Clays are used for long for the control of soil and water pollution as they are inexpensive natural materials with a high adsorption capacity for a wide range of pollutants. However their use as components in engineered waste containment systems is often limited when it comes to the control of organic contaminants as the clays are organophobic in nature. Organic modification of the natural clays, by replacing the exchangeable inorganic cations of clay with organic cations, can facilitate to overcome this limitation. On modification the clays become organophilic which can enhance their sorption capacities for organic contaminants. There are several ways by which natural clays can be modified with organic cations. The type of clay, the type of modifier, and the extent of modification play an important role in enhancing the organic sorption capacity. Sorption of organics by the organo clays depends on a large extent on the specific interactions that occur between modified clay and the organic contaminants. The interaction between the clay and the contaminants depend on the physico-chemical properties of modified clay and nature of organic contaminants. Since the properties of natural clays are likely to be altered by the modification a detailed study has been taken up to understand the physico chemical characteristics of organo clays which essentially control their organic sorption efficiency. Apart from bentonite which is widely used as a component of barrier systems, the characteristics of other types of clays on organic modification also needs to be assessed as they can also form part of the containment system frequently. Further the modification of clays is bound to bring in significant changes on their geotechnical properties which may affect their performance when used as barrier material. Only limited research has been conducted in the past on the geotechnical characteristics of organo clay. Therefore extensive studies have been carried out on the evaluation of the geotechnical characteristics of organo clays and the effect of organic modification on important geotechnical properties. Since very often inorganic and organic contaminants can occur simultaneously, admixtures of bentonite and organically modified clays needs to be employed as a part of clay barrier system. Moreover clay alone is very rarely used as component of barrier systems and significant portion of barrier material usually include non clay fraction. Hence studies have been carried out on mixtures containing different proportions of organo clay and bentonite and sand – organo clay / bentonite to evaluate their geotechnical behavior. Important geotechnical properties considered for detailed studies are swelling, compressibility and permeability. Detailed studies on the organic sorption capacities of different organically modified and unmodified clays, mixtures of bentonite and organo clays have also been conducted. The results of studies conducted are presented in 9 chapters. The organization of the thesis is as follows: Chapter 1 gives detailed background information on the sources and hazards of organic contaminants, inadequacy of conventional barriers to contain organic contaminants, the need for modification of natural clays, and the methods for organic modification of clays. Extensive review of literature has highlighted the need to study the effect of organic modification on the physico chemical and geotechnical properties of clay in different pore fluids. Organo clays were prepared using a wide range of clays viz., two types of bentonites of different regions, black cotton clay and commercially available kaolinite with a long chain organic cation. The extent of organic modification was varied by varying the amount of organic cation exchanged as function of total cation exchange capacity of the clays. Detailed physico chemical characterization of these modified and unmodified clays has been carried out with the help of different state of art techniques. The Chapter 2 brings out the effect of modification, role of type of clay and type of modifiers on the characteristics of organo clays by comparing the physico chemical characteristics of different modified and unmodified clays. The organic modification of montmorillonitc clays with long chain organic cation is found to increase their lattice spacing with the amount of modification whereas no such increase was observed on modification of kaolinitic clays even when all the exchangeable inorganic cations were replaced with the organic cations. The XRD studies revealed that the intercalated organic cations of the modified montmorillonite clays assumed mono, bi, or pseudo tri layer depending on the extent of organic modification. Irrespective of the type of clay modified or the modifier used all the organo clays tend to become e hydrophobic, and the surface area of the clays was found to decrease. A comparison of the characteristics of clays modified in laboratory with organo clay obtained commercially revealed that the organic modification was more effective for the organo clay prepared in the laboratory. As the index properties of all clays are generally correlated with their geotechnical characteristics, the effect of organic modification on the index properties of clays was studied. Chapter 3 presents the effect of organic modification on the plasticity and free swell behavior of clays. The index properties of commercially available organo clay and the unmodified clay used for its preparation were evaluated with pore fluids of different dielectric constants. Fluids of varied dielectric constants were chosen as it is one of the important characteristics to understand the behavior of clays. It was observed that the organic modification of clays reduced the plasticity of the clays in water and increased the plasticity in less polar liquids like ethanol. As the organo clays are more hydrophobic, the water holding capacity and plasticity in water is decreased to a large extent. The free swell behavior of clays in different pore fluids were assessed in terms of the modified free swell index. It was found that trend of variation of free swell index with dielectric constant for modified and unmodified clays, as in the case of plasticity is quite opposite. The swell volume of the modified clays was observed to be controlled more by surface solvation than by the development of the inter particle repulsive forces and diffused double layer. The effect of incorporating unmodified bentonite with organically modified clay on the index properties of bentonite has also been studied. The results suggested that the effect of organo clay addition to bentonite was always to reduce its plasticity and free swell in water. However in pore fluids of lower dielectric an increase in the plasticity and free swell was observed with increasing organo clay content in the mixture. This owes to the fact that organo clays can interact strongly with organic fluids, changing its fabric arrangement. As reported from literature it is well established that the swell of clays has conflicting role on the stability and permeability of clay barriers. Swelling of clays is liable to cause a reduction in hydraulic conductivity, enhance the retention times of contaminants and attribute self healing capacity to the liners. Even though extensive studies have been carried out on the swell behaviour and mechanism of swell of unmodified clays, no systematic research is reported on the effect of organic modification on swell behavior of clays especially in the presence of different pore fluids. Chapter 4 describes the results of oedometer swell tests carried out on compacted samples of modified, unmodified clays and organo clay –bentonite mixture in the presence of different pore fluids such as water, ethanol, and their mixture and carbon tetra chloride. Swelling ability of the unmodified clays was not completely suppressed even in the presence of low polar miscible organic liquids as they were molded at water contents corresponding to the optimum moisture content (OMC). The order of the swelling for the unmodified bentonites was in the order of the polarity of the pore fluids used, while the order is reversed upon organic modification of clays. The mechanism of swell in the case of organo clays in organic liquids was related to the solvation of the organic liquid by the intercalated organic cations. And unlike in the case of unmodified clays, the organo clays showed “solvent induced swelling”. Both organic modification and addition of organo clay to bentonite resulted in the suppression of the swelling of clays in water irrespective of the type of modifier or the extent of organic modification. The Chapter 5 gives a detailed account of the compressibility behavior of organically modified clays and its mixtures with bentonite when the samples were molded with water at their respective OMC and later inundated with different fluids. Significant differences were observed on the compressibility of modified and unmodified clay in different fluids. Organic modification of clays reduced their affinity to water and resulted in lowering the compressibility. However there was an increased compressibility for the organo clays when the samples were inundated with non polar liquids and the compression of the organo clay in non polar fluid was not influenced by the nature of clay nor by the type of modifier. The compressibility of the mixtures of organo clay and bentonite in non polar liquids was generally controlled by the organo clay component of the mixture. Organo clays can be recommended as additives in bentonite slurries for construction of slurry walls in order to improve the containment of organics. But the amendment should not compromise the stability and integrity of the slurry walls. Moreover the influence of addition of sorptive material like organo clay on the compressibility behavior of bentonite slurry has received little attention and needs serious consideration as the studies in the previous chapter has brought out that the compressibility of compacted bentonite reduced significantly on organic modification as well as on addition of orgno clay. The Chapter 6 deals with the compressibility behavior of slurries of unmodified bentonite, organo clay, and their mixtures molded with respective liquid limits with water and later inundated with fluids of different dielectric constants as the slurries frequently get in contact with fluids other than water during their operational life. However it was observed that the effect of polarity of the inundating liquid is masked in all the cases by the presence of large amount of initial molding water as the possible specific chemical interactions between organo clay and non polar fluids were restricted in the presence of large amount of molding water. But the slurry samples molded and inundated with non polar carbon tetra chloride showed that the organo clay samples are more compressible when molded with carbon tetrachloride. The chapter also gives a brief discussion on the effect of initial molding water content on the compressibility of organo clays and its mixtures. The compression was found to increase with increase in initial water content irrespective of the type of inundating fluid in agreement with the behavior observed in the case of unmodified clays. However the effect was less pronounced at higher applied pressures. The Chapter 7 brings out the volume change behavior of organo clay amended sand bentonite mixtures (SOB) which form potential barrier to prevent and /or remove contaminants. The compaction behavior of mixtures showed that the degree of compaction achieved was controlled mainly by the sand content and proportion of organo clay in the total fine fraction. The volume change behavior of the SOB mixtures were assessed with the help of oedometer tests conducted on mixtures compacted at OMC conditions and inundated with different fluids same as those used for the swell tests. The samples with higher sand content showed no observable swell when inundated with liquids viz., water, ethanol and their mixture as all the swollen finer particles were accommodated in the voids created by sand particles. However a high swell percentage was measured when samples with high organo clay content were inundated with carbon tetrachloride. Moreover with increased amounts of organo clay in the mix the swelling of bentonite was suppressed and the same trend continued even when the pore fluids were changed to liquids of medium polarity. The organo clays are capable of interacting strongly with non polar liquids like carbon tetra chloride, and hence an appreciable swell was noted when inundated with them especially in the case of mixtures with high organo clay content. The swell behavior of SOB mixtures with lower sand contents were controlled mostly by the interaction of the pore fluid with bentonite and organo clay, interactions between organo clay and bentonite and the polarity of the pore fluid. As the pore fluid polarity was decreased the influence of organo clay component of the mixture was more pronounced. The Chapter 8 explains the hydraulic performance of modified and unmodified clays along with that of the mixtures of organo clay with bentonite and SOB. The coefficient of permeability was calculated from the consolidation data obtained on sample molded at OMC. The permeability variations observed on changing the pore fluids were studied at each applied pressure. The hydraulic conductivity showed a decreasing trend with the increase in applied pressure for all the clays. The specific interactions of the organo clay with the pore fluids and the clay content were found to play a role in controlling the permeability. Limited tests were carried out to simulate a condition where a SOB liner is proposed as a secondary liner below a punctured geo membrane and its hydraulic performance was evaluated with diesel and water as pore fluids. The permeability coefficients with diesel as permeant were observed to decrease with increase in organo clay content of the mixture irrespective of the applied pressure where as the reverse was true when permeated with water. Thus the use of SOB as secondary liner below storage tanks so as to control the transport of contaminants leaking containments systems is established. The organic sorption efficiency of the modified and unmodified clays and the mixture were evaluated in terms of removal of total organic carbon (TOC) and reduction in chemical oxygen demand (COD) of the different leachates including municipal solid waste (MSW) leachate when treated with different types of modified and unmodified clays. All the modified clays irrespective of the type of clay or the type of modifier used showed improved organic sorption capacity. The sorption of TOC was found to follow a linear sorption mechanism in the case of organo clays and the organic contaminants were partitioned on to the organic phase attached to the organo clays. The composition, age and type of leacahte played a major role in controlling the organic sorption efficiency of organo clays in the case of MSW leachates. The studies done with different mixtures of organo clay and bentonite and SOB mixtures clearly proved that the addition of organo clay always enhanced the organic sorption efficiency of the mixtures. The results are discussed in Chapter 9. The Chapter 10 highlights the major conclusions drawn from the study. The study, apart from satisfying the research zeal on understanding the behavior of organo clays, has generated important information useful for the geo environmental engineer to arrive at appropriate design of barrier systems incorporating organically modified clay, based on the characteristics of pore fluid.

Les smectites possèdent des propriétés qui en font des candidates potentielles pour constituer une des barrières pour le stockage des déchets radioactifs en milieu géologique profond : faible perméabilité, gonflement et rétention de cations. Le cœur de cette thèse est la détermination des liens existant entre les propriétés d'hydratation, de gonflement et de<br />mobilité des cations, c'est-à-dire les propriétés de confinement du matériau.<br />L'objectif est de comprendre et prédire le comportement de l'eau dans les smectites en suivant deux axes de recherche : les aspects mécanistique et énergétique de l'hydratation des smectites. Nous avons travaillé sur la montmorillonite Na-Ca contenue dans la bentonite MX80, sous forme échangée, et monoionique (saturée par des cations alcalins ou des cations Ca).<br />L'approche traverse les différentes échelles (microscopique, mésoscopique et macroscopique)<br />et conduit à étudier les différentes composantes du système (feuillet-cation-eau), en mettant en œuvre des méthodes expérimentales de manière originale (thermoporométrie et conductivité électrique pour différentes humidités relatives (HR)) et des méthodes théoriques (calculs électrostatiques).<br />En premier lieu, l'état sec est défini par ATVC (Analyse Thermique à Vitesse Contrôlée). Ensuite une caractérisation classique de la porosité de la smectite pour l'état sec est réalisée (intrusion de mercure, adsorption d'azote) et nous permet de montrer l'existence d'une mésoporosité dont le rayon évolue entre 2 et 10 nm en fonction du cation compensateur.<br />Les expériences de thermoporométrie et de conductivité pour différents états d'hydratation<br />ont permis de suivre l'augmentation des tailles de pore et de la mobilité des cations en fonction de l'hydratation. Nous mettons notamment en évidence l'existence d'un gonflement osmotique mésoscopique pour de faibles humidités relatives (environ 50-60% HR) pour les cations Li et Na. En combinant les résultats de thermoporométrie, diffraction des Rayons X et conductivité électrique, nous sommes en mesure de proposer une séquence d'hydratation complète pour chaque cation, montrant ainsi le rôle du cation compensateur dans l'hydratation de la smectite : il est responsable de la structure de la porosité à l'état sec et de l'évolution des tailles de pore en fonction de la HR et il modifie la séquence d'hydratation par sa mobilité dans l'espace interfoliaire.<br />La distinction des différents types d'eau présents dans la structure argileuse est réalisée par thermoporométrie à différentes humidités relatives : eau liée aux cations et aux surfaces, eau structurée par la porosité et eau libre. Cette distinction est importante pour comprendre le comportement de l'argile et notamment les propriétés de diffusion. <br />L'importance de la nature du cation est également mise en évidence par le modèle énergétique. Les calculs électrostatiques utilisant le formalisme PACHA (Méthode d'Egalisation des Electronégativités) montrent que, pour les petits cations, l'énergie<br />d'hydratation du cation dans la structure argileuse est prépondérante, alors que pour les gros cations, c'est l'énergie d'hydratation des feuillets qui est prépondérante. Pour obtenir ces résultats, nous avons déterminé les enthalpies de surface pour l'état sec, qui montrent une évolution cohérente, en fonction de la charge partielle du cation, avec l'augmentation de taille de pores et donc de taille de particules. Ensuite, au moyen d'un modèle théorique, nous avons<br />calculé les énergies de gonflement, les énergies d'hydratation des surfaces et des cations se trouvant dans l'espace interfoliaire.<br />Le comportement de l'argile purifiée mixte (Na/Ca) est analysé à partir des résultats obtenus pour les composés homoioniques : l'argile mixte a un comportement plus proche de celui d'une argile calcique pour les expériences réalisées, alors que le cation Na est majoritaire. Cette observation implique des résultats sur les propriétés de l'argile différents de ceux escomptés pour les propriétés d'hydratation, de gonflement et de mobilité des cations interfoliaires dans le cadre des déchets radioactifs.

The deep geological repository concept is based on “engineered barriers systems (EBS)” that are constructed in the repository and “natural barriers” provided by the surrounding geological environment. The EBS comprises of variety of sub-systems or components, such as the waste form, canister, buffer, backfill, seals, and plugs. Geological disposal is based on the concept of multiple barriers that work together to provide containment. The buffer is made up of densely compacted bentonite or bentonite-sand mix. Bentonite has both mechanical and physico-chemical functions, to fulfill as a barrier material in DGR. The bentonite buffer should hold the containers in place and prevent collapse of the excavation. A plastic deformability of the bentonite is desired to redistribute the stresses that can result from creep in the rock, and prevent transfer of excessive stresses to the canisters. The bentonite buffer must create an impermeable zone around the containers to ensure that the radionuclide released from the vitrified waste is limited by diffusive transport rather than advective transport in groundwater. Another important property of the highly compacted bentonite is its swelling potential. Its swelling potential should be as high as possible, to guarantee the sealing of any cracks occurring in the buffer material or in the storage gallery and thus ensure good imperviousness. Besides its mechanical function, bentonite buffer must sorb escaping radionuclides and thus retard their migration to the geo-environment. The bentonite buffer must retain its mechanical and physico-chemical functions over a span of several hundred thousand years to fulfill its role as a containment barrier in DGR. The bentonite buffer should maintain its physico-chemical and hydro-mechanical integrity on exposure to groundwater. Nuclear power agencies of several countries have identified suitable bentonites for use as buffer in DGR through laboratory experiments and large scale underground testing facilities. Japan has identified Kunigel VI bentonite, South Korea-Kyungju bentonite, China-GMZ bentonite, Belgium-FoCa clay, Sweden-MX-80 bentonite, Spain-FEBEX bentonite and Canada-Avonseal bentonite as candidate bentonite buffer for deep geological repository program. Bentonite from Barmer (Rajasthan State) was identified as suitable buffer for use in Indian deep geological repositories. The influence of moisture and dissolved salt migration on the physico-chemical and hydro-mechanical properties of Barmer bentonite has not been examined. The study is important to understand the clay’s behaviour under deep geological repository conditions, where, the bentonite buffer would come in contact with groundwater. Infiltration of groundwater with variable chemical composition could alter the physico-chemical and hydro-mechanical properties of the clay. The objectives of the thesis are as follows: Examine the influence of permeation of distilled water (DW) and synthetic ground water (SGW) solutions under constant volume condition on suction, physico-chemical and moisture content/dry density characteristics of compacted Barmer bentonite specimens as function of permeation period (maximum permeation period– 30 days). Examine the influence of variation in dry density and gravimetric water content as consequence of DW and SGW solution permeation on swell pressure and unconfined compression strength of Barmer bentonite specimens. Compare experimental swell pressures of re-constituted bentonite specimens with swell pressures predicted by diffuse double layer models. Examine the influence of total dissolved solids (TDS) concentration of permeating solution on the unsaturated permeability of compacted Barmer bentonite specimens. Organization of thesis: After the first introductory chapter, a detailed review of literature is performed in Chapter 2 to review the physicochemical, mineralogical and hydro-mechanical properties of bentonites identified as buffer materials for deep geological repositories of various countries. Based on current understanding and need to perform similar studies with Barmer clay, the chapter develops the scope and objectives of the study. Chapter 3 presents a detailed experimental program of the study. Chapter 4 examines the influence of permeation of distilled water (DW) and synthetic groundwater (SGW) solutions (under constant volume conditions) on the total suction of compacted bentonite specimens at two locations in the clay. The influence of variation in dry density on the moisture migration-suction inter-relations of compacted bentonite specimens is also examined. The associated changes of DW and SGW solution migration under constant volume conditions on the physico-chemical properties, water content and dry density of compacted Barmer bentonite specimens are also examined. The experimental results brought out that matric suction mainly contributed (75 to 92 %) to total suction of the permeated specimens; the permeated specimens experienced reduction in matric suction with increase in gravimetric water content from increase in degree of saturation. Osmotic suction contributed to 10 to 25 % of the total suction of the permeated specimens and was observed to increase with gravimetric water content due to solubilization of salts contained in the voids of the compacted bentonite specimens. The total suction of compacted Barmer bentonite specimen was responsive to the total dissolved solids concentration of the permeating solutions as the specimen permeated with more saline solution (higher TDS value) exhibited lesser total suction. Upon permeation with DW and SGW solutions, the CEC of bentonite was unaltered, while, pH and TDS values were affected. Softening of the bentonite clay occurred from increase in water content and existence of compression zones (material used to seal 1mm gap in relative humidity probe aperture) that in turn facilitated dissipation of swelling stress leading to reduction in dry density values. Chapter 5 examines influence of reduction in dry density and increase in water content on the swell pressure and compression strength characteristics of compacted Barmer bentonite specimens upon DW and SGW solution migration as the results could provide insight into possible deviations from the design properties upon wetting of bentonite buffer by groundwater under deep geological repository conditions. The experimental swelling pressures are also compared with those predicted by Gouy-Chapman diffuse double layer theory. The dry density of 1.6 Mg/m specimens permeated with DW and SGW solutions reduced to 1.59 to 1.36 Mg/m and water contents increased to 18.9 to 27 % on permeation with distilled water and SGW solutions for 30 days. The reductions in dry density and increase in water content caused 30 to 70 % reductions in swell pressures and 31 to 74 % decrease in unconfined compression strength values. Specimens initially compacted to dry density of 1.8 Mg/m, experienced reduction in dry density ranging from 1.79 to 1.52 Mg/m and increase in water content from 18.6 to 24.2 % on permeation of DW and SGW solutions for 30 days. These reductions in dry density and increase in water caused the swell pressures to reduce from 4 to 55 % and unconfined compressive strengths to reduce by 31 to 67 %. Comparison of swell pressures gave -8 to 127 % variations between theoretical (from DDL theory) and experimental values due to errors associated with estimation of surface area and dissolved salt concentrations in pore water. Chapter 6 examines the influence of salinity of permeating solution on the unsaturated permeability of compacted Barmer bentonite specimens. The salinity of permeants was varied by permeating distilled water (DW) and synthetic ground water solutions under constant volume conditions over maximum period of 30 days. Experimental results showed that the saturated permeability coefficients (ksat) of specimens compacted to 1.6 Mg/m, responded to variations in TDS of the permeant. Comparatively, the ksat values of specimens compacted to 1.8 Mg/mwere unaffected by variation in TDS of the permeant. Permeation of DW and SGW solutions decreased the ksat values with time from cation hydration and growth of diffuse ion layers for both, 1.6 and 1.8 Mg/mseries specimens. Increase in gravimetric water content from DW and SGW permeation increased the kunsat values of 1.6 Mg/m specimens from reduction in total suction. Re-orientation of soil structure mobilized larger kunsat values for specimens permeated with SGW solutions than DW at similar total suction. Permeation of DW and SGW solutions had lesser impact on kunsat values of the 1.8 Mg/m specimens in comparison to the 1.6 Mg/m series specimens. Further at both densities, the influence of permeation was more evident at location closer to hydration surface. Chapter 7 summarizes the main findings of this study.

Deep geological repository (DGR) for disposal of high-level radioactive waste (HLW) is designed to rely on successive superimposed barrier systems to isolate the waste from the biosphere. This multiple barrier system comprises the natural geological barrier provided by the repository host rock and its surrounding and an engineered barrier system (EBS). The EBS represents the synthetic, engineered materials placed within the natural barrier, comprising array of components such as waste form, waste canisters, buffer materials, backfill and seals. The buffer will enclose the waste canisters from all directions and act as a barrier between canisters and host rock of the repository. It is designed to stabilise the evolving thermo-hydro-mechanical-chemical stresses in the repository over a long period (nearly 1000 years) to retard radionuclides from reaching biosphere. Bentonite clay or bentonite-sand mix have been chosen as buffer materials in EBS design in various countries pursuing deep geological repository method. The bentonite buffer is the most important barrier among the other EBS components for a geological repository. The safety of repository depends to a large extent on proper functioning of buffer over a very long period of time during which it must remain physically, chemically and mineralogically stable. The long term stability of bentonite buffer depends on varying temperature and evolution of groundwater composition of host rocks in a complex way. The groundwater in the vicinity of deep crystalline rock is often characterized by high solute concentrations and the geotechnical engineering response of bentonite buffer could be affected by the dissolved salt concentration of the inflowing ground water. Also during the initial period, radiogenic heat produced in waste canisters would radiate into buffer and the heat generated would lead to drying and some shrinkage of bentonite buffer close to canister. This could alter the dry density, moisture content and in turn the hydro-mechanical properties of bentonite buffer in DGR conditions. India has variety of bentonite deposits in North-Western states of Rajasthan and Gujarat. Previous studies on Indian bentonites suggest that bentonite from Barmer district of Rajasthan (termed as Barmer-1 bentonite) is suitable to serve as buffer material in DGR conditions. Nuclear power agencies of several countries have identified suitable bentonites for use as buffer in DGR through laboratory experiments and large scale underground testing facilities. Physico-chemical, mineralogical and engineering properties of Kunigel VI, Kyungju, GMZ, FoCa clay, MX-80, FEBEX and Avonseal bentonites have been extensively studied by Japan, South Korea, China, Belgium, Sweden, Spain, Canada. It is hence essential to examine the suitability of Barmer-1 bentonite as potential buffer in DGR and compare its physico-chemical and hydromechanical properties with bentonite buffers identified by other countries. The significant factors that impact the long-term stability of bentonite buffer in DGR include variations in moisture content, dry density and pore water chemistry. With a view to address these issues, the hydromechanical response of 70 % Barmer-1 bentonite + 30 % river sand mix (termed bentonite enhanced sand, BES specimens) under varying moisture content, dry density and pore water salt concentration conditions have been examined. The broad scope of the work includes: 1) Characterise the physico-chemical and hydro-mechanical properties of Barmer-1 bentonite from Rajasthan, India and compare its properties with bentonite buffers reported in literature. 2) Examine the influence of variations in dissolved salt concentration (of infiltrating solution), dry density and moisture content of compacted BES specimens on their hydro-mechanical response; the hydro-mechanical properties include, swell pressure, soil water characteristic curve (SWCC), unsaturated hydraulic conductivity, moisture diffusivity and unconfined compression strength. Organization of thesis: After the first introductory chapter, a detailed review of literature is performed to highlight the need for detailed characterisation of physico-chemical and hydromechanical properties of Barmer-1 bentonite for its possible application in DGR in the Indian context. Further, existing literature on hydro-mechanical response of bentonite buffer to changes in physical (degree of saturation/moisture content, dry density) and physico-chemical (solute concentration in pore water) is reviewed to define the scope and objectives of the present thesis in Chapter 2. Chapter 3 presents a detailed experimental programme of the study. Chapter 4 characterises Barmer-1 bentonite for physico-chemical (cation exchange capacity, pore water salinity, exchangeable sodium percentage) and hydro-mechanical properties, such as, swell pressure, saturated permeability, soil water characteristic curve (SWCC) and unconfined compression strength. The properties of Barmer-1 bentonite are compared with bentonite buffers reported in literature and generalized equations for determining swell pressure and saturated permeability coefficient of bentonite buffers are arrived at. Chapter 5 describes a method to determine solute concentrations in the inter-lamellar and free-solutions of compacted BES (bentonite enhanced sand) specimens. The solute concentrations in micro and macro pore solutions are used to examine the role of osmotic flow on swell pressures developed by compacted BES specimens (dry density 1.50-2.00 Mg/m3) inundated with distilled water and NaCl solutions (1000-5000 mg/L). The number of hydration layers developed by the compacted BES specimens on inundation with salt solutions in constant volume swell pressure tests is controlled by cation hydration/osmotic flow. The cation hydration of specimens compacted to dry density of 2.00 Mg/m3 is mainly driven by matric suction prevailing in the clay microtructure as the number of hydration layers developed at wetting equilibrium are independent of the total dissolved solids (TDS) of the wetting solution. Consequently, the swell pressures of specimens compacted to 2.00 Mg/m3 were insensitive to the salt concentration of the inundating solution. The cation hydration of specimens compacted to dry density of 1.50 Mg/m3 is driven by both matric suction (prevailing in the clay micro-structure) and osmotic flow as the number of hydration layers developed at wetting equilibrium is sensitive to the TDS of the wetting solution. Expectedly, the swell pressures of specimens compacted to 1.50 Mg/m3 responded to changes in salt concentration of the inundating solution. The 1.75 Mg/m3 specimens show behaviour that is intermediate to the 1.50 and 2.00 Mg/m3 series specimens. Chapter 6 examines the influence of initial degree of saturation on swell pressures developed by the compacted BES specimens (dry density range: 1.40- 2.00 Mg/m3) on wetting with distilled water from micro-structural considerations. The micro-structure of the bentonite specimens are examined in the compacted and wetted states by performing X-ray diffraction measurements. The initial degree of saturation is varied by adding requisite amount of distilled water to the oven-dried BES mix and compacting the moist mixes to the desired density. The montmorillonite fraction in the BES specimens is responsible for moisture absorption during compaction and development of swell pressure in the constant volume oedometer tests. Consequently, it was considered reasonable to calculate degree of saturation based on EMDD (effective montmorillonite dry density) values and correlate the developed swell pressure values with degree of saturation of montmorillonite voids (Sr,MF). XRD measurements with compacted and wetted specimens demonstrated that if specimens of density series developed similar number of hydration layers on wetting under constant volume condition they exhibited similar swell pressures, as was the case for specimens belonging to 1.40 and 1.50 Mg/m3 series. With specimens belonging to 1.75 and 2.00 Mg/m3 series, greater number of hydration layers were developed by specimens that were less saturated initially (smaller initial Sr,MF) and consequently such specimens developed larger swell pressures. When specimens developed similar number of hydration layers in the wetted state, the compaction dry density determined the swell pressure. Chapter 7 examines the influence of salt concentration of infiltrating solution (sodium chloride concentration ranges from 1000- 5000 mg/L) on SWCC relations, unsaturated permeability and moisture diffusivity of compacted BES specimens. Analysis of the experimental and Brooks and Corey best fit plots revealed that infiltration of sodium chloride solutions had progressively lesser influence on the micro-structure and consequently on the SWCC relations with increase in dry density of the compacted specimens. The micro-structure and SWCC relations of specimens compacted to 1.50 Mg/m3 were most affected, specimens compacted to 1.75 Mg/m3 were less affected, while specimens compacted to 2.00 Mg/m3 were unaffected by infiltration of sodium chloride solutions. Variations in dry density of compacted bentonite impacts the pore space available for moisture flow, while, salinity of wetting fluid impacts the pore structure from associated physico-chemical changes in clay structure. Experimental results showed that the unsaturated permeability coefficient is insensitive to variations in dry density and solute concentration of wetting liquid, while, the effective hydraulic diffusivity is impacted by variations in these parameters. Chapter 8 summarises the major findings of the study.

Deep geological repository (DGR) for disposal of high-level radioactive waste (HLW) is designed to rely on successive superimposed barrier systems to isolate the waste from the biosphere. This multiple barrier system comprises the natural geological barrier provided by the repository host rock and its surrounding and an engineered barrier system (EBS). The EBS represents the synthetic, engineered materials placed within the natural barrier, comprising array of components such as waste form, waste canisters, buffer materials, backfill and seals. The buffer will enclose the waste canisters from all directions and act as a barrier between canisters and host rock of the repository. It is designed to stabilise the evolving thermo-hydro-mechanical-chemical stresses in the repository over a long period (nearly 1000 years) to retard radionuclides from reaching biosphere. Bentonite clay or bentonite-sand mix have been chosen as buffer materials in EBS design in various countries pursuing deep geological repository method. The bentonite buffer is the most important barrier among the other EBS components for a geological repository. The safety of repository depends to a large extent on proper functioning of buffer over a very long period of time during which it must remain physically, chemically and mineralogically stable. The long term stability of bentonite buffer depends on varying temperature and evolution of groundwater composition of host rocks in a complex way. The groundwater in the vicinity of deep crystalline rock is often characterized by high solute concentrations and the geotechnical engineering response of bentonite buffer could be affected by the dissolved salt concentration of the inflowing ground water. Also during the initial period, radiogenic heat produced in waste canisters would radiate into buffer and the heat generated would lead to drying and some shrinkage of bentonite buffer close to canister. This could alter the dry density, moisture content and in turn the hydro-mechanical properties of bentonite buffer in DGR conditions. India has variety of bentonite deposits in North-Western states of Rajasthan and Gujarat. Previous studies on Indian bentonites suggest that bentonite from Barmer district of Rajasthan (termed as Barmer-1 bentonite) is suitable to serve as buffer material in DGR conditions. Nuclear power agencies of several countries have identified suitable bentonites for use as buffer in DGR through laboratory experiments and large scale underground testing facilities. Physico-chemical, mineralogical and engineering properties of Kunigel VI, Kyungju, GMZ, FoCa clay, MX-80, FEBEX and Avonseal bentonites have been extensively studied by Japan, South Korea, China, Belgium, Sweden, Spain, Canada. It is hence essential to examine the suitability of Barmer-1 bentonite as potential buffer in DGR and compare its physico-chemical and hydromechanical properties with bentonite buffers identified by other countries. The significant factors that impact the long-term stability of bentonite buffer in DGR include variations in moisture content, dry density and pore water chemistry. With a view to address these issues, the hydromechanical response of 70 % Barmer-1 bentonite + 30 % river sand mix (termed bentonite enhanced sand, BES specimens) under varying moisture content, dry density and pore water salt concentration conditions have been examined. The broad scope of the work includes: 1) Characterise the physico-chemical and hydro-mechanical properties of Barmer-1 bentonite from Rajasthan, India and compare its properties with bentonite buffers reported in literature. 2) Examine the influence of variations in dissolved salt concentration (of infiltrating solution), dry density and moisture content of compacted BES specimens on their hydro-mechanical response; the hydro-mechanical properties include, swell pressure, soil water characteristic curve (SWCC), unsaturated hydraulic conductivity, moisture diffusivity and unconfined compression strength. Organization of thesis: After the first introductory chapter, a detailed review of literature is performed to highlight the need for detailed characterisation of physico-chemical and hydromechanical properties of Barmer-1 bentonite for its possible application in DGR in the Indian context. Further, existing literature on hydro-mechanical response of bentonite buffer to changes in physical (degree of saturation/moisture content, dry density) and physico-chemical (solute concentration in pore water) is reviewed to define the scope and objectives of the present thesis in Chapter 2. Chapter 3 presents a detailed experimental programme of the study. Chapter 4 characterises Barmer-1 bentonite for physico-chemical (cation exchange capacity, pore water salinity, exchangeable sodium percentage) and hydro-mechanical properties, such as, swell pressure, saturated permeability, soil water characteristic curve (SWCC) and unconfined compression strength. The properties of Barmer-1 bentonite are compared with bentonite buffers reported in literature and generalized equations for determining swell pressure and saturated permeability coefficient of bentonite buffers are arrived at. Chapter 5 describes a method to determine solute concentrations in the inter-lamellar and free-solutions of compacted BES (bentonite enhanced sand) specimens. The solute concentrations in micro and macro pore solutions are used to examine the role of osmotic flow on swell pressures developed by compacted BES specimens (dry density 1.50-2.00 Mg/m3) inundated with distilled water and NaCl solutions (1000-5000 mg/L). The number of hydration layers developed by the compacted BES specimens on inundation with salt solutions in constant volume swell pressure tests is controlled by cation hydration/osmotic flow. The cation hydration of specimens compacted to dry density of 2.00 Mg/m3 is mainly driven by matric suction prevailing in the clay microtructure as the number of hydration layers developed at wetting equilibrium are independent of the total dissolved solids (TDS) of the wetting solution. Consequently, the swell pressures of specimens compacted to 2.00 Mg/m3 were insensitive to the salt concentration of the inundating solution. The cation hydration of specimens compacted to dry density of 1.50 Mg/m3 is driven by both matric suction (prevailing in the clay micro-structure) and osmotic flow as the number of hydration layers developed at wetting equilibrium is sensitive to the TDS of the wetting solution. Expectedly, the swell pressures of specimens compacted to 1.50 Mg/m3 responded to changes in salt concentration of the inundating solution. The 1.75 Mg/m3 specimens show behaviour that is intermediate to the 1.50 and 2.00 Mg/m3 series specimens. Chapter 6 examines the influence of initial degree of saturation on swell pressures developed by the compacted BES specimens (dry density range: 1.40- 2.00 Mg/m3) on wetting with distilled water from micro-structural considerations. The micro-structure of the bentonite specimens are examined in the compacted and wetted states by performing X-ray diffraction measurements. The initial degree of saturation is varied by adding requisite amount of distilled water to the oven-dried BES mix and compacting the moist mixes to the desired density. The montmorillonite fraction in the BES specimens is responsible for moisture absorption during compaction and development of swell pressure in the constant volume oedometer tests. Consequently, it was considered reasonable to calculate degree of saturation based on EMDD (effective montmorillonite dry density) values and correlate the developed swell pressure values with degree of saturation of montmorillonite voids (Sr,MF). XRD measurements with compacted and wetted specimens demonstrated that if specimens of density series developed similar number of hydration layers on wetting under constant volume condition they exhibited similar swell pressures, as was the case for specimens belonging to 1.40 and 1.50 Mg/m3 series. With specimens belonging to 1.75 and 2.00 Mg/m3 series, greater number of hydration layers were developed by specimens that were less saturated initially (smaller initial Sr,MF) and consequently such specimens developed larger swell pressures. When specimens developed similar number of hydration layers in the wetted state, the compaction dry density determined the swell pressure. Chapter 7 examines the influence of salt concentration of infiltrating solution (sodium chloride concentration ranges from 1000- 5000 mg/L) on SWCC relations, unsaturated permeability and moisture diffusivity of compacted BES specimens. Analysis of the experimental and Brooks and Corey best fit plots revealed that infiltration of sodium chloride solutions had progressively lesser influence on the micro-structure and consequently on the SWCC relations with increase in dry density of the compacted specimens. The micro-structure and SWCC relations of specimens compacted to 1.50 Mg/m3 were most affected, specimens compacted to 1.75 Mg/m3 were less affected, while specimens compacted to 2.00 Mg/m3 were unaffected by infiltration of sodium chloride solutions. Variations in dry density of compacted bentonite impacts the pore space available for moisture flow, while, salinity of wetting fluid impacts the pore structure from associated physico-chemical changes in clay structure. Experimental results showed that the unsaturated permeability coefficient is insensitive to variations in dry density and solute concentration of wetting liquid, while, the effective hydraulic diffusivity is impacted by variations in these parameters. Chapter 8 summarises the major findings of the study.