M.G.F.; Mota, M.F.; Patricio, A.C.L.; Silva, M.M., E-mail: wsl_20@yahoo.com.br [Universidade Federal de Campina Grande (LABNOV/UFCG), PB (Brazil). Unidade Academica de Engenharia Quimica. Lab. de Desenvolvimento de Novos Materiais

2012-07-01

The smectite clays have high adsorption capacity and cation exchange. Due to its chemical and physical characteristics, they can be effectively used as adsorbent of pollutants (such as metal ions). The initial objective of this study was to characterize the clay Brasgel through the techniques of X-Ray Diffraction (XRD), X-Ray Spectrometry by Energy Dispersive (EDX) and nitrogen adsorption (BET method), seeking its use in removing lead (Pb{sup 2+}) from synthetic effluents. System was used in finite bath to assess the potential removal of lead (Pb{sup 2+}), following a 2{sup 2} factorial experimental design with three center point experiments, taking as input variables: pH and initial concentrations of lead (Pb{sup 2+}). The clay has Brasgel clay in its composition that characterize it as a smectite clay. By having a large surface area, this clay showed great potential on the adsorption of metal ions. (author)

Clay mineralogy and geochemistry of the soils derived from metamorphic and mafic igneous parent rocks in Lahijan area

International Nuclear Information System (INIS)

Ramezanpour, H.; Hesami, R.; Zanjanchi, M. A.

2007-01-01

The mineralogical and geochemical composition of the soils of three representative pedons formed on basaltic andesite, andesitic basalt and phyllite were investigated. Results by x-ray diffraction showed that progressive weathering of rocks have been marked by gradual accumulation of Al, Fe, Ti, Mg, H 3 O + and depletion of Na, K, Ca and Si in the soil; although, predominant clay, loss and gain trend of elements was different on the various rocks. Based on x-ray diffraction analysis, minerals in basaltic andesite and andesitic basalt were similar but, the intensity of mica to smectite or vermiculite transformation for latter was relatively higher than the former. This process revealed the degradation mineral because of two reasons: (i) - smectite and vermiculite increased whereas mica decreased in surface horizons. (i i)-Irregular mixed layer of mica-smectite or vermiculite was present in deeper part (170 cm) of the soils from andesitic basalt but shallower depth (75 em) of the soils from basaltic andesite. Clay minerals in phyllite were mica and chlorite that stratified with vermiculite. However, the absence of smectite in phyllite might be attributed to more acidic condition or position of the Fe ion in the mineral lattice of chlorite (higher Fe in the interlayer hydroxide sheet)

Speciation of uranium in surface-modified, hydrothermally treated, (UO2)2+-exchanged smectite clays

International Nuclear Information System (INIS)

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

1997-01-01

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

JOINTS AND SYN-SEDIMENTARY FAULTS NETWORKS IN MARINE CLAYS AND MUDSTONES. Importance for Radwaste storage

Science.gov (United States)

Arnould, M.

2009-12-01

There is a number of marine clays, mudstones, marls, 100 to 200 m thick, showing smectites, mixed layers illite/smectite, with a small percentage of organic matter and sulphides with a variable clay, silt, and carbonate content. I published (Arnould , 2006) examples from Lower Cambrian to Miocene in age and from the Baltic shore to Spain in Europe. Observations were made mostly in quarries and pits down to more than 40 m and in underground research laboratories (URL). Only visible on fresh cuts amongst a variety of fissures there is always a network of joints. Schematically one family is the bedding (horizontal) the two others are normal to the bedding and orthogonal between them. The orientations of vertical joints are different from the orientations of pits and quarries’s walls. The networks are intrinsic. It was first well described by Skempton & al (1969) in Eocene London Clay. Joints are matt in texture, clean, without filling or cement. The order of magnitude of their linear dimensions is decimeter to meter. It is necessary to start from the original sediment: mud. Deposited in flakes mud has a bee’s nest microscopic structure. Each nest is full of water. Hence mud may have a water content up to 300%, reported to its dry weight. Paradoxically mud is impervious. As proposed by Cosgrove (2001) progressive but discontinuous hydraulic fracturing could be the origin of vertical joints, with drainage upwards and compaction of the sediment. Geological observations show that ioints are formed during the sedimentation process. There is also a world literature concluding at the necessary early fracturing of mudstones and marls hosts of sand dykes. Very few faults are identified in field observations and on exploration logs. But it is obvious that drainage and compaction of mud over thousands square kilometers induced differential settlements with many syn-sedimentary non tectonic faults constituting another discontinuity network. These faults inside the same

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

Lability of soil organic carbon in tropical soils with different clay minerals

DEFF Research Database (Denmark)

Bruun, Thilde Bech; Elberling, Bo; Christensen, Bent Tolstrup

2010-01-01

Soil organic carbon (SOC) storage and turnover is influenced by interactions between organic matter and the mineral soil fraction. However, the influence of clay content and type on SOC turnover rates remains unclear, particularly in tropical soils under natural vegetation. We examined the lability...... of SOC in tropical soils with contrasting clay mineralogy (kaolinite, smectite, allophane and Al-rich chlorite). Soil was sampled from A horizons at six sites in humid tropical areas of Ghana, Malaysian Borneo and the Solomon Islands and separated into fractions above and below 250 µm by wet sieving....... Basal soil respiration rates were determined from bulk soils and soil fractions. Substrate induced respiration rates were determined from soil fractions. SOC lability was significantly influenced by clay mineralogy, but not by clay content when compared across contrasting clay minerals. The lability...

Clay Mineralogy of Brazilian Oxisols with Shrinkage Properties

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Samara Alves Testoni

2017-08-01

Full Text Available ABSTRACT Shrinkage capacity (caráter retrátil in Portuguese is a new diagnostic characteristic recently introduced in the Brazilian System of Soil Classification (SiBCS to indicate shrink and swell properties observed in subtropical soils from highland plateaus in southern Brazil, specifically in Oxisols with brown colors. In soils located in road cuts exposed to drying for some weeks, strong shrinkage of soil volume is observed in these soils, resulting in the formation of pronounced vertical cracks and large and very large prismatic structures, which crumble in blocks when handled. We hypothesize that such properties are related to their clay mineralogy, although there are no conclusive studies about this, the motive for the present study. Samples of the A and B horizons from six Oxisols with expansive capacity from the states of Santa Catarina and Rio Grande do Sul were analyzed. One Rhodic Hapludox, from the state of Paraná, without expansive capacity, was used for comparison. All the soils are very clayey, originated from basalt, and have similar iron oxide content. For identification of clay mineralogy, X-ray diffraction techniques were employed, together with the use of NEWMOD® software to investigate and describe the interstratified minerals. The results showed that most expansive soils have a similar mineralogical composition, with kaolinite, interstratified kaolinite-smectite (K-S, and hydroxy-Al interlayered smectites (HIS, unlike the non-expansive Rhodic Hapludox, which exhibited kaolinite with significant amounts of gibbsite and low amount of interstratified K-S. According to the mineralogical assemblage identified in the expansive soils, we can affirm that the mechanism of smectite expansion and contraction is related to the shrinkage capacity of the soil, considering that the level of hydroxy-Al intercalation is low. In addition, these mechanisms also are related to the presence of quasicrystals and domains that control the

Aspects of clay/concrete interactions

International Nuclear Information System (INIS)

Oscarson, D.W.; Dixon, D.A.; Onofrei, M.

1997-01-01

In the Canadian concept for nuclear fuel waste management, both clay-based materials and concrete are proposed for use as barriers, seals or supporting structures. The main concern when clays and concrete are in proximity is the generation of a high-pH environment by concrete since clay minerals are relatively unstable at high pH. Here we examine the OH - -generating capacity of two high-performance concretes when in contact with several solutions. We also investigate various aspects of claylconcrete interactions. They are: (1) the alkalimetric titration of clay suspensions, (2) the effect of Ca(OH) 2 (portlandite) on the swelling and hydraulic properties of compacted bentonite, and (3) the influence of cement grout on a backfill clay retrieved from the 900-d Buffer/Container Experiment at the Underground Research Laboratory of AECL. The results indicate that although high-performance concretes establish significantly lower poresolution pH (9 to 10) than does ordinary portland cement, the pH is still somewhat higher than that of clay/groundwater systems of about pH 8. Hence, even if high-performance concrete is used in a disposal vault, the potential still exists for clay minerals to alter over long periods of time if in contact with this concrete. The data show, however, that clays have a substantial buffering capacity, and clay-based barriers can thus neutralize much of the OH - potentially released from concrete in a vault. Moreover, even after reacting for 120 d at 85 o C with up to 5 wt.% Ca(OH) 2 , compacted bentonite (dry density = 1.2 Mg/m 3 ) retains much of its swelling capacity and has a permeability low enough (hydraulic conductivity ≤ 10 -11 m/s) to ensure that molecular diffusion will be the main transport mechanism through compacted clay-based barriers. Furthermore, according to X-ray diffractometry, the clay mineral component of backfill was not altered by contact with a cement grout for 900 d in the Buffer/Container Experiment

Verification of substitution of bentonites by montmorillonitic clays summary report on Czech montmorillonitic clays

International Nuclear Information System (INIS)

Carlson, L.; Keto, P.

2006-10-01

Czech bentonites and smectite-rich clays were characterised in order to study if they could be used as buffer and backfill materials instead of non-Czech commercial bentonites. The characterisation work was orgnized by RAWRA (the Czech Radioactive Waste Repository Authority) and the main part of the work was performed in the Czech Republic at Charles University and at Czech Technical University. Parallel and complementary characterisation was conducted in Finland in Sweden. This report was compiled with the aim to summarise the results, and to compare the methods and results gained in different testing laboratories. The characterisation included mineralogical, chemical and geotechnical investigations and experiments on thermal stability and sorption. There were some variations between the results gained in different laboratories. This was mainly due to differences between the testing methods used but also due to heterogeneity of the samples. The Czech bentonite-clays from Rokle and Strance clay deposits contained relatively high amount of swelling minerals and thus can be considered as potential buffer and backfill materials. (orig.)

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

On the effect of hot water vapor on MX-80 clay

International Nuclear Information System (INIS)

Pusch, Roland

2000-10-01

Earlier experiments with smectite clay exposed to hot water vapor have indicated that the expandability may be largely lost. If such conditions prevail in a HLW repository the buffer clay may deteriorate and lose its isolating potential. The present study aimed at checking this by hydrothermal treatment at 90 to 110 deg C of rather dense MX-80 clay with subsequent oedometer testing for determining the hydration rate, swelling pressure and hydraulic conductivity, which are all expected to be quite different from those of untreated clay if the expandability is actually reduced. The results show that the swelling pressure of MX-80 clay is not noticeably altered by exposing it to vapor with a temperature of up to 110 deg C for one month while the hydraulic conductivity is increased by about 10% due to some permanent microstructural alteration. The overall change in physical properties of MX-80 clay under the prevailing laboratory conditions is not very significant

On the effect of hot water vapor on MX-80 clay

Energy Technology Data Exchange (ETDEWEB)

Pusch, Roland [Geodevelopment AB, Lund (Sweden)

2000-10-01

Earlier experiments with smectite clay exposed to hot water vapor have indicated that the expandability may be largely lost. If such conditions prevail in a HLW repository the buffer clay may deteriorate and lose its isolating potential. The present study aimed at checking this by hydrothermal treatment at 90 to 110 deg C of rather dense MX-80 clay with subsequent oedometer testing for determining the hydration rate, swelling pressure and hydraulic conductivity, which are all expected to be quite different from those of untreated clay if the expandability is actually reduced. The results show that the swelling pressure of MX-80 clay is not noticeably altered by exposing it to vapor with a temperature of up to 110 deg C for one month while the hydraulic conductivity is increased by about 10% due to some permanent microstructural alteration. The overall change in physical properties of MX-80 clay under the prevailing laboratory conditions is not very significant.

Modelling of the physico-chemical behaviour of clay minerals with a thermo-kinetic model taking into account particles morphology in compacted material.

Science.gov (United States)

Sali, D.; Fritz, B.; Clément, C.; Michau, N.

2003-04-01

Modelling of fluid-mineral interactions is largely used in Earth Sciences studies to better understand the involved physicochemical processes and their long-term effect on the materials behaviour. Numerical models simplify the processes but try to preserve their main characteristics. Therefore the modelling results strongly depend on the data quality describing initial physicochemical conditions for rock materials, fluids and gases, and on the realistic way of processes representations. The current geo-chemical models do not well take into account rock porosity and permeability and the particle morphology of clay minerals. In compacted materials like those considered as barriers in waste repositories, low permeability rocks like mudstones or compacted powders will be used : they contain mainly fine particles and the geochemical models used for predicting their interactions with fluids tend to misjudge their surface areas, which are fundamental parameters in kinetic modelling. The purpose of this study was to improve how to take into account the particles morphology in the thermo-kinetic code KINDIS and the reactive transport code KIRMAT. A new function was integrated in these codes, considering the reaction surface area as a volume depending parameter and the calculated evolution of the mass balance in the system was coupled with the evolution of reactive surface areas. We made application exercises for numerical validation of these new versions of the codes and the results were compared with those of the pre-existing thermo-kinetic code KINDIS. Several points are highlighted. Taking into account reactive surface area evolution during simulation modifies the predicted mass transfers related to fluid-minerals interactions. Different secondary mineral phases are also observed during modelling. The evolution of the reactive surface parameter helps to solve the competition effects between different phases present in the system which are all able to fix the chemical

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

Science.gov (United States)

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

2018-03-01

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

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

Science.gov (United States)

Bristow, Thomas F.; Blake, David F.

2014-01-01

The Mars Science Laboratory (MSL) Rover, Curiosity spent approx 150 sols at Yellowknife Bay (YKB) studying a section of fluvio-lacustrine sedimentary rocks (with potential indications of volcanic influence), informally known as the Yellowknife Bay formation. YKB lies in a distal region of the Peace Vallis alluvial fan, which extends from the northern rim of Gale Crater toward the dune field at the base of Mt Sharp. Sedimentological and stratigraphic observations are consistent with the Yellowknife Bay formation being part of a distal fan deposit, which could be as young as middle Hesperian to even early Amazonian in age (approx. 3.5 to 2.5 Ga). The Yellowknife Bay formation hosts a unit of mudstone called the Sheepbed member. Curiosity obtained powdered rock samples from two drill holes in the Sheepbed Member, named John Klein and Cumberland, and delivered them to instruments in Curiosity. Data from CheMin, a combined X-ray diffraction (XRD)/X-ray fluorescence instrument (XRF), has allowed detailed mineralogical analysis of mudstone powders revealing a clay mineral component of approx. 20 wt.% in each sample. The clay minerals are important indicators of paleoenvironmental conditions and sensitive recorders of post-depositional alteration processes. The XRD pattern of John Klein reveals a 02l band consistent with a trioctahedral phyllosilicate. A broad peak at approx. 10A with a slight inflexion at approx. 12A indicates the presence of 2:1 type clay minerals in the John Klein sample. The trioctahedral nature of the clay minerals, breadth of the basal reflection, and presence of a minor component with larger basal spacing suggests that John Klein contains a trioctahedral smectite (probably saponite), whose interlayer is largely collapsed because of the low-humidity conditions. The XRD patterns show no evidence of corrensite (mixed-layer chlorite/smectite) or chlorite, which are typical diagenetic products of trioctahedral smectites when subjected to burial and

A model for predicting embankment slope failures in clay-rich soils; A Louisiana example

Science.gov (United States)

Burns, S. F.

2015-12-01

A model for predicting embankment slope failures in clay-rich soils; A Louisiana example It is well known that smectite-rich soils significantly reduce the stability of slopes. The question is how much smectite in the soil causes slope failures. A study of over 100 sites in north and south Louisiana, USA, compared slopes that failed during a major El Nino winter (heavy rainfall) in 1982-1983 to similar slopes that did not fail. Soils in the slopes were tested for per cent clay, liquid limits, plasticity indices and semi-quantitative clay mineralogy. Slopes with the High Risk for failure (85-90% chance of failure in 8-15 years after construction) contained soils with a liquid limit > 54%, a plasticity index over 29%, and clay contents > 47%. Slopes with an Intermediate Risk (55-50% chance of failure in 8-15 years) contained soils with a liquid limit between 36-54%, plasticity index between 16-19%, and clay content between 32-47%. Slopes with a Low Risk chance of failure (soils with a liquid limit plasticity index soil characteristics before construction. If the soils fall into the Low Risk classification, construct the embankment normally. If the soils fall into the High Risk classification, one will need to use lime stabilization or heat treatments to prevent failures. Soils in the Intermediate Risk class will have to be evaluated on a case by case basis.

Structural characterization of bentonite clays for utilization as nanofillers in nanocomposites

International Nuclear Information System (INIS)

Oliveira, Carlos Ivan Ribeiro de; Rocha, Marisa Cristina Guimares; Vogas, Arthur Considera

2014-01-01

Clays of different composition have been used in the development of polymer nanocomposites. However, the utilization of bentonite clays has been emphasized in Brazil, mainly due to their availability.The best known and studied deposits of bentonite clays are located in the state of Paraiba. However, these deposits are becoming exhausted after decades of exploitation. In this context, the aim of this work is to proceed the physical-mineralogical characterization of bentonite clays recently discovered in Cubati, PB. In order to achieve this objective, the samples underwent a particle size classification step and were characterized by X-ray fluorescence, X-ray diffraction, infrared spectroscopy, thermal analysis and scanning electron microscopy. Results of X-ray diffraction showed that the samples are composed of smectite, and kaolinite and quartz. The characterization of the samples by FTIR confirmed these results. Results of chemical analysis showed that the clays have predominantly different exchangeable cations. (author)

Grain surface features and clay mineralogy of the quaternary sediments from Western Deccan Trap Region, India, and their palaeoclimatic significance

Directory of Open Access Journals (Sweden)

Veena U. Joshi

2011-06-01

Full Text Available Quartz sand grains obtained from a deeply gullied topography along the banks of two tributaries of River Pravara in Maharashtra (India have been examined with a scanning electron microscope (SEM. Quartz grains have been selected after a heavy mineral separation and micro-photographs of each grain were taken at various angles and magnifications. The sediments reveal features resulting from mechanical grinding as well as from chemical alteration. Conchoidal fractures, cleavage planes, grooves, v-shaped indentations etc. are the mechanical features documented on the grains whereas solution pits of varying sizes and intensity, precipitation surfaces, oriented v-pits, solution crevasses and etching are the features of chemical origin. Several evidences indicate that the samples have undergone digenetic changes. Few grains show the features of intense chemical breakdown. The overall assemblages of the grain surface features suggest that the samples have been subjected to subaqueous transport for a considerable period of time. The minor chemical features such as solution pits or semi circular arcuate steps found in abundance on these grains are due to the dissolution of the sediments in a low energy fluviatile environment. For clay mineralogy, fractions between <2 and <0.2 mm were separated out from the sediments. The clay fractions were then subjected to examination by X-ray diffraction (XRD of oriented K/Ca saturated samples using a Philips Diffractometer and Ni-filtered Cu Ka radiation with the scanning speed of 10 2Ө min -1. The main clay minerals for all the samples are identical and show the presence of hydroxy-interlayered smectites with minor quantities of mica, kaolinite, smectites, quartz and feldspar. The first weathering product of the Deccan Basalt (DB is the dioctahedral smectite. Since the present semi aridic climatic condition of the study area can not transform a smectite to HIS and either smectite to kaolin, it is quite likely that

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

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

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.

On the role of clay and its mineralogic components in low- and intermediary-level radioactive waste disposal

International Nuclear Information System (INIS)

Craciun, C.; Balan, V.

2001-01-01

In site selection for radioactive waste disposal a special attention is paid to clay and its mineralogic components as it has an important potential of retarding for both the radionuclides in radioactive wastes and fluid dynamics in the disposal site. The most frequent reaction implied in the radioisotope migration from liquid to solid phase is the cationic exchange. This work aimed at finding the relationship of clay and its mineralogic components, on one hand, and the exchange properties of the deposits, on the other hand. These relationships are based on the data obtained from about 50 cores sampled in 5 drillings performed in Saligny site, selected for radioactive waste disposal. Four levels different from physical, chemical and mineralogical properties were evidenced. The ionic exchange rate, with values within 5 to 30 me/100 g, has a trend of reflecting the clay contents. The relations between the cationic exchange rate and the clay contents appears to be linear with correlation coefficients varying within 0.81 - 0.97. The mineralogical composition of clay includes smectite (predominantly), illite and kaolin. Close, linear relations between the cationic exchange rate and the smectite fraction in clay and deposits were established with correlation coefficients within 0.74-0.76 and 0.85-0.95, respectively. These results show that the potential of the investigated deposits of acting as natural barriers with retarding effects on both radionuclides and the fluids in the disposal zone is strongly correlated to the amount and the content of the clay in these deposits

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

Science.gov (United States)

Bristow, Thomas; Blake, David; Bish, David L.; Vaniman, David; Ming, Douglas W.; Morris, Richard V.; Chipera, Steve; Rampe, Elizabeth B.; Farmer, Jack, D.; Treiman, Allan H;

The structure of actinide ions exchanged into native and modified zeolites and clays

International Nuclear Information System (INIS)

Wasserman, S. R.; Soderholm, L.; Giaquinta, D. M.

2000-01-01

X-ray absorption spectroscopy (XAS) has been used to investigate the structure and valence of thorium (Th 4+ ) and uranyl (UO 2 2+ ) cations exchanged into two classes of microporous aluminosilicate minerals: zeolites and smectite clays. XAS is also employed to examine the fate of the exchanged cations after modification of the mineral surface using self-assembled organic films and/or exposure to hydrothermal conditions. These treatments serve as models for the forces that ultimately determine the chemical fate of the actinide cations in the environment. The speciation of the cations depends on the pore size of the aluminosilicate, which is fixed for the zeolites and variable for the smectites

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

Distribution of clay minerals in the process streams produced by the extraction of bitumen from Athabasca oil sands

Energy Technology Data Exchange (ETDEWEB)

Kaminsky, H.A.W.; Etsell, T.H.; Ivey, D.G. [Alberta Univ., Edmonton, AB (Canada). Dept. of Chemical and Materials Engineering; Omotoso, O. [Natural Resources Canada, Devon, AB (Canada). CETC

2009-02-15

The clay minerals present in the oil sands were studied with particular reference to how they are partitioned in bitumen ore during the extraction process. Bitumen production from surface-mined oil sands accounts for nearly two-thirds of the total bitumen production in Alberta. Every cubic meter of mined ore results in 1.3 cubic meters of mature fine tailings (MFT). The characteristic differences between the clay minerals that report to the froth versus the tailings streams were also examined to determine which minerals could impact different unit operations in the bitumen extraction process. X-ray diffraction and random powder samples were used to quantify the clay minerals. Particle size distribution and clay activity balances were also conducted. The degree of partitioning during the conditioning and flotation stages in a batch extractor was determined by the surface properties of the clay minerals. The water-continuous tailings stream was separated into fine and coarse tailings fractions through sedimentation. The study showed that bitumen-clay interactions may be dominated by kaolinite or iron oxides. Clays are responsible for the poor settling behaviour of MFTs. The clay minerals present in the oil sands include illite, illite-smectite, kaolinite, kaolinite-smectite, and chlorite. The close proximity of the tailings ponds to the Athabasca River and volatile organic compounds (VOCs) emission require that the ponds be reclaimed to a natural landscape before mine closure. In addition to its impact on fine tailings reclamation, clay mineralogy plays a role in extraction froth flotation and emulsion stability during froth treatment. The mineralogy of the froth solids was found to be different from the mineralogy of the middlings and tailings solids. 39 refs., 6 tabs., 6 figs.

Clay fraction mineralogy of a Cambisol in Brazil

International Nuclear Information System (INIS)

Anastacio, A. S.; Fabris, J. D.; Stucki, J. W.; Coelho, F. S.; Pinto, I. V.; Viana, J. H. M.

2005-01-01

Clay minerals having a 2:1 (tetrahedral:octahedral sheet) structure may be found in strongly weathering soils only if the local pedo-climatic environment prevents them from further weathering to other minerals such as iron oxides. The clay minerals impart important chemical properties to soils, in part by virtue of changes in the redox state of iron in their crystal structures. Knowing the chemical nature of soil clays is a first step in evaluating their potential reactivity with other soil constituents and processes, such as the chemical decomposition of organic substrates to be potentially used in environmental remediation. The purpose of this work was to characterize the iron oxides and iron-bearing clay minerals from a B horizon of a Cambisol developed on tuffite in the State of Minas Gerais, Brazil, using chemical analysis, powder X-ray diffraction, Moessbauer spectroscopy, and thermal analysis. The iron oxides of this NaOH-treated clay-fraction were found to contain mainly maghemite (γFe 2 O 3 ) and superparamagnetic goethite (αFeOOH). Kaolinite (Al 2 Si 2 O 5 (OH) 4 ), smectite, and minor portions of anatase (TiO 2 ) were identified in the CBD-treated sample.

The Ypresian clays as alternative host rock for radioactive waste disposal in Belgium. A transferability study

International Nuclear Information System (INIS)

Van Baelen, Herve; Wouters, Laurent; Brassinnes, Stephane; Van Geet, Maarten; Vandenberghe, Noel

2012-01-01

-layer phases, but less kaolinite. The smectites in the Ypresian clays partly originate from weathered volcanic ash layers, re-mobilised and deposited into the basin during the early Eocene, but there are indications as well for the direct sedimentation of ash layers within the basin, which subsequently transformed into authigenic smectite. Scanning electron microscopy images reveal that the compaction fabric of the Ypresian clays is, at least in a number of samples, less pronounced than for Boom Clay. An additional difference is possibly the presence of a bi-modal pore size distribution, the larger pore size population being absent in undisturbed Boom Clay. Nevertheless the total porosity measured in both host rocks is comparable, but decreases with depth in the case of the Ypresian clays. From a mechanical point of view, Ypresian clays seem to behave less stiff and appears to be more sensitive to failure. Concerning the thermal properties, contrasting results have been obtained. In a first research effort, the thermal conductivity was smaller than for Boom Clay; more recently, however, a higher conductivity than for Boom Clay was obtained, illustrating the sensitivity of thermal-conductivity measurements to the experimental conditions. The measured hydraulic conductivity covers a comparable range to Boom Clay, but displays larger vertical variations. The diffusion accessible porosity and apparent diffusion coefficient obtained on clay cores are in the same order, but a decrease with depth has been observed for the Ypresian clays. Analysis of the pore water chemistry indicates that it is of the NaCl-type and can be categorised as brackish to salty. Especially in the upper part of the Ypresian clays, the results show a very high vertical variation, which does probably not reflect the natural variability, but reflects the difficulties of obtaining a representative pore water by squeezing. The same safety concept as the one developed on Boom Clay can be envisaged, but some

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

Science.gov (United States)

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

2017-04-01

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

Clarification of olive mill and winery wastewater by means of clay-polymer nanocomposites

Energy Technology Data Exchange (ETDEWEB)

Rytwo, Giora, E-mail: rytwo@telhai.ac.il [Tel Hai College, Dept. of Environmental Sciences, Upper Galilee 12210 (Israel); Environmental Physical Chemistry Laboratory, MIGAL, Galilee Technological Center, Kiryat Shmona (Israel); Lavi, Roy; Rytwo, Yuval; Monchase, Hila [Environmental Physical Chemistry Laboratory, MIGAL, Galilee Technological Center, Kiryat Shmona (Israel); Dultz, Stefan [Institute of Soil Science, Leibniz University Hannover, Herrenhaeuser Str. 2, D-30419 Hannover (Germany); Koenig, Tom N. [Environmental Physical Chemistry Laboratory, MIGAL, Galilee Technological Center, Kiryat Shmona (Israel)

2013-01-01

Highly polluted effluents from olive mills and wineries, among others, are unsuitable for discharge into standard sewage-treatment plants due to the large amounts of organic and suspended matter. Efficiency of all management practices for such effluents depends on an effective pretreatment that lowers the amount of suspended solids. Such pretreatments are usually based on three separate stages, taking a total of 2 to 6 h: coagulation-neutralizing the colloids, flocculation-aggregating the colloids into larger particles, and separation via filtration or decanting. Previous studies have presented the concept of coagoflocculation based on the use of clay-polymer nanocomposites. This process adds a higher density clay particle to the flocs, accelerating the process to between 15 and 60 min. This study examined suitable nanocomposites based on different clays and polymers. The charge of the compounds increased proportionally to the polymer-to-clay ratio. X-ray diffraction (XRD) measurements indicated that in sepiolite-based nanocomposites there is no change in the structure of the mineral, whereas in smectite-based nanocomposites, the polymer intercalates between the clay layers and increases the spacing depending on the polymer-to-clay ratio. Efficiency of the coagoflocculation process was studied with a dispersion analyzer. Sequential addition of olive mill or winery effluents with a boosting dose of nanocomposites may yield a very efficient and rapid clarification pretreatment. Highlights: Black-Right-Pointing-Pointer Nanocomposites yielded clarification of olive mill (OMW) and winery effluents (WW). Black-Right-Pointing-Pointer In smectite based nanocomposites intercalation of the polymer was measured. Black-Right-Pointing-Pointer In sepiolite based nanocomposites no changes in the spacing were observed. Black-Right-Pointing-Pointer Colloidal neutralization is the main clarification process in WW but not in OMW. Black-Right-Pointing-Pointer Several cycles of

Organosilane grafted acid-activated beidellite clay for the removal of non-ionic alachlor and anionic imazaquin

International Nuclear Information System (INIS)

Paul, Blain; Martens, Wayde N.; Frost, Ray L.

2011-01-01

Clay adsorbents were prepared via two-step method to remove nonionic alachlor and anionic imazaquin herbicides from water. Firstly, layered beidellite clay, a member of smectite family, was treated with acid in hydrothermal process; secondly, common silane coupling agents, 3-chloro-propyl trimethoxysilane or triethoxy silane, were grafted on the acid treated samples to prepare adsorbent materials. The organically modified clay samples were characterized by powder X-ray diffraction, N 2 gas adsorption, and FTIR spectroscopy. It was found that the selective modification of clay samples displayed higher adsorption capacity for herbicides compared with acid activated clay. And the amount of adsorption is increased with increasing the grafting amount of silane groups. Clay grafted with 3-chloro-propyl trimethoxysilane is an excellent adsorbent for both alachlor and imazaquin but triethoxy (octyl) silane grafted clay is more efficient only for alachlor removal.

Clay Mineralogy of Coal-Hosted Nb-Zr-REE-Ga Mineralized Beds from Late Permian Strata, Eastern Yunnan, SW China: Implications for Paleotemperature and Origin of the Micro-Quartz

Directory of Open Access Journals (Sweden)

Lixin Zhao

2016-05-01

Full Text Available The clay mineralogy of pyroclastic Nb(Ta-Zr(Hf-REE-Ga mineralization in Late Permian coal-bearing strata from eastern Yunnan Province; southwest China was investigated in this study. Samples from XW and LK drill holes in this area were analyzed using XRD (X-ray diffraction and SEM (scanning electronic microscope. Results show that clay minerals in the Nb-Zr-REE-Ga mineralized samples are composed of mixed layer illite/smectite (I/S; kaolinite and berthierine. I/S is the major component among the clay assemblages. The source volcanic ashes controlled the modes of occurrence of the clay minerals. Volcanic ash-originated kaolinite and berthierine occur as vermicular and angular particles, respectively. I/S is confined to the matrix and is derived from illitization of smectite which was derived from the original volcanic ashes. Other types of clay minerals including I/S and berthierine precipitated from hydrothermal solutions were found within plant cells; and coexisting with angular berthierine and vermicular kaolinite. Inferred from the fact that most of the I/S is R1 ordered with one case of the R3 I/S; the paleo-diagenetic temperature could be up to 180 °C but mostly 100–160 °C. The micro-crystalline quartz grains (<10 µm closely associated with I/S were observed under SEM and were most likely the product of desiliconization during illitization of smectite.

Investigations of excavated clay-stone as backfill/seal material

International Nuclear Information System (INIS)

Zhang, Chun-Liang

2012-01-01

Document available in extended abstract form only. Crushed clay-stone produced by excavation activities of repository drifts has been investigated as backfill/seal material at the GRS laboratory. The raw aggregate with coarse grains is considered to be used for backfilling the repository openings and, in mixture with bentonite, for sealing the boreholes, drifts and shafts. The GRS research programme focused on characterizing the thermo-hydro-mechanical properties of the excavated Callovo-Oxfordian clay-stone (COX) and the clay-stone-bentonite mixtures, including mechanical compaction, gas and water permeability as function of porosity, water retention and saturation, swelling capacity, and thermal properties of the materials. The most important results are presented in this paper. Figure 1 shows the compaction and permeability behaviour of the excavated clay-stone with grains up to a size of 32 mm. The results were obtained on large samples of 280 mm diameter and 680 mm height under quasi-hydrostatic compression. The porosity and permeability decrease with increasing load. The porosity-mean stress relation is non-linear and may be expressed by an exponential function. The backfill becomes stiffer at low porosities and can sustain certain deviatoric loads. At porosity of ∼21 %, the strength is characterized by an inherent cohesion of 3.7 MPa and an internal friction angle of 12 deg.. Additionally, the compaction is also dependent on time or loading rate, water content, and temperature. The compaction of the porous backfill material leads to a reduction in permeability. The measured gas permeability decreases much faster at low porosities below ∼25 %. The gas permeability at porosity of ∼20 % becomes as low as that of 10 -20 - 10 -21 m 2 for the intact clay rock. This is probably due to disconnection of the pore network during the compaction. As sealing material, powdered COX clay-stone was mixed with MX80 bentonite powder in different ratios and compacted to

Swelling pressure in compacted bentonite below 0°C

International Nuclear Information System (INIS)

Birgersson, Martin; Karnland, Ola; Nilsson, Ulf

2010-01-01

Document available in extended abstract form only. Bentonite is a common component in many concepts for underground storage of high level radioactive waste. During its lifetime, an underground repository will be subject to various ambient temperatures. Backfilled tunnels, shafts and investigation bore holes closest to ground level will experience periods of temperature below 0 deg. C. From a safety assessment perspective, it is therefore essential to investigate and understand the behavior of bentonite below 0 deg. C. A large set of laboratory tests have been performed where fully water saturated samples of bentonites have been exposed to temperatures in the range -10 deg. C - +25 deg. C. The swelling pressure response has been recorded continuously. The samples have been varied with respect to bentonite type (e.g. calcium or sodium dominated), smectite content and density. The general observation is that the pressure of the bentonite lowers in a temperature range between 0 deg. C and a specific (negative) temperature T c , which is strongly correlated to the swelling pressure measured above 0 deg. C. Consequently, Tc decreases (i.e. becomes more negative) with increased density or smectite content. At T c , swelling pressure is completely lost. Furthermore, a very weak pressure dependence is observed at temperatures above 0 deg. C. This dependence is however strictly dependent on sample density. For any type of bentonite at high enough densities above 0 deg. C, the slope of the P-T curve is negative and becomes more negative with increasing density. For Na-dominated bentonites at lower densities, on the other hand, the slope is positive. An important observation is that no pressure increase was observed for any of the tested bentonite samples as the transition to temperatures below 0 deg. C was made. Since water expands as it freezes, this observation indicates that no ice is formed in compacted bentonite as the 0 deg. C level is passed. The observed swelling

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.

Reduction of cracking and shrinkage in compressed clay beams during dying

International Nuclear Information System (INIS)

Lakho, N.A.; Zardari, M.A.; Memon, N.A.

2016-01-01

Uncontrolled evaporation of moisture from compressed clay beams can cause surface cracks, resulting in reduction of strength. This paper presents various treatments applied to clay beams during the process of casting, compacting and drying in order to curtail the possibility of cracking and to decrease percentage of drying shrinkage. Following treatments were applied to the beams during casting and drying: (i) a steel plate and double layer of plastic sheet was provided between the beam and the plank, (ii) the beam was enveloped with a propylene fabric sheet during casting and (iii) beams were covered with plastic sheet during drying. Using these treatments, the clay beams were cast and compacted at various intensities of compaction. The results show that the drying shrinkage was reduced to minimum and the cracks were curtailed. The rate of drying shrinkage was decreased depending upon the level of compaction. Thus at the higher degree of compaction, more density of clay beams was achieved, which resulted in higher degree of compressive strength in baked and unbaked state. (author)

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

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

Heteroaggregation of titanium dioxide nanoparticles with natural clay colloids.

Science.gov (United States)

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

2015-06-02

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

Placement of pre-compacted and in situ compacted dense backfill materials in shaft seals

International Nuclear Information System (INIS)

Martino, J.; Dixon, D.; Kim, C.S.

2010-01-01

Document available in extended abstract form only. In 2003, a decision was made to discontinue operation of Atomic Energy of Canada Limited's (AECL's) Underground Research Laboratory (URL) and ultimately to decommission and permanently close the underground portion of this facility. As part of the Nuclear Legacy Liability Program (NLLP) being funded by Natural Resources Canada (NRCan), an ongoing program of work is being undertaken to decommission and deal with facilities that are no longer part of AECL's mandate or operations. The URL is included in these facilities. Part of this work is the installation of seals at the intersection of the access and ventilation shafts and an ancient thrust fault, Fracture Zone 2 (FZ2), approximately 275 m below surface. These seals are being installed in order to limit the potential for mixing of deeper saline and shallower, less saline groundwater. The seal design in each shaft is similar with a heavily reinforced lower concrete component, a central bentonite clay-sand component and an upper un-reinforced concrete component. The main shaft at the URL at the location of the seal is circular (∼5-m diameter), and was excavated using careful drill and blast techniques. The seal itself consists of two keyed, conical sectioned, 3-m-thick by 5 to 6-m diameter concrete segments that confine a 6-m-thick swelling clay section. The ventilation shaft at the URL is 1.8 m in diameter and was excavated using raise-boring. The ventilation shaft will consist of two keyed, conical sectioned, 2-m-thick concrete by 1.8 to 2.8 m diameter concrete segments confining a 5-m-thick assembly of pre-compacted clay-sand blocks. The concrete is a low pH concrete designed for repository use, which can develop a 70 MPa unconfined compressive strength after 28 days. It has a pH of less than 11 achieved by substitution of 75% of the cement powder with silica fume and ground silica so the likelihood of free calcium and an alkaline plume is

Shear Strength of Remoulding Clay Samples Using Different Methods of Moulding

Science.gov (United States)

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

2016-07-01

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

Late-Quaternary variations in clay minerals along the SW continental margin of India: Evidence of climatic variations

Digital Repository Service at National Institute of Oceanography (India)

Chauhan, O.S.; Sukhija, B.S.; Gujar, A.R.; Nagabhushanam, P.; Paropkari, A.L.

Down-core variations in illite, chlorite, smectite and kaolinite (the major clays) in two sup(14)C-dated cores collected along the SW continental margin of India show that illite and chlorite have enhanced abundance during 20-17, 12.5, 11-9.5, and 5...

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.)

Tests for the characterization of bentonite used in the manufacture of clay geo synthetic barriers (GBR-C)

International Nuclear Information System (INIS)

Leiro, A.; Mateo, B.; Garcia, H.; Llorente, S.

2011-01-01

Bentonites are clays essentially composed of the smectite minerals. they are used in the manufacture of Clay Geosynthetic Barriers )GBR-C) which are low-permeability geosynthetic materials, forming part of the lining technologies and construction waterproofing systems. This article shows a series of testing to evaluate the quality of the bentonite for such use. Correlation between different testing has also been established in order to identify the most suitable ones for their characterization. (Author) 8 refs.

Seismic slip on clay nano-foliation

Science.gov (United States)

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

2017-12-01

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

Adsorption of hydrogen gas and redox processes in clays.

Science.gov (United States)

Didier, Mathilde; Leone, Laura; Greneche, Jean-Marc; Giffaut, Eric; Charlet, Laurent

2012-03-20

In order to assess the adsorption properties of hydrogen gas and reactivity of adsorbed hydrogen, we measured H(2)(g) adsorption on Na synthetic montmorillonite-type clays and Callovo-Oxfordian (COx) clayrock using gas chromatography. Synthetic montmorillonites with increasing structural Fe(III) substitution (0 wt %, 3.2 wt %, and 6.4 wt % Fe) were used. Fe in the synthetic montmorillonites is principally present as structural Fe(III) ions. We studied the concomitant reduction of structural Fe(III) in the clays using (57)Fe Mössbauer spectrometry. The COx, which mainly contains smectite/illite and calcite minerals, is also studied together with the pure clay fraction of this clayrock. Experiments were performed with dry clay samples which were reacted with hydrogen gas at 90 and 120 °C for 30 to 45 days at a hydrogen partial pressure close to 0.45 bar. Results indicate that up to 0.11 wt % of hydrogen is adsorbed on the clays at 90 °C under 0.45 bar of relative pressure. (57)Fe Mössbauer spectrometry shows that up to 6% of the total structural Fe(III) initially present in these synthetic clays is reduced upon adsorption of hydrogen gas. No reduction is observed with the COx sample in the present experimental conditions.

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)

Effects of magnesium minerals representative of the Callovian-Oxfordian clay-stone on borosilicate glass alteration

International Nuclear Information System (INIS)

Debure, M.

2012-01-01

Borosilicate glasses dissolution has been studied in presence of magnesium minerals. Those minerals (dolomite, illite, smectite...) belong to the Callovo-Oxfordian (COx) clay-stone layer, studied in France as a potential site for nuclear waste disposal. Such minerals contain magnesium, an element able to sustain glass alteration when it is available in solution. In the confined media of the wastes disposal, the solids reactivity controls the solution composition and can be the driving force of nuclear glass alteration. Experiments show that magnesium carbonates (hydro-magnesite and dolomite) increase in the glass alteration: the precipitation of magnesium silicates consumes silicon which slows down the formation of the glass passivating layer. The lower the magnesium mineral solubility, the lower the glass alteration. The purified clay phases (illite, smectite...) from the COx layer increase the glass alteration. Half the magnesium was replaced by sodium during the purification process. In such conditions, the effect of clay phases on glass alteration is in part due to the acidic pH-buffering effect of the clay fraction. The GRAAL model implemented in the geochemical transport code HYTEC has confirmed and quantified the mechanisms put in evidence in the experiments. Cells diffusion experiments where the two solids were separated by an inert diffusion barrier allow to valid reactive transport modelling. Such experiments are more representative of the glass package which will be separated from the COx by corrosion products. They show that glass alteration rate is reduced when solids are not close. (author) [fr

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.

Clay fraction mineralogy of a Cambisol in Brazil

Energy Technology Data Exchange (ETDEWEB)

Anastacio, A. S.; Fabris, J. D., E-mail: jdfabris@ufmg.br [Federal University of Minas Gerais, Campus - Pampulha, Department of Chemistry (Brazil); Stucki, J. W. [Department of Natural Resources and Environmental Sciences (United States); Coelho, F. S.; Pinto, I. V. [Federal University of Minas Gerais, Campus - Pampulha, Department of Chemistry (Brazil); Viana, J. H. M. [Embrapa Milho e Sorgo (Brazil)

2005-11-15

Clay minerals having a 2:1 (tetrahedral:octahedral sheet) structure may be found in strongly weathering soils only if the local pedo-climatic environment prevents them from further weathering to other minerals such as iron oxides. The clay minerals impart important chemical properties to soils, in part by virtue of changes in the redox state of iron in their crystal structures. Knowing the chemical nature of soil clays is a first step in evaluating their potential reactivity with other soil constituents and processes, such as the chemical decomposition of organic substrates to be potentially used in environmental remediation. The purpose of this work was to characterize the iron oxides and iron-bearing clay minerals from a B horizon of a Cambisol developed on tuffite in the State of Minas Gerais, Brazil, using chemical analysis, powder X-ray diffraction, Moessbauer spectroscopy, and thermal analysis. The iron oxides of this NaOH-treated clay-fraction were found to contain mainly maghemite ({gamma}Fe{sub 2}O{sub 3}) and superparamagnetic goethite ({alpha}FeOOH). Kaolinite (Al{sub 2}Si{sub 2}O{sub 5}(OH){sub 4}), smectite, and minor portions of anatase (TiO{sub 2}) were identified in the CBD-treated sample.

Study of process variables on organophilization of Cubati-PB bentonite clays with ionic surfactants

International Nuclear Information System (INIS)

Silva, C.D. da; Lima, R.C.O.; Costa, J.M.R.; Silva, E.I.A.; Neves, G.A.; Ferreira, H.C.

2012-01-01

The organophilic clays used as agent in the composition dispersed in petroleum drilling fluids, play important roles during drilling. This work aims at the development of several varieties of smectites Cubati-PB for use in drilling fluids for oil with the use of ionic surfactants. We used the following materials: natural bentonite clay Cinza Superior and Verde Superior, from the district of Cubati-PB and ionic quaternary ammonium salt: Praepagen WB®, with 45% active matter. The organoclays were characterized by the laser diffraction, chemical composition by x-ray, differential thermal analysis, thermal gravimetric analysis and x-ray diffraction. Globally found that clays have diffraction and thermal behavior typical of bentonite clay. The results showed showed that the clay used has the potential for application in the process of organophilic and, with respect the process variables has been observed that they do not alter the process organophilization. (author)

Pengaruh Proses Pelapukan Clay Shale terhadap Perubahan Parameter Rasio Disintegritas (DR

Directory of Open Access Journals (Sweden)

Idrus M Alatas

2017-04-01

Full Text Available The background of this research because of the frequent occurrence of the failure in the geotechnical design of clay shale caused by weathering. Disintegration ratio is a comparison of physical changes due to weathering at certain times of the initial conditions. Changes in physical properties due to clay shale weathering determined by the disintegration ratio (DR.Clay shale weathering will occur more quickly as a result of wetting and drying cycles when compared with the drying process. While due to the increased number of cycles of wetting at the same time, causing weathering on clay shale will be faster again. Until the 80th day of drying time, the magnitude DRof Semarang-Bawenclay shaleand Hambalang are the same, namely DR = 0.916 (completelly durable. However, due to wetting and drying cycles on day 32, samples of Semarang-Bawenclay shale is DR = 0.000 or non durable completelly, while on Hambalang clay shale in same day DR between 0.2117 to 0.3344. Generally Semarang-Bawen clay shale will be faster weathered than Hambalang clay shale. It is caused by the mineralogy content of Semarang-Bawen clay shale has dominated by Smectite, and Hambalangclay shalehas dominated mineral Kaolinite and Illlite.

Final report of the borehole, shaft, and tunnel sealing test. Vol.2

International Nuclear Information System (INIS)

Pusch, R.; Boergesson, L.; Ramqvist, G.

1987-01-01

Shaft sealing by use of highly compacted bentonite was investigated in a 14 m long shaft in which two plugs were constructed with a central sand-filled central space for injecting water. A first reference test with concrete plugs was followed by a main test in which the plug material consisted of blocks of highly compacted sodium bentonite powder. In the latter test, the outflow from the injection chamber was only a few percent of that with the concrete plugs, which demonstrates the excellent sealing properties of the clay. The main effect was that practically no water flow took place along the rock/clay interface. The longevity of smectite clay in crystalline rock is sufficient to make bentonite plugs operative for several thousand years. (authors)

Mechanical interaction between swelling compacted clay and fractured rock, and the leaching of clay colloids

NARCIS (Netherlands)

Grindrod, P.; Peletier, M.A.; Takase, H.

1999-01-01

We consider the interaction between a saturated clay buffer layer and a fractured crystalline rock engineered disturbed zone. Once saturated, the clay extrudes into the available rock fractures, behaving as a compressible non-Newtonian fluid. We discuss the modelling implications of published

Clay mineralogical studies on Bijawars of the Sonrai Basin: palaeoenvironmental implications and inferences on the uranium mineralization

International Nuclear Information System (INIS)

Jha, Surendra Kumar; Shrivastava, J.P.; Bhairam, C.L.

2012-01-01

Clays associated with the Precambrian unconformity-related (sensu lato) uranium mineralization that occur along fractures of Rohini carbonate, Bandai sandstone and clay-organic rich black carbonaceous Gorakalan shale of the Sonrai Formation from Bijawar Group is significant. Nature and structural complexity of these clays have been studied to understand depositional mechanism and palaeoenvironmental conditions responsible for the restricted enrichment of uranium in the Sonrai basin. Clays ( chlorite> illite > smectite mineral assemblages, whereas, Solda Formation contains kaolinite > illite > chlorite clays. It has been found that the former mineral assemblage resulted from the alteration process is associated with the uranium mineralization and follow progressive reaction series, indicating palaeoenvironmental (cycles of tropical humid to semi-arid/arid) changes prevailed during maturation of the Sonrai basin. The hydrothermal activity possibly associated with Kurrat volcanics is accountable for the clay mineral alterations

Desorption of intrinsic cesium from smectite: inhibitive effects of clay particle organization on cesium desorption.

Science.gov (United States)

Fukushi, Keisuke; Sakai, Haruka; Itono, Taeko; Tamura, Akihiro; Arai, Shoji

2014-09-16

Fine clay particles have functioned as transport media for radiocesium in terrestrial environments after nuclear accidents. Because radiocesium is expected to be retained in clay minerals by a cation-exchange reaction, ascertaining trace cesium desorption behavior in response to changing solution conditions is crucially important. This study systematically investigated the desorption behavior of intrinsic Cs (13 nmol/g) in well-characterized Na-montmorillonite in electrolyte solutions (NaCl, KCl, CaCl2, and MgCl2) under widely differing cation concentrations (0.2 mM to 0.2 M). Batch desorption experiments demonstrated that Cs(+) desorption was inhibited significantly in the presence of the environmental relevant concentrations of Ca(2+) and Mg(2+) (>0.5 mM) and high concentrations of K(+). The order of ability for Cs desorption was Na(+) = K(+) > Ca(2+) = Mg(2+) at the highest cation concentration (0.2 M), which is opposite to the theoretical prediction based on the cation-exchange selectivity. Laser diffraction grain-size analyses revealed that the inhibition of Cs(+) desorption coincided with the increase of the clay tactoid size. Results suggest that radiocesium in the dispersed fine clay particles adheres on the solid phase when the organization of swelling clay particles occurs because of changes in solution conditions caused by both natural processes and artificial treatments.

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.

Feasibility of using overburden clays for sealing purposes and laboratory testing of the clays

Energy Technology Data Exchange (ETDEWEB)

Mann, J. (Vyzkumny Ustav pro Hnede Uhli, Most (Czechoslovakia))

1992-03-01

Studies properties of overburden clay from North Bohemian surface coal mines for use as sealants of industrial and household waste that will be dumped at Czechoslovak surface mine sites. Basic requirements of sealing layers are optimum compressibility and impermeability by suitable compacting. Laboratory soil mechanical tests of different clay samples were carried out using the Proctor standard tests (PCS) and the Norwegian Geonor A/S - m 45 instrument. Laboratory tests were used to select the best available clay types with optimum density and moisture content. Experimental results of laboratory tests are provided.

Long-term performance of geosynthetic clay liners in cappings

International Nuclear Information System (INIS)

Maubeuge, K.P. von; Fricke, A.

1998-01-01

Geosynthetic clay liners (GCLs) are relatively thin composite materials combining bentonite clay and geosynthesis (usually geotextiles). GCLs have been employed by the waste industry for well over a decade now, and their level of usage is rapidly increasing world-wide. In landfill facilities, GCLs are generally used to replace or augment compacted clay liners. Until recently, the decision to do so has primarily been based on the availability of clay material on site (i.e., economic considerations). However, the advantages in using a GCL over other sealing elements such as compacted clay are not only economic but technically based, and the economic benefits extend beyond the construction phase, as a thin GCL can increase the revenue earning potential of a facility. This paper will highlight the shear behaviour of GCLs and demonstrate the long-term stability. (orig.)

SPRAYED CLAY TECHNOLOGY FOR THE DEEP REPOSITORY OF HIGH-LEVEL RADIOACTIVE WASTE

Directory of Open Access Journals (Sweden)

Lucie Hausmannová

2012-07-01

Full Text Available The sealing barrier will play very important role in the Czech disposal concept of high level radioactive waste. It follows Swedish SKB3 design where granitic rock environment will host the repository. Swelling clay based materials as the most favorable for sealing purposes were selected. Such clays must fulfill certain requirements (e.g. on swelling properties, hydraulic conductivity or plasticity and must be stable for thousands of years. Better sealing behavior is obtained when the clay is compacted. Technology of the seal construction can vary according to its target dry density. Very high dry density is needed for buffer (sealing around entire canister with radioactive waste. Less strict requirements are on material backfilling the access galleries. It allows compaction to lower dry density than in case of buffer. One of potential technology for backfilling is to compact clay layers in most of the gallery profile by common compaction machines (rollers etc. and to spray clay into the uppermost part afterwards. The paper introduces the research works on sprayed clay technology performed at the Centre of Experimental Geotechnics of the Czech Technical University in Prague. Large scale in situ demonstration of filling of short drift in the Josef Gallery is also mentioned.

Clay mineral facies and lateritization in basalts of the southeastern Parana Basin, Brazil

International Nuclear Information System (INIS)

Oliveira, M.T.G. de; Formoso, M.L.L.; Trescases, J.J.; Meunier, A.

1998-01-01

Seventeen samples from two lateritic profiles, each with five facies, were studied. These profiles occur on the old planation surface of the plateau basalts of the southern part of ParanáBasin, Brazil. Optical microscopy, X-ray diffraction, electron microprobe, Mössbauer spectroscopy and Fourier Transform Infrared Spectra were used to obtain information about the nature and chemical composition of each weathering facies. In addition, scanning electron microscopy and analyses of clay minerals were performed to detect microcrystalline environmental changes. Both profiles have two major parts: a loose red-clay latosol separated from an underlying mottled clay and an alterite facies; a stone line may or may not be present between the latosol and the underlying units. In both profiles the latosol consists principally of kaolinite, hematite and goethite. Two alterite facies, shaped by differential weathering, are also present in the lower profile: a halloysite–nontronite clayey matrix with a well developed fissure system occurs in the argillaceous alterite and a network of Al–goethite aggregates is typical of the highly porous cortex of the boulder alterite that is found in the stone line and below it. Gibbsite has crystallized in the large pores of porphyritic boulder alterite but is absent in the small pores of the subaphyric boulder alterite. Clay minerals observed in fissures include halloysite associated with goethite and manganese oxides. The basalt has hydrothermal green-clays (mixed layers and trioctahedral smectites) that formed between primary plagioclase, pyroxene and Ti–magnetite crystals while fresh corestones of the boulder alterite have cryptocrystalline iron-rich material. The study of these profiles shows one principal evolutionary trend for clay minerals. This trend is from smectite and mixed layers that form green clays in altered bedrock at the base of the profile to an intermediate association of nontronite and halloysite in the argillaceous

Compaction and Plasticity Comparative Behaviour of Soft Clay Treated with Coarse and Fine Sizes of Ceramic Tiles

Science.gov (United States)

Al-Bared, Mohammed Ali Mohammed; Marto, Aminaton; Sati Hamonangan Harahap, Indra; Kasim, Fauziah

2018-03-01

Recycled blended ceramic tiles (RBT) is a waste material produced from ceramic tile factories and construction activities. RBT is found to be cost effective, sustainable, environmental-friendly and has the potential to be used as an additive in soft soil stabilization. Recent reports show that massive amounts of RBT are dumped into legal or illegal landfills every year consuming very large spaces and creating major environmental problems. On the other hand, dredged marine clay obtained from Nusajaya, Johor, Malaysia has weak physical and engineering characteristics to be considered as unsuitable soft soil that is usually excavated, dumped into landfills and replaced by stiff soil. Hence, this study investigates the suitability of possible uses of RBT to treat marine clay. Laboratory tests included Standard proctor tests and Atterberg limits tests. The plasticity of marine clay was evaluated by adding 10%, 20%, 30% and 40% of 0.3 mm RBT. In addition, the compaction behaviour of treated marine clay was compared by adding two different sizes (0.3 mm and 1.18 mm diameter) of RBT. For both coarse and fine sizes of RBT, 10%, 20%, 30% and 40% of the dry weight of the soft clay were added. The mixture of each combination was examined in order to evaluate the Maximum Dry Density (MDD) and the optimum moisture content (OMC) for the treated soft clay. MDD and OMC for soft untreated samples were 1.59 Mg/m3 and 22%, respectively. Treated samples with 10%, 20%, 30% and 40% of 0.30 mm size RBT resulted in a significant reduction of OMC ranged from 19 to 15% while MDD resulted in increment ranged from 1.69 to 1.77 Mg/m3. In addition, samples treated with 10%, 20%, 30% and 40% of 1.18 mm size RBT resulted in major reduction of OMC ranged from 15 to 13.5% while MDD increased effectively from 1.75 to 1.82 Mg/m3. For all mix designs of soft clay-RBT, MDD was gradually increasing and OMC was sharply reducing with further increments of both sizes of RBT.

Compaction and Plasticity Comparative Behaviour of Soft Clay Treated with Coarse and Fine Sizes of Ceramic Tiles

Directory of Open Access Journals (Sweden)

Al-Bared Mohammed Ali Mohammed

2018-01-01

Full Text Available Recycled blended ceramic tiles (RBT is a waste material produced from ceramic tile factories and construction activities. RBT is found to be cost effective, sustainable, environmental-friendly and has the potential to be used as an additive in soft soil stabilization. Recent reports show that massive amounts of RBT are dumped into legal or illegal landfills every year consuming very large spaces and creating major environmental problems. On the other hand, dredged marine clay obtained from Nusajaya, Johor, Malaysia has weak physical and engineering characteristics to be considered as unsuitable soft soil that is usually excavated, dumped into landfills and replaced by stiff soil. Hence, this study investigates the suitability of possible uses of RBT to treat marine clay. Laboratory tests included Standard proctor tests and Atterberg limits tests. The plasticity of marine clay was evaluated by adding 10%, 20%, 30% and 40% of 0.3 mm RBT. In addition, the compaction behaviour of treated marine clay was compared by adding two different sizes (0.3 mm and 1.18 mm diameter of RBT. For both coarse and fine sizes of RBT, 10%, 20%, 30% and 40% of the dry weight of the soft clay were added. The mixture of each combination was examined in order to evaluate the Maximum Dry Density (MDD and the optimum moisture content (OMC for the treated soft clay. MDD and OMC for soft untreated samples were 1.59 Mg/m3 and 22%, respectively. Treated samples with 10%, 20%, 30% and 40% of 0.30 mm size RBT resulted in a significant reduction of OMC ranged from 19 to 15% while MDD resulted in increment ranged from 1.69 to 1.77 Mg/m3. In addition, samples treated with 10%, 20%, 30% and 40% of 1.18 mm size RBT resulted in major reduction of OMC ranged from 15 to 13.5% while MDD increased effectively from 1.75 to 1.82 Mg/m3. For all mix designs of soft clay-RBT, MDD was gradually increasing and OMC was sharply reducing with further increments of both sizes of RBT.

Planning of experimental removal of cadmium in finite bath system using the chocolate clay B as adsorbent; Caracterizacao de adsorvente (argila chocolate B) visando a remocao de cadmio

Energy Technology Data Exchange (ETDEWEB)

Mota, J.D.; Rodrigues, M.G.F.; Lima, W.S.; Souza, R.S., E-mail: wsl_20@yahoo.com.br, E-mail: meiry@deq.ufcg.edu.br [Universidade Federal de Campina Grande (LABNOV/UFCG), PB (Brazil). Unidade Academica de Engenharia Quimica. Lab. de Desenvolvimento de Novos Materiais

2012-07-01

The smectite clays are characterized by having a high cation exchange capacity and ability to remove metal ions. They have great industrial importance, for its abundance and low cost. The first part of this work was to characterize the clay called Chocolate B through the techniques of X-Ray Diffraction, X-Ray Spectroscopy and Energy Dispersive Physical Adsorption of Nitrogen. The second part of the work aims to evaluate the significance of the variables: pH and initial concentration on removal of cadmium in a batch system. In the experimental design used was a 2{sup 2} factorial analysis with the addition at the central point, and evaluated the percentage of removal (Rem%) and removal capacity (EQF). XRD results corroborating the chemical analysis (EDX), characterized as a B Chocolate smectite clays. Statistical analysis showed a strong influence of variable pH on the removal of cadmium. (author)

Geothermal alteration of clay minerals and shales: diagenesis

Energy Technology Data Exchange (ETDEWEB)

Weaver, C.E.

1979-07-01

The objective of this report is to perform a critical review of the data on the mineral and chemical alterations that occur during diagenesis and low-grade metamorphism of shale and other clay-rich rocks - conditions similar to those expected from emplacement of heat-producing radioactive waste in a geologic repository. The conclusions drawn in this document are that the following type of alterations could occur: smectite alteration, ion mobilization, illitic shales, kaolinite reactions, chlorite reactions, organic reactions, paleotemperatures, low temperature shales, high temperature shales, and phase equilibrium changes.

Geothermal alteration of clay minerals and shales: diagenesis

International Nuclear Information System (INIS)

Weaver, C.E.

1979-07-01

The objective of this report is to perform a critical review of the data on the mineral and chemical alterations that occur during diagenesis and low-grade metamorphism of shale and other clay-rich rocks - conditions similar to those expected from emplacement of heat-producing radioactive waste in a geologic repository. The conclusions drawn in this document are that the following type of alterations could occur: smectite alteration, ion mobilization, illitic shales, kaolinite reactions, chlorite reactions, organic reactions, paleotemperatures, low temperature shales, high temperature shales, and phase equilibrium changes

Use of organophilic clays in purification of oily wastewater; Uso de argilas organofilicas na purificacao de efluentes oleosos

Energy Technology Data Exchange (ETDEWEB)

Silva, A.A. [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Engenharia de Processos], email: adriana_anp@yahoo.com.br; Pereira, K.R de O.; Wiebeck, H.; Valenzuela-Diaz, F.R. [Universidade de Sao Paulo (EPUSP), SP (Brazil). Escola Politecnica. Dept. de Engenharia Metalurgica e de Materiais; Rodrigues, M. G.F. [Universidade Federal de Campina Grande (UFCG), PB (Brazil). CCT. Dept. de Engenharia Quimica

2006-07-01

Water mixed with oil is produced in great volume in industrial processes and in petroleum refineries. This mixture must be treated to return to environment or can be reused in the same process. The refine of this water is expensive and presents a difficult execution. The process of separation of oil in water used organophilic clays can be a new option. In this work, the process of preparation of organophilic clays using smectitic clay polycationic and a industrial sodium bentonite both from Paraiba State, Brazil is described. The samples were characterized by two techniques: X-ray Diffraction and Thermal Analysis. After preparation of the organophilic clays it was determined theirs swelling in organic solvents and oil adsorption capacity. The organophilic clays presented higher capacity of oil adsorption when compared to activated carbon. (author)

Synchrotron SAXS/WAXD and rheological studies of clay suspensions in silicone fluid.

Science.gov (United States)

Zhang, Li-Ming; Jahns, Christopher; Hsiao, Benjamin S; Chu, Benjamin

2003-10-15

Suspensions of two commercial smectite clays, montmorillonite KSF and montmorillonite K10, in a low-viscosity silicone oil (Dow Corning 245 Fluid) were studied by simultaneous synchrotron small-angle X-ray scattering (SAXS)/wide-angle X-ray diffraction (WAXD) techniques and rheological measurements. In the 0.5% (w/v) KSF clay suspension and two K10 clay suspensions (0.5% and 1.0%), WAXD profiles below 2theta=10.0 degrees did not display any characteristic reflection peaks associated with the chosen montmorillonite clays, while corresponding SAXS profiles exhibited distinct scattering maxima, indicating that both clays were delaminated by the silicone oil. In spite of the large increase in viscosity, the clay suspensions exhibited no gel characteristics. Dynamic rheological experiments indicated that the clay/silicone oil suspensions exhibited the behavior of viscoelasticity, which could be influenced by the type and the concentration of the clay. For the K10 clay suspensions, the frequency-dependent loss modulus (G") was greater in magnitude than the storage modulus (G') in the concentration range from 0.5 to 12.0%. The increase in the clay concentration shifted the crossover point between G' and G" into the accessible frequency range, indicating that the system became more elastic. In contrast, the KSF clay suspension exhibited lower G' and G" values, indicating a weaker viscoelastic response. The larger viscoelasticity response in the K10 clay suspension may be due to the acid treatment generating a higher concentration of silanol groups on the clay surface.

Polypropylene reinforced with organophilic clay and brazilian nut fibers

International Nuclear Information System (INIS)

Rocha-Gomes, L.V.; Mondelo-Garcia, F.J.; Vaccioli, K.; Valera, S.T.; Silva-Valenzuela, M.G.; Valenzuela-Diaz, F.R.

2014-01-01

Polymer nanocomposites have been shown to possess better properties when compared with traditional composites. This study aims to investigate the effects of the addition of organophilic clay and Brazilian nut fiber on the polypropylene (PP). First, 5%, 10% and 20% PP/compatibilizer maleic anhydride (PP-g-MA) by weight was added to Pure PP, respectively. From the results, 5% PP-g-MA was defined for preparing the nanocomposites. Samples were prepared containing 5% PP / PP-g-MA reinforced with 5% organophilic Brazilian smectite clay and 5%, 10% and 15% Brazilian nut fiber. Specimens were tested for tensile strength and impact. The materials were characterized by laser diffraction particle size and X-ray diffraction, and the nanocomposites, by mechanical strength and impact. The best result was obtained by inserting 15% fiber. (author)

Characterization of bentonite clay from Cubati, PB, Brazil

International Nuclear Information System (INIS)

Batista, A.P.; Marques, L.N.; Campos, L.A.; Neves, G.A.; Ferreira, H.C.; Menezes, R.R.

2009-01-01

The bentonite of the State of Paraiba are commercially used in numerous technological sectors, particularly in oil drilling muds. However, these bentonite deposits are becoming exhausted after decades of exploitation. Thus, the aim of this work was to characterize physically, mineralogically and technologically bentonite clays from Cubati city, PB. The samples were dried at 60 deg C and characterized through X-ray fluorescence, particle size distribution, X-ray diffraction, differential thermal and gravimetric analyzes and scanning electronic microscopy. The natural bentonite clays were transformed into sodium bentonite by Na_2CO_3 solution treatment. It was estimated the rheological properties of the suspensions: apparent and plastic viscosities and water loss. The results showed that the samples are polycationic bentonite clays, containing amounts of MgO, CaO and K_2O similar to those of bentonite from Boa Vista, PB, and are composed of smectite, kaolinite and quartz. The samples presented fractions of particles size under 2 μm of 30 and 32%. The rheological properties showed that the samples presented technological potential to be used in drilling muds. (author)

Model shear tests of canisters with smectite clay envelopes in deposition holes

International Nuclear Information System (INIS)

Boergesson, L.

1986-01-01

The consequences of rock displacement across a deposition hole has been investigated by some model tests. The model was scaled 1:10 to a real deposition hole. It was filled with a canister made of solid copper surrounded by highly compacted water saturated MX-80 bentonite. Before shear the swelling pressure was measured by six transducers in order to follow the water uptake process. During shear, pressure, strain, force and deformation were measured in altogether 18 points. The shearing was made at different rates in the various tests. An extensive sampling after shear was made through which the density, water content, degree of saturation, homogenization and the effect of shear on the bentonite and canister could be studied. One important conlusion from these tests was that the rate dependence is about 10% increased shear resistance per decade increased rate of shear. This resulted also in a very clear increase in strain in the canister with increased rate. The results also showed that the saturated bentonite has excellent stress distributing properties and that there is no risk of destroying the canister if the rock displacement is smaller than the thickness of the bentonite cover. The high density of the clay makes the bentonite produce such a high swelling pressure that the material will be very stiff. In the case of a larger shear deformation corresponding to ≅ 50% of the bentonite thickness the result will be a rather large deformation of the canister. A lower density would be preferable if it can be accepted with respect to other required isolating properties. The results also showed that three-dimensional FEM calculation using non-linear material properties is necessary to simulate the shear process. The rate dependence may be taken into account by adapting the properties to the actual rate of shear but might in a later stage be included in the model by giving the material viscous properties. (orig./HP)

Sorption of Cesium on smectite-rich clays from the Bohemian Massif (Czech Republic) and their mixtures with sand.

Science.gov (United States)

Vejsada, J; Jelínek, E; Randa, Z; Hradil, D; Prikryl, R

2005-01-01

Sorption is an important process for the transport of radionuclides through backfill materials in a radioactive waste underground repository. Within this study, sorption of Cs on selected Czech clay materials and their mixtures with sand was investigated by batch tests. The experiments were performed under oxic conditions at 25 degrees C. Synthetic groundwater as a liquid phase and unconditioned clays (as they were provided by their producer) were used to reach the natural conditions as close as possible. Distribution ratios (Rds) of Cs for all selected clays rise with increase of the clay fraction in clay/sand mixtures in agreement with previous works studying sorption behaviour of such mixtures. The rise of Rds is from 10(2) cm3 g(-1) for mixtures with 80% of sand to 10(3) cm3 g(-1) for pure clays. There are significant differences between natural and technologically modified clays.

Variation of crack intensity factor in three compacted clay liners exposed to annual cycle of atmospheric conditions with and without geotextile cover.

Science.gov (United States)

Safari, E; Jalili Ghazizade, M; Abduli, M A; Gatmiri, B

2014-08-01

Performance of compacted clay liners commonly used as landfill barrier systems can be subject to decline in terms of hydraulic conductivity if left exposed to atmospheric conditions for an extended period of time prior to placement of overlaying layers. The resulting desiccation cracking can lead to increased hydraulic conductivity. Desiccation crack intensity was studied for three clayey soils commonly used for construction of landfill barrier system in a relatively large scale test setup exposed to real time atmospheric conditions over a complete annual cycle. A white separator geotextile cover was presumed to be capable of reducing the intensity of desiccation cracking through absorbing and maintaining higher amounts of moisture and reducing the temperature of the soil surface in comparison to a directly exposed soil surface. Desiccation cracking was monitored using a digital imaging technique for three compacted clay liners in two sets, one open to air and the second covered with the white geotextile. Crack intensity factor approached a relatively stable phase after certain cycles corresponding to atmospheric dry wet cycles. The results indicated that the white separator geotextile was capable of reducing the crack intensity factor by 37.4-45.9% throughout the experiment including the cyclic phase of desiccation cracking. During the stable phase, the maximum reduction in crack intensity factor of 90.4% as a result of applying geotextile cover was observed for the soil with the lowest plastic index and clay content and therefore the lowest magnitude of crack intensity factor. The other two soils with similar clay content but different plastic index showed 23.6% and 52.2% reductions in crack intensity factor after cyclic phase when covered with geotextile. Copyright © 2014 Elsevier Ltd. All rights reserved.

Mineralogy and sealing properties of various bentonites and smectite-rich clay materials

Energy Technology Data Exchange (ETDEWEB)

Karnland, Ola; Olsson, Siv; Nilsson, Ulf (Clay Technology AB (SE))

2006-12-15

The present work includes a coherent study of Wyoming bentonite with respect to the most relevant properties for use in a repository, and a parallel study of other potential buffer and tunnel backfilling materials. The reason for this is twofold; to quantify the effect of mineralogical variations on the various important sealing properties of bentonite, and to verify that there are alternative potential sources of bentonite. The latter is motivated by the fact that Sweden alone plans to deposit at least 6,000 copper canisters which include approximately 130,000 metric tones bentonite buffer material and several times more as tunnel backfill material. Different types of sealing clay materials may also be relevant to use, since the demands on the clay will be different at the various locations in a repository. Alternative sources of bentonite would consequently be valuable in order to secure quality, supply, and price. Important aspects on buffer and tunnel backfilling materials may be summarized as: Original sealing properties. Hazardous substances in any respect. Short-term effects of ground-water chemistry. Long-term stability, i.e. effects of temperature and ground-water chemistry. Availability. Costs. The focus in this study is on the first three items. The long-term stability is indirectly considered in that mineralogical composition is determined. The availability is only considered in such a way that most of the analyzed materials represent huge clay formations, which contain much more material than needed for a repository. The cost aspects have not been included, mainly because the present day price is not relevant due to the time frame of the construction of a repository

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.

Water-clay interactions. Experimental study

International Nuclear Information System (INIS)

Gaucher, Eric

1998-01-01

Clay minerals contribute to the chemical composition of soil and sediment groundwaters via surface and dissolution/precipitation reactions. The understanding of those processes is still today fragmentary. In this context, our experimental purpose is to identify the contribution of each reaction in the chemical composition of water in a water/clay System. Kaolinite, illite, montmorillonite are the reference clays. After a fine mineralogical study, the exchange equilibria between K + and H + are characterised. Different exchange sites are identified and the exchange capacities and selectivity coefficients are quantified. Then, mixtures of the three clays are equilibrated with acidic and basic (I≤10 -2 M) solutions at 25 deg. C, 60 deg. C, 80 deg. C, during 320 days. The System evolution is observed by chemical analysis of the solutions and mineralogical analysis by TEM. We show that montmorillonite is unstable compared to the kaolinite/amorphous silica assemblage for solutions of pH<7. Aqueous silica is probably controlled by the kinetics of dissolution of the montmorillonite in moderate pH media. In more acidic solutions, amorphous silica precipitates. Al is under control of 'kaolinite' neo-formations. The use of the selectivity coefficients in a numerical simulation shows that K + concentration depends on exchange reactions. The pH has a more complicated evolution, which is not completely understood. This evolution depends on both exchange equilibria and organic acid occurrence. In this type of experiments, we have demonstrated that the equilibrium equations between smectite and kaolinite are inexact. The problem of the thermodynamic nature of clays remains and is not resolved by these solubility experiments. (author) [fr

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

Science.gov (United States)

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

2016-12-01

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

Survival of microorganisms in smectite clays - Implications for Martian exobiology

Science.gov (United States)

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

1992-01-01

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

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

Digital Repository Service at National Institute of Oceanography (India)

Rao, V.P.; Rao, B.R.

-Goa (93 samples) For the convenience of description, the Saurashtra-Goa region has been divided into the Saurashtra, Gulf of Cambay-Ratnagiri and Ratnagiri-Goa sectors based on variations in clay mineral abundances. The boundaries between these sectors... are approximate and variations in the mineral abundances tend to grade one to the other. Smectite is the most abundant mineral in the inner shelf sediments of all the sectors [Fig. 3(Ba), 3(Ca) and Provenance and distribution of clay minerals 1763 0 Sm*ctlt* m...

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.

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.

Clay mineral formation under oxidized conditions and implications for paleoenvironments and organic preservation on Mars.

Science.gov (United States)

Gainey, Seth R; Hausrath, Elisabeth M; Adcock, Christopher T; Tschauner, Oliver; Hurowitz, Joel A; Ehlmann, Bethany L; Xiao, Yuming; Bartlett, Courtney L

2017-11-01

Clay mineral-bearing locations have been targeted for martian exploration as potentially habitable environments and as possible repositories for the preservation of organic matter. Although organic matter has been detected at Gale Crater, Mars, its concentrations are lower than expected from meteoritic and indigenous igneous and hydrothermal reduced carbon. We conducted synthesis experiments motivated by the hypothesis that some clay mineral formation may have occurred under oxidized conditions conducive to the destruction of organics. Previous work has suggested that anoxic and/or reducing conditions are needed to synthesize the Fe-rich clay mineral nontronite at low temperatures. In contrast, our experiments demonstrated the rapid formation of Fe-rich clay minerals of variable crystallinity from aqueous Fe 3+ with small amounts of aqueous Mg 2+ . Our results suggest that Fe-rich clay minerals such as nontronite can form rapidly under oxidized conditions, which could help explain low concentrations of organics within some smectite-containing rocks or sediments on Mars.

Clay mineral formation under oxidized conditions and implications for paleoenvironments and organic preservation on Mars

Energy Technology Data Exchange (ETDEWEB)

Gainey, Seth R.; Hausrath, Elisabeth M.; Adcock, Christopher T.; Tschauner, Oliver; Hurowitz, Joel A.; Ehlmann, Bethany L.; Xiao, Yuming; Bartlett, Courtney L. (CIW); (UNLV); (CIT); (SBU)

2017-11-01

Clay mineral-bearing locations have been targeted for martian exploration as potentially habitable environments and as possible repositories for the preservation of organic matter. Although organic matter has been detected at Gale Crater, Mars, its concentrations are lower than expected from meteoritic and indigenous igneous and hydrothermal reduced carbon. We conducted synthesis experiments motivated by the hypothesis that some clay mineral formation may have occurred under oxidized conditions conducive to the destruction of organics. Previous work has suggested that anoxic and/or reducing conditions are needed to synthesize the Fe-rich clay mineral nontronite at low temperatures. In contrast, our experiments demonstrated the rapid formation of Fe-rich clay minerals of variable crystallinity from aqueous Fe3+ with small amounts of aqueous Mg2+. Our results suggest that Fe-rich clay minerals such as nontronite can form rapidly under oxidized conditions, which could help explain low concentrations of organics within some smectite-containing rocks or sediments on Mars.

Organic Control of Dioctahedral and Trioctahedral Clay Formation in an Alkaline Soil System in the Pantanal Wetland of Nhecolândia, Brazil.

Science.gov (United States)

Barbiero, Laurent; Berger, Gilles; Rezende Filho, Ary T; Meunier, Jean-François; Martins-Silva, Elisângela R; Furian, Sonia

2016-01-01

Recent studies have focused on the formation of authigenic clays in an alkaline soil system surrounding lakes of the Nhecolândia region, Pantanal wetland. The presence of trioctahedral Mg-smectites (stevensite and saponite types), which requires low Al and Fe contents in the soil solution for its formation, contrasts with the neoformation of dioctahedral Fe-mica (glauconite, and Fe-illite), which instead requires solutions relatively enriched in Al and Fe. This study aims to understand the conditions of co-existence of both, Mg-smectite and Fe-mica a common clay association in former or modern alkaline soil systems and sediments. The study was carried out along an alkaline soil catena representative of the region. The soil organization revealed that Mg-smectite occur in top soil close to the lake, whereas Fe-mica dominate in the clay fraction of deeper greenish horizons a few meters apart. We propose here that this spatial distribution is controlled by the lateral transfer of Fe and Al with organic ligands. Alkaline organic rich solutions (DOC up to 738 mg L-1) collected in the watertable were centrifuged and filtered through membranes of decreasing pore size (0.45 μm, 0.2 μm, 30 KDa, 10 KDa, 3 KDa) to separate colloidal and dissolved fractions. Fe, Al, Si, Mg and K were analysed for each fraction. Although the filtration had no influence on Si and K contents, almost 90% of Fe (up to 2.3 mg L-1) and Al (up to 7 mg L-1) are retained at the first cutoff threshold of 0.45μm. The treatment of the same solutions by oxygen peroxide before filtration shows that a large proportion of Fe and Al were bonded to organic colloids in alkaline soil solution at the immediate lake border, allowing Mg-smectite precipitation. The fast mineralization of the organic matter a few meters apart from the lake favors the release of Fe and Al necessary for Fe-mica neoformation. In comparison with chemical and mineralogical characteristics of alkaline environments described in the

Organic Control of Dioctahedral and Trioctahedral Clay Formation in an Alkaline Soil System in the Pantanal Wetland of Nhecolândia, Brazil

Science.gov (United States)

Meunier, Jean-François; Martins-Silva, Elisângela R.; Furian, Sonia

2016-01-01

Recent studies have focused on the formation of authigenic clays in an alkaline soil system surrounding lakes of the Nhecolândia region, Pantanal wetland. The presence of trioctahedral Mg-smectites (stevensite and saponite types), which requires low Al and Fe contents in the soil solution for its formation, contrasts with the neoformation of dioctahedral Fe-mica (glauconite, and Fe-illite), which instead requires solutions relatively enriched in Al and Fe. This study aims to understand the conditions of co-existence of both, Mg-smectite and Fe-mica a common clay association in former or modern alkaline soil systems and sediments. The study was carried out along an alkaline soil catena representative of the region. The soil organization revealed that Mg-smectite occur in top soil close to the lake, whereas Fe-mica dominate in the clay fraction of deeper greenish horizons a few meters apart. We propose here that this spatial distribution is controlled by the lateral transfer of Fe and Al with organic ligands. Alkaline organic rich solutions (DOC up to 738 mg L-1) collected in the watertable were centrifuged and filtered through membranes of decreasing pore size (0.45 μm, 0.2 μm, 30 KDa, 10 KDa, 3 KDa) to separate colloidal and dissolved fractions. Fe, Al, Si, Mg and K were analysed for each fraction. Although the filtration had no influence on Si and K contents, almost 90% of Fe (up to 2.3 mg L-1) and Al (up to 7 mg L-1) are retained at the first cutoff threshold of 0.45μm. The treatment of the same solutions by oxygen peroxide before filtration shows that a large proportion of Fe and Al were bonded to organic colloids in alkaline soil solution at the immediate lake border, allowing Mg-smectite precipitation. The fast mineralization of the organic matter a few meters apart from the lake favors the release of Fe and Al necessary for Fe-mica neoformation. In comparison with chemical and mineralogical characteristics of alkaline environments described in the

Organic Control of Dioctahedral and Trioctahedral Clay Formation in an Alkaline Soil System in the Pantanal Wetland of Nhecolândia, Brazil.

Directory of Open Access Journals (Sweden)

Laurent Barbiero

Full Text Available Recent studies have focused on the formation of authigenic clays in an alkaline soil system surrounding lakes of the Nhecolândia region, Pantanal wetland. The presence of trioctahedral Mg-smectites (stevensite and saponite types, which requires low Al and Fe contents in the soil solution for its formation, contrasts with the neoformation of dioctahedral Fe-mica (glauconite, and Fe-illite, which instead requires solutions relatively enriched in Al and Fe. This study aims to understand the conditions of co-existence of both, Mg-smectite and Fe-mica a common clay association in former or modern alkaline soil systems and sediments. The study was carried out along an alkaline soil catena representative of the region. The soil organization revealed that Mg-smectite occur in top soil close to the lake, whereas Fe-mica dominate in the clay fraction of deeper greenish horizons a few meters apart. We propose here that this spatial distribution is controlled by the lateral transfer of Fe and Al with organic ligands. Alkaline organic rich solutions (DOC up to 738 mg L-1 collected in the watertable were centrifuged and filtered through membranes of decreasing pore size (0.45 μm, 0.2 μm, 30 KDa, 10 KDa, 3 KDa to separate colloidal and dissolved fractions. Fe, Al, Si, Mg and K were analysed for each fraction. Although the filtration had no influence on Si and K contents, almost 90% of Fe (up to 2.3 mg L-1 and Al (up to 7 mg L-1 are retained at the first cutoff threshold of 0.45μm. The treatment of the same solutions by oxygen peroxide before filtration shows that a large proportion of Fe and Al were bonded to organic colloids in alkaline soil solution at the immediate lake border, allowing Mg-smectite precipitation. The fast mineralization of the organic matter a few meters apart from the lake favors the release of Fe and Al necessary for Fe-mica neoformation. In comparison with chemical and mineralogical characteristics of alkaline environments described

NMR and Electrochemical Investigation of the Transport Properties of Methanol and Water in Nafion and Clay-Nanocomposites Membranes for DMFCs

Directory of Open Access Journals (Sweden)

Vincenzo Baglio

2012-06-01

Full Text Available Water and methanol transport behavior, solvents adsorption and electrochemical properties of filler-free Nafion and nanocomposites based on two smectite clays, were investigated using impedance spectroscopy, DMFC tests and NMR methods, including spin-lattice relaxation and pulsed-gradient spin-echo (PGSE diffusion under variable temperature conditions. Synthetic (Laponite and natural (Swy-2 smectite clays, with different structural and physical parameters, were incorporated into the Nafion for the creation of exfoliated nanocomposites. Transport mechanism of water and methanol appears to be influenced from the dimensions of the dispersed platelike silicate layers as well as from their cation exchange capacity (CEC. The details of the NMR results and the effect of the methanol solution concentration are discussed. Clays particles, and in particular Swy-2, demonstrate to be a potential physical barrier for methanol cross-over, reducing the methanol diffusion with an evident blocking effect yet nevertheless ensuring a high water mobility up to 130 °C and for several hours, proving the exceptional water retention property of these materials and their possible use in the DMFCs applications. Electrochemical behavior is investigated by cell resistance and polarization measurements. From these analyses it is derived that the addition of clay materials to recast Nafion decreases the ohmic losses at high temperatures extending in this way the operating range of a direct methanol fuel cell.

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.

Mineral potential of clays that cover the gypsum deposits in Araripina-PE region

International Nuclear Information System (INIS)

Lira, B.B.; Anjos, I.F. dos; Rego, S.A.B.C.

2011-01-01

In the present work the applicability of the clays that cover the deposits of Gypsum Plaster in the region of Araripina - PE for use as the ceramic pigments and for bricks production in the red ceramic industry was analyzed. The clay minerals contained the illite, kaolinite and smectite, with high proportion of the last one. The possibility of industrial application of this mineral clay is considerable; however, the mining industries that mine and process the gypsum in the region do not take the clays into account as the potential mineral. In general, industries use the clay minerals in manufacturing processes or as key raw materials, or as the alternatives for some kinds of the chemical processing industries. This paper aims to highlight the potential of materials that cover the deposits of gypsum in reference. The material sampled from different deposit layers was characterized and the physical treatment of ore was applied. The results showed that the material analyzed can be used in various kinds of industry, such as the production of natural ceramic pigments. (author)

Effects of sand compaction pile (SCP) driving on the strength of clay outside the improved area; Sand compaction pile no dasetsu ga jiban kairyo ikigai no nendo jiban no kyodo ni oyobosu eikyo

Energy Technology Data Exchange (ETDEWEB)

Matsuda, H. [Yamaguchi University, Yamaguchi (Japan); Takahashi, S. [Ministry of Transport, Tokyo (Japan); Fujiwara, K. [Penta-Ocean Construction Co. Ltd., Tokyo (Japan); Kitayama, N. [Fukken Co. Ltd., Hiroshima (Japan)

1998-06-21

This paper describes effects of the disturbance by the sand compaction pile (SCP) driving operations on the shear strength of clay outside the improved area and the border of region affected by the SCP driving. About 1,400 soil specimens were taken before and after the SCP driving inside and outside the improved area during the foundation improvement at Tokuyama-Shimomatsu Port in Yamaguchi Prefecture. Soil test data of the specimens and strength characteristics of disturbed clay specimens were investigated through the laboratory experiments. The results obtained are as follows. According to the multi-directional simple shear test results, the shear strength immediately after the cyclic shear decreased in 10 to 30% compared with that before the cyclic shear. When recompaction was conducted before the cyclic shear, however, it increased in 50% compared with that before the cyclic shear. The strength of clay decreased by the SCP driving even outside the improved area. When the internal frictional angle of clay, friction coefficient of the improved boundary and driving depth of SCP were determined, it was possible to estimate an area affected by the SCP driving using a combined sliding plane. 21 refs., 18 figs.

Electron paramagnetic resonance studies on silver atoms and clusters in regularly interstratified clay minerals

International Nuclear Information System (INIS)

Yamada, H.; Tamura, K.; Shimomura, S.; Sadlo, J.; Turek, J.; Michalik, J.

2004-01-01

The formation and stabilization of reduced silver species in the regularly interstratified clay minerals, trioctahedral smectite/chlorite (tri-Sm/Ch) and dioctahedral smectite/mica (di-Sm/M), have been studied by electron paramagnetic resonance (EPR) spectroscopy. Both minerals loaded with Ag + cations after degassing and dehydration were γ-irradiated at 77 K and monitored by EPR as the temperature increased. Some samples were exposed to water or methanol vapor after dehydration. In both hydrated and dehydrated samples only the doublets to Ag 0 atoms were observed with no evidence of the formation of Ag clusters. However, the EPR parameter of silver atoms in both matrices are different. In tri-Sm/Ch the narrow anisotropic EPR lines overlap with the broader isotropic lines, whereas in di-Sm/M only broad lines are recorded. The hyperfine splitting - A iso (Ag 0 ) is larger in tri-Sm/Ch than in di-Sm/M. Also the stability of Ag 0 in both clay minerals is distinctly different. Ag 0 doublet in di-Sm/M disappears completely above 230 K, Whereas in tri-Sm/Ch it is still recorded at 310 K. It is proposed, basing on the EPR results that Ag 0 atoms appear at different sites in both matrices: - in tri-Sm/Ch in the middle of smectite interlayer and in hexagonal cavities in the silicate sheets of tetrahedron layer and in di-Sm.M in hexagonal cavities only. When samples had been exposed to methanol before irradiation, the silver clusters become stabilized in the interlayer sites. In tri-Sm/M matrix the silver dimer Ag 2 + formed by gamma-irradiation at 77 K is transformed to tetrameric cluster, Ag 4 + at 150 K. In di-Sm/M the radiation-induced silver agglomeration proceeds in a similar way, but with a slower rate and Ag tetramer is formed only above 190 K. In both clay minerals, Ag 4 + clusters decay above 250 K. (author)

Porosity model for simultaneous radionuclide transfer in compact clay

International Nuclear Information System (INIS)

Grambow, B.; Ribet, S.; Landesman, C.; Altman, S.

2010-01-01

Document available in extended abstract form only. Both, a mono and a dual porosity model have been developed to describe diffusion in bentonite as function of compaction, which give similar results for the diffusion coefficients. There are little advantages but more computation time for the dual porosity model compared to the mono-porosity model. A significant change in paradigm has been proposed to describe diffusion accessible porosity in bentonite: Only a single micro-porosity value is considered for anions, cations and neutral species. Hydration water in the interlayers is considered as part of the solid phase and is not considered as a constitutive part of overall porosity. Since hydration water takes part of the solid phase, it is now possible to explicitly account for retention of HTO by formulating exchange between HTO and water in the interlayers. In the adaptation of the model to experimental data, a single fit constant, the geometric factor G = 7 was used, common to all ions and neutral species and for densities between 0.2 and 1.8 kg.dm -3 . The only input parameters to describe the effect of dry density on diffusion coefficients are the micro porosity (total porosity minus interlayer porosity) and the hydration numbers of exchanging cations in the interlayers, both of which can be measured by independent means (DRX, water sorption isotherms). The modelling of simultaneous mass transfer of HTO, Cs, Br and Ni has been undertaken. From the results apparent diffusion coefficients were obtained. Effective diffusion coefficients can of course only be compared to literature data if the the same porosity hypothesis is used for Da-De conversion as used in literature (total porosity for anions and HTO, micro-porosity for anions). Then, the calculated apparent diffusion coefficients for HTO match closely the measured values in the mentioned density range. Considering large experimental data uncertainty the agreement between anion diffusion data and calculations

The physical properties and compaction characteristics of swelling soils

International Nuclear Information System (INIS)

Komine, Hideo; Ogata, Nobuhide

1990-01-01

Expansive soils have recently attracted increasing attention as the back filling material for the repositories of high level nuclear wastes or as the material for improving extremely soft grounds. However, since very little has been known concerning the physical and mechanical properties of such materials, it is necessary to clarify the swelling, compaction and thermal characteristics of expansive soils. For this purpose, various kinds of index tests and a series of static compaction tests were performed using several kinds of swelling soils in order to investigate the relationship between the fundamental physical properties and the compaction characteristics. Since the ordinary testing method stipulated in JIS is difficult to perform for such expansive soils, the new method was proposed to obtained the reliable values of specific gravity, grain size distribution and liquid/plastic limits. By this method, some representative values were presented for various kinds of clay including bentonite. As the results of static compaction tests, the compaction characteristics of clay were strongly dependent on the plastic limit of clay. The maximum dry density and optimum water content were strongly dependent on both plastic limit and compaction pressure. (K.I.)

Numerical simulation of mechanical compaction of deepwater shallow sediments

Science.gov (United States)

Sun, Jin; Wu, Shiguo; Deng, Jingen; Lin, Hai; Zhang, Hanyu; Wang, Jiliang; Gao, Jinwei

2018-02-01

To study the compaction law and overpressure evolution in deepwater shallow sediments, a large-strain compaction model that considers material nonlinearity and moving boundary is formulated. The model considers the dependence of permeability and material properties on void ratio. The modified Cam-Clay model is selected as the constitutive relations of the sediments, and the deactivation/reactivation method is used to capture the moving top surface during the deposition process. A one-dimensional model is used to study the compaction law of the shallow sediments. Results show that the settlement of the shallow sediments is large under their own weight during compaction. The void ratio decreases strictly with burial depth and decreases more quickly near the seafloor than in the deeper layers. The generation of abnormal pressure in the shallow flow sands is closely related to the compaction law of shallow sediments. The two main factors that affect the generation of overpressure in the sands are deposition rate and permeability of overlying clay sediments. Overpressure increases with an increase in deposition rate and a decrease in the permeability of the overlying clay sediment. Moreover, an upper limit for the overpressure exists. A two-dimensional model is used to study the differential compaction of the shallow sediments. The pore pressure will still increase due to the inflow of the pore fluid from the neighboring clay sediment even though the deposition process is interrupted.

Geochemical Investigation of Clay Minerals in Marte, Borno State, Nigeria

Directory of Open Access Journals (Sweden)

F. D. Adams

2017-10-01

Full Text Available Clay deposit collected from various locations in Marte (Northern Borno, were studied to determine their physical and chemical characteristics in order to evaluate their suitability for industrial uses. Major and trace element analyses were carried out on clay samples using Inductively Couple Plasma-Optical Emission Spectrometry (ICP-OES and X- Ray Fluorescence (XRF. The result of the chemical analysis of the ten (10 samples collected showed significant amounts of SiO2 and Al2O3. Silica content ranges from 51.48 to 62.44 % while alumina varies from 12.49 to 19.00 %. The calcium oxide ranges from 1.17 to 3.39 %, Na2O ranges from 1.1 to 8.61 %, K2O from 1.54 to 3.66 %, MgO varies from 0.04 to0.14 %, Fe2O3 varies from 0.3 to 2.7 % and MnO ranges from 0.01 to 1.03 %. The result showed that the clays are mainly smectite with quartz and felspar as the main non-clay minerals. Generally, the geochemical results of the samples do not meet the standard for industrial utilization when compared to the Industrial specifications. However, for industrial utilization, some of the clay samples may be used after necessary beneficiations.

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

Science.gov (United States)

Cai, G.

2013-12-01

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

Column treatment of brewery wastewater using clay fortified with stone-pebbles

International Nuclear Information System (INIS)

Oladoja, N.A.; Ademoroti, C.M.A.; Idiaghe, J.A.; Oketola, A.A.

2006-01-01

The study aimed at providing a low-cost treatment for brewery wastewater, which was achieved by mixing clay with stone-pebbles to improve the low permeability of water through clay beds. The combination (clay/stone-pebbles) was used in columns for the treatment of brewery wastewater. The crystal chemistry of the clay samples was studied using X-ray diffractometer. Three principal clay minerals (kaolin, illite and smectite) were detected in the samples. Atomic absorption spectrophotometer was used to study the geochemistry of the clay samples. The results of the geochemical studies showed that all the samples were hydrated aluminosilicates. Performance efficiency studies were conducted to determine the best combination ratio of clay to stone-pebbles, which showed that combination ratio 3:1 (clay/stone pebbles, w/w) performed better. The flow-rate studies showed that brewery wastewater had longer residence time in non fortified clay than in fortified clay. The flow-rate of the wastewater in the percolating media varied from one medium to another. Two modes of treatment (batch and continuous) were used. The effluent passed through the continuous treatment mode had better quality characteristics as compared with the effluent passed through the batch treatment mode. The effect of repeated use of the fortified column on the performance efficiency was also studied. The pH, total solids, and the chemical oxygen demand (COD) of the effluent was monitored over time. The results of the COD monitored over time were analysed using breakthrough curves. The different columns were found to have different bed volumes at both the break through and exhaustion points. (author)

Diffusion of strongly sorbing cations (60Co and 152Eu) in compacted Febex bentonite

International Nuclear Information System (INIS)

Garcia-Gutierrez, M.; Missana, T.; Alonso, U.; Mingarro, M.; Cormenzana, J.L.

2010-01-01

Document available in extended abstract form only. Compacted bentonite is used as an engineered barrier in high-level radioactive waste (HLRW) repositories because is a swelling clay of very low permeability and high sorption capability for many solutes. The transport of radionuclides through compacted bentonite is a diffusion-controlled process retarded by sorption. Performance assessment calculations of a repository need diffusion coefficients data of relevant radionuclides. Several studies on diffusion behaviour of neutral, anionic and weakly sorbing elements on clay exist while very few studies are available for moderately sorbing elements, and almost no studies for Eu, a highly sorbing element are reported. In this study, diffusion experiments with strongly sorbing radionuclides, as 60 Co and 152 Eu, have been performed through compacted FEBEX bentonite. Diffusion essays with these strongly sorbing radionuclides are not straightforward to carry out because they are very time consuming essays, but also because sorption on the diffusion cells, tubing, filters and reservoirs, typically used in the classical through-diffusion or in-diffusion methods make hard the interpretation of the experimental results and the calculation of the diffusion coefficients. FEBEX bentonite was selected as Spanish reference buffer materials, and used in many national and international projects. The clay comes from the Cortijo de Archidona deposit (Almeria, Spain), and has a smectite content greater than 90% (93 ± 2%), with quartz (2 ± 1%), plagioclase (3 ± 1%), cristobalite (2 ± 1%), potassic feldspar, calcite, and trydimite as accessory minerals. The specific weight of the FEBEX bentonite is 2.7 g/cm 3 . Diffusion experiments were performed using the instantaneous plane source method. In this setup, a paper filter tagged with a tracer is introduced between two compacted tablets, avoiding contact between the tracer and the experimental vessels. The tracer can diffuse into both

Use of x-ray radiographic methods in the study of clay liners

International Nuclear Information System (INIS)

Malone, P.G.; May, J.H.; Brown, K.W.; Thomas, J.C.

1986-01-01

X-ray radiography has been widely used in soil investigation to study the distribution of layers in soil cores and the effects of changing conditions (loading or impact) on soil structure. X-ray radiographic techniques also can be useful in studying clays or clay soils used in liners. Laboratory investigations were undertaken to demonstrate that X-ray radiographic techniques could be used to detect density and soil structure changes that usually accompany variations in hydraulic conductivity of clay liners. An example of a real-time test of a simulated bentonite and sand, liner attacked with acid lead nitrate and examples of radiographic examination of clay soil (non-calcareous smectite) samples that have been permeated by lead acetate or lead nitrate are presented. The changes in density and structure can be related to changes observed in hydraulic conductivity during permeation. X-ray radiography easily can be applied to field samples of soil or clay liner materials to detect density and structural changes that occur as the liner and permeating fluid interact. X-ray techniques have applications in both understanding failure mechanisms and forecasting liner performance

Clay particles as binder for earth buildings materials: a fresh look into rheology of dense clay suspensions

Science.gov (United States)

Landrou, Gnanli; Brumaud, Coralie; Habert, Guillaume

2017-06-01

In the ceramic industry and in many sectors, clay minerals are widely used. In earthen construction technique, clay plays a crucial role in the processing. The purpose of this research is to understand and modify the clay properties in earth material to propose an innovative strategy to develop a castable earth-based material. To do so, we focused on the modification of clay properties at fresh state with inorganic additives. As the rheological behaviour of clays is controlled by their surface charge, the addition of phosphate anion allows discussing deep the rheology of concentrated clay suspensions. We highlighted the thixotropic and shear thickening behaviour of a dispersed kaolinite clay suspensions. Indeed, by adding sodium hexametaphosphate the workability of clay paste increases and the behaviour is stable during time after a certain shear is applied. Moreover, we stress that the aging and the shift in critical strain in clay system are due to the re-arrangement of clay suspension and a decrease of deformation during time. The understanding of both effect: thixotropy and aging are crucial for better processing of clay-based material and for self-compacting clay concrete. Yet, studies need to pursue to better understand the mechanism.

Hydraulic conductivity of compacted clay frozen and thawed in situ

International Nuclear Information System (INIS)

Benson, C.H.; Othman, M.A.

1993-01-01

A large specimen of compacted clay (diameter = 298 mm; thickness = 914 mm) was subjected to freeze-thaw in the field for 60 days. Afterward, the hydraulic conductivity was measured. The hydraulic conductivity of the entire specimen remained essentially unchanged, but increases in hydraulic conductivity of 1.5-2 orders of magnitude were observed above the freezing plane. The increase in hydraulic conductivity was highest at the top of the specimen and decreased with depth. Changes in hydraulic conductivity also occurred at depths 150 mm below the freezing plane, where desiccation occurred because of water redistribution. Numerous horizontal and vertical cracks formed in the soil mass. Dissection of the sample after permeation revealed that the cracks were laden with water. Cracking was greatest at the surface and became less frequent with depth. For depths greater than 150 mm below the freezing plane, cracking was absent. The frequency of cracks is consistent with principles of mechanistic models of soil freezing. The results of laboratory tests were used to predict the hydraulic conductivity of the large specimen. Tests were conducted on specimens subjected to various freeze-thaw cycles, temperature gradients, and states of stress. It was found that the predicted hydraulic conductivities were lower than those measured on the large specimen, but they closely resembled the trend in hydraulic conductivity with depth

The effects of waste leachates on the hydraulic conductivity of natural clays

Energy Technology Data Exchange (ETDEWEB)

Fernandez, F

1989-01-01

Sanitary land filling remains a viable alternative for disposal of the ever increasing volumes of municipal solid waste. Current landfill design practice requires the presence of a clay barrier (liner) that may consist of either a natural stratum or compacted clay borrow. The liner acts as a hydraulic barrier to control the flux of contaminants from the waste into the adjacent groundwater. In order to do this clay liners are required to have low hydraulic conductivity, k (typically 10{sup {minus}8} cm/s) that shall not increase during exposure to waste leachate. This thesis reports the assessment of compatibility between natural clays from Sarnia, Ontario, and various leachates ranging from municipal solid waste leachate to concentrated organic solvents. The studies were performed using specially designed fixed-ring permeameters that allowed controlling confining effective stresses, volume changes in the soil specimen and chemistry of the influent and effluent permeants. The Sarnia clays appeared to be compatible with domestic waste leachate, showing slight reductions in k. Extensive retardation of potassium from the leachate required long testing periods (up to twelve pore volumes) before the soils were deemed to be in chemical equilibrium. Concentrated, water-soluble organics (ethanol and dioxane) increased the hydraulic conductivity of compacted clays by 100 to 1,000-fold, thus destroying their effectiveness as liners. Water-compacted clays appeared remarkably resistant to penetration by concentrated hydrophobic solvents such as cyclohexane. Large hydraulic gradients (up to {approximately}900) were required to produce breakthrough along compaction induced fractures. However, alcohols and surfactants can facilitate the entry of hydrophobic liquids into the double layers causing large increased in k.

Lime as an Anti-Plasticizer for Self-Compacting Clay Concrete

Directory of Open Access Journals (Sweden)

Gnanli Landrou

2016-04-01

Full Text Available This paper focuses on the modification of clay properties with inorganic additives to deflocculate and flocculate inorganic soil for the development of a material that would be as easy to use as the current concrete products, but with a much lower environmental impact. Considering that the rheological behaviour of clays is controlled by their surface charge, we first introduce potential determining ions to deflocculate the clay particles and to reduce the yield stress of the earth material. Their efficiency is characterized using zeta potential measurements and rheological tests. We then achieve the flocculation of clay particles by using natural minerals that slowly dissolve in the interstitial liquid and ultimately precipitate calcium silicate hydrate (C–S–H. The precipitation products are identified by X-ray diffraction and the consequences of this delayed precipitation are followed by oscillatory rheometric measurements. Finally, it is suggested that in this process, C–S–H precipitation is not used as a binding vector but as an anti-plasticizer that removes the inorganic dispersant additives.

LABORATORY TESTING OF BENTONITE CLAYS FOR LANDFILL DESIGN AND CONSTRUCTION

Directory of Open Access Journals (Sweden)

Biljana Kovačević Zelić

2007-12-01

Full Text Available Top and bottom liners are one of the key construction elements in every landfill. They are usually made as compacted clay liners (CCLs composed of several layers of compacted clay with strictly defined properties or by the use of alternative materials such as: GCL – geosynthetic clay liner, BES – bentonite enhanced soils or bentonite/polymer mixtures. Following the state of the art experiences in the world, GCLs are used in Croatian landfills for several years, as well. Depending upon the location and the obeying function, GCLs have to fulfill certain conditions. A legislated compatibility criterion has to be proven by various laboratory tests. In the paper are presented the results of direct shear and chemical compatibility tests of GCLs as well as the results of permeability measurement of kaolin clay (the paper is published in Croatian .

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.)

Catsius Clay Project. Calculation and Testing of Behaviour of Unsaturated Clay as Barrier in Radioactive Waste Repositories. Stage 2: Validation Exercises at Laboratory scale

Energy Technology Data Exchange (ETDEWEB)

Alonso, E E; Alcoverro, J

1999-07-01

Stage 2 of CATSIUS CLAY Project: Validation Exercises at Laboratory Scale includes two Benchmarks, Benchmark 2.1: Oedometer Suction Controlled Tests on Samples of compacted Boom Clay and Benchmark 2.2: Small Scale Weltting-Heating Test on Compacted Bentonite. BM 2.1 had two parts: BM 2.1A (volumetric deformation upon wetting-drying cycles) and BM 2.1 B (swelling pressure test). In BM 2.1A, participants were asked to model the results of a series of five tests on samples of compacted Boom clay. In BM 2.1B, a swelling pressure test in which suction, vertical and horizontal stresses were monitored, was proposed as a blind exercise. Participants were asked to use, without further changes, the models calibrated in BM 2.1A. This exercise provides an evaluation of the capabilities of current mechanical constitutive models for unsaturated clay behaviour. It was found that, even if a calibration exercise on the basis of known experimental data is satisfactory, blind predictions of tests involving different paths may prove difficult. The test set up for BM 2.2 consisted of a stainless stell cell filled with highly expansive compacted bentonite (S2 clay from Almeria, Spain). The clay was subjected to a simultaneous central heating and a progressive water inflow through the botton plate. Temperature at various locations within the sample and the boundary radial stress were monitored throughout the test. Water content distribution was also measured at the end of the experiment. Predictions for this benchmark required the solution of field equations for flow, temperature distribution and mechanical analysis. Model parameters were derived from the extensive set of available experiments on this clay. Comparison between model predictions and measurements revealed the significance of water transport in vapour phase, the difficulties to predict boundary stresses and the general good agreement between measured and calculated temperatures. The report provides a detailed accojnt of the

Catsius Clay Project. Calculation and Testing of Behaviour of Unsaturated Clay as Barrier in Radioactive Waste Repositories. Stage 2: Validation Exercises at Laboratory scale

International Nuclear Information System (INIS)

Alonso, E. E.; Alcoverro, J.

1999-01-01

Stage 2 of CATSIUS CLAY Project: Validation Exercises at Laboratory Scale includes two Benchmarks, Benchmark 2.1: Oedometer Suction Controlled Tests on Samples of compacted Boom Clay and Benchmark 2.2: Small Scale Weltting-Heating Test on Compacted Bentonite. BM 2.1 had two parts: BM 2.1A (volumetric deformation upon wetting-drying cycles) and BM 2.1 B (swelling pressure test). In BM 2.1A, participants were asked to model the results of a series of five tests on samples of compacted Boom clay. In BM 2.1B, a swelling pressure test in which suction, vertical and horizontal stresses were monitored, was proposed as a blind exercise. Participants were asked to use, without further changes, the models calibrated in BM 2.1A. This exercise provides an evaluation of the capabilities of current mechanical constitutive models for unsaturated clay behaviour. It was found that, even if a calibration exercise on the basis of known experimental data is satisfactory, blind predictions of tests involving different paths may prove difficult. The test set up for BM 2.2 consisted of a stainless stell cell filled with highly expansive compacted bentonite (S2 clay from Almeria, Spain). The clay was subjected to a simultaneous central heating and a progressive water inflow through the botton plate. Temperature at various locations within the sample and the boundary radial stress were monitored throughout the test. Water content distribution was also measured at the end of the experiment. Predictions for this benchmark required the solution of field equations for flow, temperature distribution and mechanical analysis. Model parameters were derived from the extensive set of available experiments on this clay. Comparison between model predictions and measurements revealed the significance of water transport in vapour phase, the difficulties to predict boundary stresses and the general good agreement between measured and calculated temperatures. The report provides a detailed accojnt of the

Effect of chemical retention on anionic species diffusion in compacted clays

International Nuclear Information System (INIS)

Bazer-Bachi, Frederic

2005-01-01

Anionic radioisotopes are of particular importance within the framework of the calculated health risk associated with high-level and long-lived intermediate-level underground radioactive waste disposal. Therefore, the objective of this work is the construction of a transport model coupled with chemistry in order to quantify the behaviour of anionic solutes in the Callovo-Oxfordian (CO_x) argillite, the argillaceous host rock of the ANDRA Meuse/Haute-Marne underground laboratory. An experimental methodology was defined to characterize this migration, several experimental methods being implemented: batch experiments, laboratory columns and through-diffusion cells. The study of the diffusion of the non-sorbing anionic tracer "3"6Cl"- highlighted the fact that, due to anionic exclusion, anions only had access to a part of the porosity. The retention of "3"5SO_4"2"- and "1"2"5I- on CO_x argillite was then characterized, quantified by batch experiments and confirmed by other experimental methods. Nevertheless, their migration was less retarded than expected by a model based on batch experiments and on "3"6Cl"- diffusive data. This difference was explained by anion exclusion which reduced sorption site accessibility. Thus, the intensity of this phenomenon has to be considered to model anion migration in compacted clays. (author) [fr

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

Science.gov (United States)

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

2015-03-01

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

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.

Study of the structural modifications in activated clays by Moessbauer spectroscopy and X-ray diffractometry

Energy Technology Data Exchange (ETDEWEB)

Huaypar, Yezena, E-mail: yhuaypar@yahoo.es; Bravo, Jorge, E-mail: jbravoc@unmsm.edu.pe [Universidad Nacional Mayor de San Marcos, Facultad de Ciencias Fisicas (Peru); Gutarra, Abel; Gabriel, Erika [Universidad Nacional de Ingenieria, Facultad de Ciencias (Peru)

2007-02-15

In this work we study the changes induced on the structure of a smectite clay by chemical acid activation with HCl using X-ray diffractometry (XRD) and transmission Moessbauer spectroscopy (TMS) techniques. By XRD we were able to determine the mineralogical composition of the clay samples and measure the changes in the interplanar distance associated to the structural modifications in the clays. We measured a reduction in the interplanar distance and reflection intensity as the acid concentration in the activation process increased. TMS allowed us identify and characterize the structural sites occupied by ferric and ferrous iron cations. In addition, we were able to monitor the effects caused by the chemical acid activation on the valence state of the iron cations that occupy these structural sites in the clay. For the treatment at low acid concentration, keeping time and temperature of activation constant, our results showed a strong effect on the ferrous and ferric iron sites, reducing and increasing their adsorption relative areas respectively.

Study of the structural modifications in activated clays by Moessbauer spectroscopy and X-ray diffractometry

International Nuclear Information System (INIS)

Huaypar, Yezena; Bravo, Jorge; Gutarra, Abel; Gabriel, Erika

2007-01-01

In this work we study the changes induced on the structure of a smectite clay by chemical acid activation with HCl using X-ray diffractometry (XRD) and transmission Moessbauer spectroscopy (TMS) techniques. By XRD we were able to determine the mineralogical composition of the clay samples and measure the changes in the interplanar distance associated to the structural modifications in the clays. We measured a reduction in the interplanar distance and reflection intensity as the acid concentration in the activation process increased. TMS allowed us identify and characterize the structural sites occupied by ferric and ferrous iron cations. In addition, we were able to monitor the effects caused by the chemical acid activation on the valence state of the iron cations that occupy these structural sites in the clay. For the treatment at low acid concentration, keeping time and temperature of activation constant, our results showed a strong effect on the ferrous and ferric iron sites, reducing and increasing their adsorption relative areas respectively.

Clay particles as binder for earth buildings materials: a fresh look into rheology of dense clay suspensions

Directory of Open Access Journals (Sweden)

Landrou Gnanli

2017-01-01

Full Text Available In the ceramic industry and in many sectors, clay minerals are widely used. In earthen construction technique, clay plays a crucial role in the processing. The purpose of this research is to understand and modify the clay properties in earth material to propose an innovative strategy to develop a castable earth-based material. To do so, we focused on the modification of clay properties at fresh state with inorganic additives. As the rheological behaviour of clays is controlled by their surface charge, the addition of phosphate anion allows discussing deep the rheology of concentrated clay suspensions. We highlighted the thixotropic and shear thickening behaviour of a dispersed kaolinite clay suspensions. Indeed, by adding sodium hexametaphosphate the workability of clay paste increases and the behaviour is stable during time after a certain shear is applied. Moreover, we stress that the aging and the shift in critical strain in clay system are due to the re-arrangement of clay suspension and a decrease of deformation during time. The understanding of both effect: thixotropy and aging are crucial for better processing of clay-based material and for self-compacting clay concrete. Yet, studies need to pursue to better understand the mechanism.

Accurate control testing for clay liner permeability

Energy Technology Data Exchange (ETDEWEB)

Mitchell, R J

1991-08-01

Two series of centrifuge tests were carried out to evaluate the use of centrifuge modelling as a method of accurate control testing of clay liner permeability. The first series used a large 3 m radius geotechnical centrifuge and the second series a small 0.5 m radius machine built specifically for research on clay liners. Two permeability cells were fabricated in order to provide direct data comparisons between the two methods of permeability testing. In both cases, the centrifuge method proved to be effective and efficient, and was found to be free of both the technical difficulties and leakage risks normally associated with laboratory permeability testing of fine grained soils. Two materials were tested, a consolidated kaolin clay having an average permeability coefficient of 1.2{times}10{sup -9} m/s and a compacted illite clay having a permeability coefficient of 2.0{times}10{sup -11} m/s. Four additional tests were carried out to demonstrate that the 0.5 m radius centrifuge could be used for linear performance modelling to evaluate factors such as volumetric water content, compaction method and density, leachate compatibility and other construction effects on liner leakage. The main advantages of centrifuge testing of clay liners are rapid and accurate evaluation of hydraulic properties and realistic stress modelling for performance evaluations. 8 refs., 12 figs., 7 tabs.

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.

[Effects of Long-term Implementation of the Flow-Sediment Regulation Scheme on Grain and Clay Compositions of Inshore Sediments in the Yellow River Estuary].

Science.gov (United States)

Wang, Miao-miao; Sun, Zhi-gao; Lu, Xiao-ning; Wang, Wei; Wang, Chuan-yuan

2015-04-01

Based on the laser particle size and X-ray diffraction (XRD) analysis, 28 sediment samples collected from the inshore region of the Yellow River estuary in October 2013 were determined to discuss the influence of long-term implementation of the flow-sediment regulation scheme (FSRS, initiated in 2002) on the distributions of grain size and clay components (smectite, illite, kaolinite and chlorite) in sediments. Results showed that, after the FSRS was implemented for more than 10 years, although the proportion of sand in inshore sediments of the Yellow River estuary was higher (average value, 23.5%) than those in sediments of the Bohai Sea and the Yellow River, silt was predominated (average value, 59.1%) and clay components were relatively low (average value, 17.4%). The clay components in sediments of the inshore region in the Yellow River estuary were close with those in the Yellow River. The situation was greatly changed due to the implementation of FSRS since 2002, and the clay components were in the order of illite > smectite > chlorite > kaolinite. This study also indicated that, compared to large-scale investigation in Bohai Sea, the local study on the inshore region of the Yellow River estuary was more favorable for revealing the effects of long-term implementation of the FSRS on sedimentation environment of the Yellow River estuary.

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

Hydration of swelling clays: multi-scale sequence of hydration and determination of macroscopic energies from microscopic properties

International Nuclear Information System (INIS)

Salles, F.

2006-10-01

smectites: it is responsible for the structure of porosity in a dry state and of the evolution of the pore sizes as a function of the RH and it modifies the hydration sequence by its mobility inside the interlayer space. The distinction between various types of water in the smectite structure is also achieved by thermo-poro-metry at different RH: water bound to the cations and surfaces, water structured by porosity and free water. This distinction is important to understand the behaviour of smectite and in particular the diffusion properties in clayey materials. The importance of the cation nature is also highlighted by the energetic model. Electrostatic calculations using the PACHA formalism (Electronegativities Equalization method) show that, for the small cations, the hydration energy of the layers is predominant. To obtain these results, we determine the surface enthalpies for the dry state, which show a coherent evolution as a function of the cation partial charge with the increase of pore sizes and thus with particle sizes. Then, using a theoretical model, we calculated swelling energies, surface hydration energies and cation hydration energies. The behaviour of mixed purified clay displays a behaviour closer to that of a calcic clay for the experiments carried out, in contradiction with the fact that the Na cation is the most abundant. This observation implies results on the clay properties, different from that expected for hydration properties, swelling and interlayer cation mobility within the framework of the radioactive waste. (author)

Structural characterization of bentonite clays for utilization as nanofillers in nanocomposites; Caracterizacao estrutural de argilas bentoniticas para utilizacao como nanocargas

Energy Technology Data Exchange (ETDEWEB)

Oliveira, Carlos Ivan Ribeiro de; Rocha, Marisa Cristina Guimares; Vogas, Arthur Considera, E-mail: carlosivanr@gmail.com [Universidade do Estado do Rio de Janeiro (UERJ), Nova Friburgo, RJ (Brazil). Instituto Politecnico; Silva, Ana Lucia Nazareth da [Universidade Federal do Rio de Janeiro (IMA/UFRJ), RJ (Brazil). Instituto de Macromoleculas Professora Eloisa Mano; Bertolino, Luiz Carlos [Centro de Tecnologia Mineral (CETEM/MCTI), Rio de Janeiro, RJ (Brazil)

2014-07-01

Clays of different composition have been used in the development of polymer nanocomposites. However, the utilization of bentonite clays has been emphasized in Brazil, mainly due to their availability.The best known and studied deposits of bentonite clays are located in the state of Paraiba. However, these deposits are becoming exhausted after decades of exploitation. In this context, the aim of this work is to proceed the physical-mineralogical characterization of bentonite clays recently discovered in Cubati, PB. In order to achieve this objective, the samples underwent a particle size classification step and were characterized by X-ray fluorescence, X-ray diffraction, infrared spectroscopy, thermal analysis and scanning electron microscopy. Results of X-ray diffraction showed that the samples are composed of smectite, and kaolinite and quartz. The characterization of the samples by FTIR confirmed these results. Results of chemical analysis showed that the clays have predominantly different exchangeable cations. (author)

Basic research of developed the evaluation model of buffer material

International Nuclear Information System (INIS)

Kawamura, K.; Ichikawa, Y.; Suzuki, S.; Shibata, M.; Sato, H.; Ueno, K.

2003-07-01

For the better understanding of mass transport property of the buffer material of the high-level radioactive waste disposal, the unified method of molecular dynamics simulations (MD) and homogenization analysis (HA) method and model were developed. Interaction of atoms and multi-body potential model which needed in MD calculation was improved. Na-smectite surface and water molecule system were calculated by MD, the structure of water molecule, viscosity of water nearby the Na-smectite surface and distribution of diffusion coefficient of which were estimated. According to the results of the MD calculation, first water layer adjacent to Na-smectite surface was structured, and about 1nm thick diffuse layer was observed in which viscosity of water in higher than ordinary water. Structure modeling for Na-smectite including edge was also discussed. The HA analysis needs the results of the micro-scale properties from MD calculation and the microstructure of the field, i.e. microstructure of buffer material. Microstructure of compacted Na-smectite were studied by Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM) and X-ray diffraction (XRD). On the basis of the simplified observation results, the equation was formulated that the external pore size was expressed as a function of the number of clay layers and dry density. Using MD simulation results and pore structure model, diffusion coefficient of water molecule in compacted Na-smectite were calculated by the unified MD/HA analysis method. For this analysis Multi-scale HA method which can handle for porous media consists of various scale particles was developed. Calculated diffusion coefficient of water was in agreement with the results of diffusion experiment of triturated water (HTO). Regarding solute diffusion through compacted bentonite, experimental results are accumulated and discussed. Modelling frameworks for diffusion and sorption of ion were also developed. (author)

Use of clays as buffers in radioactive repositories

International Nuclear Information System (INIS)

Pusch, R.

1983-05-01

For use as canister overpack, highly compacted bentonite is superior to illite and any reasonably montmorillonite-rich bentonite will do which is not too rich in sulphur. The organic content should be low and heat treatment may be required to bring this content down to an acceptable level. Heating to slightly more than 400degreeC does not affect the physical properties of neither montmorillonite, nor illite to a significant extent. Bentonite is also very suitable for use as sealing plugs in the form of highly compacted blocks. For use as backfill in tunnels and shafts, illitic clay is a candidate material which can be compacted on site to the rather high density that is required. Where a swelling capacity is needed, such as in the top part of tunnels, bentonite-based backfills are suitable and if Na saturated clay is used the bentoite fraction can be kept low. Thus, a 10 percent content of Na bentonite by weight should generally be sufficient for a well compacted mixture with respect to the required hydraulic conductivity, while a 20-30 percent content may be needed to arrive at a sufficient swelling power. The choice of a suitable clay material requires that the substance be properly characterized and tested. It is concluded that rather rigorous analyses are necessary as concerns overpacks, including mineralogical and granulometrical tests and the determination of the swelling characteristics as well as of certain chemical features. For backfills and for the current checking of all sorts of clay for use as buffer materials, the natural water content, the liquid limit and the swelling ability have to be determined, since they are the fingerprints of this type of soil. (author)

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.)

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.

Development of a simple model for the simultaneous degradation of concrete and clay in contact

International Nuclear Information System (INIS)

Neretnieks, Ivars

2014-01-01

Highlights: • The rate at which concrete and bentonite in contact degrade each other is modelled. • In portlandite and bentonite receding degradation fronts develop and move. • The model results compare well with results from complex models. - Abstract: In nuclear waste repositories concrete and bentonite are used, sometimes in contact with each other. The rate of mutual degradation of concrete and bentonite by alkaline fluids from concrete is explored using a simple model. The model considers dissolution of a soluble compound in the concrete (e.g. portlandite), which is gradually dissolved as the solubilised hydroxide and the cation(s) diffuse towards and into the bentonite in which smectite degrades by interaction with the solutes. Accounting for only the diffusion resistances in concrete and clay, the solubility of the concrete compound and the hydroxide consumption capacity of the smectite, results in a very simple analytical model. The model is tested against several published modelling results that account for reaction kinetics, reactive surface, and equilibrium data for tens to many tens of different secondary minerals. In the models that include several specified minerals often assumptions need to be made on which minerals can form. This introduces subjective assumptions. The degradation rates using the simple model are within the range of results obtained by the complex models. In the studies of the data used in these models it was found that the uncertainties in thermodynamic data are considerable and can give contradictory information on under what conditions smectite degrades. Some smectite models and thermodynamic data suggest that smectite will transform to other minerals spontaneously if there were no kinetic restrictions

Determination of membrane behaviour during transport of pollutants n clay barriers

International Nuclear Information System (INIS)

Musso, M.; Pejon, O.

2010-01-01

The study of the transport of contaminants in clay barriers had a extensive development in environmental geotechnics. The most studied transport processes are solutes by advection - dispersion and diffusion generated by hydraulic and chemical gradients respectively. Greater attention should be given to the chemical - osmotic flow and behavior membrane clay barriers, since in one case the water molecules move through the existence of a chemical gradient and on the other the means totally or partially inhibits the passage of solutes. The team developed to measure these processes was constructed based on items international literature and performance was verified using two types of materials KCl solution . One material is a bentonite geocomposite (Geosynthetic Clay Liner GCL ) similar to that used by other researchers. The other material is a soil barrier compacted clay (Compacted Clay Liner CCL) Fm. Corumbataí (Permian), belonging to the Paraná basin in the state of Sao Paulo, Brazil . The results show the proper performance of the equipment built . Osmotic pressure generation and membrane performance was verified for both samples. Further corroborated influence of the type of clay mineral in the osmotic pressure generated value and membrane behavior

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.

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.)

Clarification of olive mill and winery wastewater by means of clay-polymer nanocomposites.

Science.gov (United States)

Rytwo, Giora; Lavi, Roy; Rytwo, Yuval; Monchase, Hila; Dultz, Stefan; König, Tom N

2013-01-01

Highly polluted effluents from olive mills and wineries, among others, are unsuitable for discharge into standard sewage-treatment plants due to the large amounts of organic and suspended matter. Efficiency of all management practices for such effluents depends on an effective pretreatment that lowers the amount of suspended solids. Such pretreatments are usually based on three separate stages, taking a total of 2 to 6h: coagulation-neutralizing the colloids, flocculation-aggregating the colloids into larger particles, and separation via filtration or decanting. Previous studies have presented the concept of coagoflocculation based on the use of clay-polymer nanocomposites. This process adds a higher density clay particle to the flocs, accelerating the process to between 15 and 60 min. This study examined suitable nanocomposites based on different clays and polymers. The charge of the compounds increased proportionally to the polymer-to-clay ratio. X-ray diffraction (XRD) measurements indicated that in sepiolite-based nanocomposites there is no change in the structure of the mineral, whereas in smectite-based nanocomposites, the polymer intercalates between the clay layers and increases the spacing depending on the polymer-to-clay ratio. Efficiency of the coagoflocculation process was studied with a dispersion analyzer. Sequential addition of olive mill or winery effluents with a boosting dose of nanocomposites may yield a very efficient and rapid clarification pretreatment. Copyright © 2012 Elsevier B.V. All rights reserved.

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.

Is montmorillonite-rich clay of MX-80 type the ideal buffer for isolation of HLW?

International Nuclear Information System (INIS)

Pusch, R.

1999-12-01

Four commercial clays, saponite, mixed-layer smectite-mica, kaolinite, and palygorskite, have been examined as possible alternatives to MX-80 buffer. General estimates based on the microstructural constitution and hydration potential as well as actual laboratory testing show that except for normally graded kaolinite, they would all serve acceptably in a repository. MX-80 is, however, superior with respect to hydraulic conductivity and retardation of diffusive transport of relevant cations and, like saponite and palygorskite, it has a high swelling pressure, that may in fact be too high. The mixed-layer clay is less but sufficiently expandable and is concluded to have better thermal and rheological properties as well as gas release capacity. It is hence the number one competitor to MX-80

Is montmorillonite-rich clay of MX-80 type the ideal buffer for isolation of HLW?

Energy Technology Data Exchange (ETDEWEB)

Pusch, R [Geodevelopment AB, Lund (Sweden)

1999-12-01

Four commercial clays, saponite, mixed-layer smectite-mica, kaolinite, and palygorskite, have been examined as possible alternatives to MX-80 buffer. General estimates based on the microstructural constitution and hydration potential as well as actual laboratory testing show that except for normally graded kaolinite, they would all serve acceptably in a repository. MX-80 is, however, superior with respect to hydraulic conductivity and retardation of diffusive transport of relevant cations and, like saponite and palygorskite, it has a high swelling pressure, that may in fact be too high. The mixed-layer clay is less but sufficiently expandable and is concluded to have better thermal and rheological properties as well as gas release capacity. It is hence the number one competitor to MX-80.

Discrete analysis of clay layer tensile strength

International Nuclear Information System (INIS)

Le, T.N.H.; Ple, O.; Villard, P.; Gourc, J.P.

2010-01-01

The Discrete Element Method is used to investigate the tensile behaviour and cracks mechanisms of a clay material submitted to bending loading. It is the case of compacted clay liners in landfill cap cover application. Such as the soil tested in this study is plastic clay, the distinct elements model was calibrated with previous data results by taking into account cohesive properties. Various contact and cohesion laws are tested to show that the numerical model is able to reproduce the failure mechanism. Numerical results are extending to simulate a landfill cap cover and comparing to experimental large scale field bending tests achieved in a real site of storage. (authors)

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

Caracterização da argila bentonítica para utilização na remoção de chumbo de efluentes sintéticos Characterization of smectite clays for application in the removal of lead from synthetic effluents

Directory of Open Access Journals (Sweden)

M. G. F. Rodrigues

2004-09-01

Full Text Available Este artigo tem como principal objetivo caracterizar argilas esmectíticas chocolate de Boa-Vista, Estado da Paraíba (Brasil na sua forma natural e após tratamento químico, visando a sua utilização na remoção de Pb2+ de efluentes sintéticos. Os métodos de caracterização utilizados foram fluorescência de raios X, difração de raios X, microscopia eletrônica de varredura e espectroscopia de raios X por energia dispersiva. Neste trabalho foi estabelecido o procedimento para remoção de Pb2+ a partir de um efluente inorgânico sintético, utilizando argila natural. Para avaliar a influência dos principais parâmetros, como pH, tratamento e granulometria da argila sobre a remoção do Pb2+, foi utilizado o planejamento fatorial e os melhores resultados obtidos foram: pH 4,5, granulometria entre 35 e 48 mesh, e argila natural.The main objective of this paper is to characterize the Chocolate smectite clays of Boa-Vista, State of Paraíba (Brazil, in their natural form, and after chemical treatment for their application in the removal of Pb2+ from synthetic effluents. The following methods were used: X-ray fluorescence, X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. In is work the procedures for Pb2+ removal from a synthetic inorganic effluent using a natural clay were established. To evaluate the influence of the main parameters, such as pH, clay treatment and granulometry, on Pb2+ removal, factorial planning was used and the best results obtained were pH 4.5, granulometry in the range of 35 to 48 mesh and natural clay.

Impact of the changes in the chemical composition of pore water on chemical and physical stability of natural clays. A review of natural cases and related laboratory experiments and the ideas on natural analogues for bentonite erosion/non-erosion

Energy Technology Data Exchange (ETDEWEB)

Puura, Erik (Eridicon OUe, Tartu (Estonia)); Kirsimaee, Kalle (Univ. of Tartu, Inst. of Ecology and Earth Sciences, Tartu (Estonia))

2010-01-15

A scientific literature survey was compiled with the specific objective to find information for smectite mobilization and/or retention in natural clay formations caused by contact with water with low ionic concentrations such as can be expected during and after an ice age. Evidence was sought if smectite particles are lost from the clay to the water and if accessory minerals that remain could form a growing filter slowing down or stopping further loss of smectite. Bentonites are present in geological layers for hundreds of millions of years. There is limited exchange with surrounding layers, eg K transported into the bentonite layer from surrounding shale layers leading to the increased illite % in smectite-illite of the bentonite. Another process is silicification of surrounding layers leading to lowered permeability of surrounding rocks. Geological literature data on historical bentonites do not consider colloid formation in low ionic strength water as relevant mechanism for smectite mobilization. However there are no studied cases where this could be a relevant mechanism (as proposed by colloid release scenario). Soil researchers have studied the mechanism of colloid release in laboratory experiments and have found that there has to be an abrupt change in infiltrating water quality leading to 'osmotic explosion'. Clogging the pores in the lower part of the soil column has followed, leading to dramatic decrease of hydraulic conductivity in vertical profile and increased surface runoff. So, although limited, there are literature evidences of clay colloids release from bentonites/smectites caused by low-ionic circumneutral water. The geological settings to look for natural analogue studies include (1) Bentonite/smectite similar to what is used in repository. (2) Water similar to the composition of glacial meltwater. (3) Scenario similar to what is proposed in the bentonite erosion project. The problem related to the study of historical bentonite profiles

Impact of the changes in the chemical composition of pore water on chemical and physical stability of natural clays. A review of natural cases and related laboratory experiments and the ideas on natural analogues for bentonite erosion/non-erosion

International Nuclear Information System (INIS)

Puura, Erik; Kirsimaee, Kalle

2010-01-01

A scientific literature survey was compiled with the specific objective to find information for smectite mobilization and/or retention in natural clay formations caused by contact with water with low ionic concentrations such as can be expected during and after an ice age. Evidence was sought if smectite particles are lost from the clay to the water and if accessory minerals that remain could form a growing filter slowing down or stopping further loss of smectite. Bentonites are present in geological layers for hundreds of millions of years. There is limited exchange with surrounding layers, eg K transported into the bentonite layer from surrounding shale layers leading to the increased illite % in smectite-illite of the bentonite. Another process is silicification of surrounding layers leading to lowered permeability of surrounding rocks. Geological literature data on historical bentonites do not consider colloid formation in low ionic strength water as relevant mechanism for smectite mobilization. However there are no studied cases where this could be a relevant mechanism (as proposed by colloid release scenario). Soil researchers have studied the mechanism of colloid release in laboratory experiments and have found that there has to be an abrupt change in infiltrating water quality leading to 'osmotic explosion'. Clogging the pores in the lower part of the soil column has followed, leading to dramatic decrease of hydraulic conductivity in vertical profile and increased surface runoff. So, although limited, there are literature evidences of clay colloids release from bentonites/smectites caused by low-ionic circumneutral water. The geological settings to look for natural analogue studies include (1) Bentonite/smectite similar to what is used in repository. (2) Water similar to the composition of glacial meltwater. (3) Scenario similar to what is proposed in the bentonite erosion project. The problem related to the study of historical bentonite profiles is the

Clay minerals related to the circulation of geothermal fluids in boreholes at Rittershoffen (Alsace, France)

Science.gov (United States)

Vidal, Jeanne; Patrier, Patricia; Genter, Albert; Beaufort, Daniel; Dezayes, Chrystel; Glaas, Carole; Lerouge, Catherine; Sanjuan, Bernard

2018-01-01

Two geothermal wells, GRT-1 and GRT-2, were drilled into the granite at Rittershoffen (Alsace, France) in the Upper Rhine Graben to exploit geothermal resources at the sediment-basement interface. Brine circulation occurs in a permeable fracture network and leads to hydrothermal alteration of the host rocks. The goal of the study was to characterize the petrography and mineralogy of the altered rocks with respect to the permeable fracture zones in the granitic basement. As clay minerals are highly reactive to hydrothermal alteration, they can be used as indicators of present-day and paleo-circulation systems. Special attention has been paid to the textural, structural and chemical properties of these minerals. The fine-grained clay fraction (smectite ( 10% smectite) provide a promising guide for identifying the fracture zones that control the present-day circulation of geothermal fluids in the Rittershoffen wells. However, multistage paleo-circulation systems could lead to an abundance of heterogeneous and fine-grained illitic minerals that could plug the fracture system. The permeability of fracture zones in the GRT-1 well was likely reduced because of an intense illitization, and the well was stimulated. The occurrence of chlorite in the permeable fracture zones of GRT-2 is indicative of less intense illitization, and the natural permeability is much higher in GRT-2 than in GRT-1.

Hydraulic performance of compacted clay liners under simulated daily thermal cycles.

Science.gov (United States)

Aldaeef, A A; Rayhani, M T

2015-10-01

Compacted clay liners (CCLs) are commonly used as hydraulic barriers in several landfill applications to isolate contaminants from the surrounding environment and minimize the escape of leachate from the landfill. Prior to waste placement in landfills, CCLs are often exposed to temperature fluctuations which can affect the hydraulic performance of the liner. Experimental research was carried out to evaluate the effects of daily thermal cycles on the hydraulic performance of CCLs under simulated landfill conditions. Hydraulic conductivity tests were conducted on different soil specimens after being exposed to various thermal and dehydration cycles. An increase in the CCL hydraulic conductivity of up to one order of magnitude was recorded after 30 thermal cycles for soils with low plasticity index (PI = 9.5%). However, medium (PI = 25%) and high (PI = 37.2%) plasticity soils did not show significant hydraulic deviation due to their self-healing potential. Overlaying the CCL with a cover layer minimized the effects of daily thermal cycles, and maintained stable hydraulic performance in the CCLs even after exposure to 60 thermal cycles. Wet-dry cycles had a significant impact on the hydraulic aspect of low plasticity CCLs. However, medium and high plasticity CCLs maintained constant hydraulic performance throughout the test intervals. The study underscores the importance of protecting the CCL from exposure to atmosphere through covering it by a layer of geomembrane or an interim soil layer. Copyright © 2015 Elsevier Ltd. All rights reserved.

Influence of Olea europea L. and Ficus Carrica L. fine root activity on the K biodisponibility and clay mineralogy of the rhizosphere

Directory of Open Access Journals (Sweden)

Sophia Mouas-Bourbia

2015-10-01

Full Text Available The objective of this study was to compare the effect of fine root activity of Olea europea L. and Ficus carrica L. of soil in its immediate vicinity (in the so-called rhizosphere zone. The study was conducted on two stations in Northern Algeria: Guendoul and Bouira. Olea europea L. and Ficus carrica L. roots significantly modified some chemical properties of rhizosphere soil. Increases of soil carbon, KNH4+ and KHNO3- were observed in the Olea europea L. and Ficus carrica L rhizosphere soil at both stations. Bulk and rhizosphere soil clay mineralogy was similar. Interstratified illite-smectite, smectite-illite and illite were predominant in the clay fraction. Chlorite and kaolinite were less represented. The decomposition of XRD diffractograms of two soil clay fractions using the Decomp program revealed that Olea europea L. roots promote nK+ storage in interlayer position. Indeed, the lower abscissa position of the gravity center (cg of the X-ray patterns, the peak displacement of clays populations PCI, I/S, S/I toward illite peak position indicates an increase of “illite-like” layer content in the vicinity of Olea europea L. roots. Olea europea L. roots appeared to have more influence on the rhizosphere soil than Ficus carrica L. roots probably because of its higher root biomass and the greater activity of the tree in winter (contrary to Ficus Carrica L., Olea europea L. keep their leaves in winter. The two species underground activity seems to be well reflected in their respective rhizosphere.