Suite à une anthropisation généralisée des ressources aquatiques et des écosystèmes associés, on retrouve de nombreux contaminants chimiques organiques à l’état de traces dans l’environnement aquatique. En parallèle de ces contaminants, dans les milieux aquatiques on retrouve également des molécules rassemblées sous la dénomination « matière organique dissoute (MOD) », qui sont des mélanges complexes de molécules et macromolécules, qui peuvent s’associer à ces contaminants et influencer leur comportement et leur distribution. Les interactions entre MOD et contaminants peuvent s’avérer difficiles à étudier étant donné qu’elles sont dépendantes de nombreux facteurs tels que la nature des contaminants et de la MOD, ainsi que des paramètres physico-chimiques du milieu. L’objectif de ces travaux était donc d’étudier ces interactions. Les contaminants organiques choisis ont été les Hydrocarbures Aromatiques Polycycliques (HAP) et les substances pharmaceutiques. D’autre part, plusieurs types de MOD d’origine naturelle ou commerciale ont été utilisés. Pour étudier les interactions, plusieurs techniques analytiques ont été développées dont la micro-extraction sur phase solide couplée à la chromatographie en phase gazeuse et à la spectrométrie de masse et l’extinction de fluorescence. / In relation with a widespread human impact on aquatic resources and ecosystems, many organic chemical contaminants are present at trace levels in aquatic environments. In parallel to these contaminants, dissolved organic matter (DOM), which is composed of complex mixtures of molecules and macromolecules, is also found and could be associated with these contaminants and influence their behavior and distribution. Interactions between DOM and contaminants can be very difficult to understand because they depend on many factors such as the nature of contaminants and DOM, as well as on environmental physico-chemical parameters. The aim of this work was thus to study these interactions. Organic contaminants studied were Polycyclic Aromatic Hydrocarbons (PAHs) and pharmaceuticals. On the other hand, several types of natural and commercial DOM have been used. To study the interactions, several analytical techniques have been developed like solid phase microextraction coupled to gas chromatography and mass spectrometry and fluorescence quenching.

Une étude approfondie a été menée dans deux zones distinctes (Estarreja au Portugal, noté EST, et Casier Peyraud 6 en France, noté PEY) pour évaluer les niveaux de contamination, ainsi que leurs comportements dans des anthroposols et les risques potentiels de ces contaminants pour des organismes vivants du sol. L’objectif principal étant d’évaluer la mobilité environnementale des retardateurs de flamme bromés (RFBs) dans un écosystème terrestre, notamment vers les vers de terre (Eisenia fetida) et les plants (luzerne (Medicago sativa), cresson (Nasturtium officinale), moutarde blanche (Sinapsis alba), dans une prospective d’évaluation du risque de transferts de ces molécules.Le facteur de bioaccumulation (BAF) ainsi que les indices SET et ERITME ont été calculés. Le BAF permet de déterminer si une substance est accumulée dans un organisme donné et s’il existe un risque d’entrée et de diffusion tout au long de la chaine alimentaire. Les indices SET et ERITME permettent de classer les sites testés en fonction du transfert efficace des COs par les anthroposols aux organismes testés, et d’avoir une idée du risque potentiel pour l’écosystème. L’indice SET donne une idée globale de l’excès de transfert pour tous les contaminants dans les matrices étudiées. L’indice ERITME permet d’évaluer le risque environnemental global inhérent associé à l’excès de transfert des contaminants considérés. Compte tenu des valeurs ERITME, les matrices étudiées peuvent être classées dans un ordre de toxicité qui est aussi conforme pour l’ensemble des organismes testés (E. fetida, luzerne, cresson et moutarde). / A comprehensive study was conducted in two distinct areas (Estarreja in Portugal, noted EST, and Casier Peyraud 6 in France, noted PEY) to assess the contamination levels as well as their behavior in soils and the potential risks posed by these contaminants to soil organisms. The principal aim was to evaluate the environmental mobility of brominated flame retardants (BFRs) in a terrestrial ecosystem, namely to earthworms (Eisenia fetida) and plants (alfalfa (Medicago sativa), watercress (Nasturtium officinale) and white mustard (Sinapis alba)), concerning the BFRs transfer risk evaluation. The Bioaccumulation factor (BAF) as well as the SET and ERITME indexes were calculated. The BAF allow to determine if a substance is accumulated in a certain organism and if there exists the risk of entry and diffusion along the food chain. SET and ERITME indexes allow to rank the tested sites according to the effective OCs transfer from anthroposoils to the tested organisms and have an idea of the potential risk to the ec system. The SET index gives a global idea of the excess of transfer for all the contaminants in the studied matrices. The ERITME index allows to evaluate the possible inherent global environmental risk associated with the excess of transfer on the considered contaminants. Considering the ERITME values, the studied matrices can be classified in an apparent increasing order of toxicity that it is also in accordance with the levels of OCs found in the all the tested organisms (E. fetida, alfalfa, cress and mustard).

Condensed phase membrane introduction mass spectrometry (CP-MIMS) is a direct, in situ analysis technique that is well suited to persistent organic pollutants, pesticides, and other small molecules. In CP-MIMS, neutral analytes permeate a hollow fibre membrane, typically polydimethylsiloxane (PDMS), driven by a concentration gradient. Analytes are subsequently dissolved by a liquid (condensed) solvent acceptor phase that is continuously flowed through the membrane lumen, which finally entrains the analytes to a mass spectrometer for detection. The membrane rejects charged and particulate matrix components, therefore eliminating sample cleanup that is otherwise necessary for conventional (i.e., chromatographic) techniques. However, larger analytes may suffer from relatively lengthy response times and lower sensitivity. A heptane cosolvent was therefore doped into the PDMS membrane, resulting in a polymer inclusion membrane (PIM). Through a system coupling CP-MIMS to electrospray ionization (ESI), the use of a PIM for model compounds resulted in faster response (~3×) and improved sensitivity (~3.5×, parts per trillion level detection limits). While effective for the demonstration of the PIM, pairing ESI with CP-MIMS represents an inherent incongruity: ESI is effective for polar, hydrophilic analytes, whereas CP-MIMS (i.e., PDMS membranes) is effective for hydrophobic analytes. CP-MIMS was therefore coupled with liquid electron ionization (LEI) as a more suitable ionization strategy. In LEI, the post-membrane solvent flow is entrained at nanolitre per minute flowrates to a LEI source, where the liquid is sequentially nebulized, vaporized, and ionized. The CP-MIMS-LEI coupling was optimized for the measurements of polycyclic aromatic hydrocarbon (PAH) isomer classes from aqueous samples, demonstrating low ng/L detection limits and response times (≤1.6 min). CP-MIMS-LEI was also applied to PAH isomer classes from soil samples, demonstrating rapid sample throughput (15 samples/hr) and low μg/kg detection limits, and additionally was quantitatively comparable to conventional techniques. A similar CP-MIMS-LEI system was applied to online monitoring of catalytic oxidation and alkylation reactions, demonstrating quantitative, real-time results for harsh, complex organic reaction mixtures. A significant analytical improvement was conducted by intentionally exploiting the already present liquid acceptor phase as an in situ means of providing liquid chemical ionization (CI) reagents for improved analyte sensitivity and selectivity (i.e., CP-MIMS-LEI/CI). Acetonitrile and diethyl ether were used as a combination acceptor phase/CI reagent system (i.e., proton transfer reagents) for the direct analysis of bis(2-ethylhexyl)phthalate from house dust (6 mg/kg detection limit). CP-MIMS-LEI/CI was then applied to PAHs from soils. Using methanol and dichloromethane combination acceptor phase/CI reagents, CP-MIMS-LEI/CI was shown to quantify and resolve PAH isomers from direct soil analyses via diagnostic PAH adduct ions: [M+CH2Cl+CH3OH-HCl]+ or [M+CHCl2-HCl]+. Using these selective ions, CP-MIMS-LEI/CI was again shown to be rapid (15 soils/hr), sensitive (ng/g detection limits) and quantitatively comparable to gas chromatography-MS for PAH measurements (average percent difference of -9% across 9 PAHs in 8 soil samples). The results across this thesis present a compelling argument for direct, quantitative screening from complex samples using CP-MIMS-LEI/CI, particularly given the simple workflow and short analytical duty cycle. / Graduate

Ph. D. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / Aromatic organic contaminants are difficult to biodegrade, and thus effective green technologies are required to remove these pollutants from the ecosystem. Tetracycline antibiotic, an organic water pollutant, can be degraded by heterogeneous photocatalysis using an appropriate catalyst, with capability in converting the visible light energy into active species. The thesis focused on silver nanoparticles anchored on silver bromide (Ag/AgBr) as a plasmonic catalyst dispersed on activated carbon (ACK), were used as a photocatalyst (AABR-ACK) in tetracycline removal. The aim is to develop a catalyst that is active in low intensity visible light, whilst the addition of activated carbon will increase the light absorption and separate the charge pairs, after the photocatalyst has been excited by the visible light. The activated carbons were derived from pinecone pyrolyzed in a microwave. The pinecone mass to potassium hydroxide impregnation ratio and microwave pyrolysis time influenced the activated carbon properties. An impregnation ratio of 2.24 and microwave pyrolysis time of 16 minutes at constant microwave power of 400 W yielded the activated carbon with the best-developed porous structure and electrochemical properties. This activated carbon was used during the optimisation of the Ag/AgBr activated carbon (AABR-ACK) catalysts preparation using a thermal polyol precipitation method and response surface methodology. The most active catalyst was the AABR-ACK 11 obtained by a preparation temperature of 140 ºC, time (17.50 minutes), mass of surfactant and activated carbon (0.26 g and 0.03 g) respectively. This catalyst had an ordered nanospheres morphology, reduced electron-hole recombination rate, better electrochemical properties and exhibited enhanced activity on the tetracycline antibiotic removal in comparison to other Ag/AgBr activated carbon catalysts. A percentage degradation of 92% was obtained in 180 minutes were obtained with the AABR-ACK 11 catalyst. The photocatalyst prepared using the best activated carbon derived from pinecone developed in this study was compared to photocatalysts prepared using commercial activated carbon and biochar. The Ag/AgBr activated carbon catalysts using pinecone-derived activated carbon degraded the tetracycline to 92%, which is significantly higher than the percentage degradations (80% and 74%) for the catalyst prepared using commercial activated carbon and biochar catalysts respectively. The higher activity of the Ag/AgBr activated carbon catalysts using pinecone-derived activated carbon was due to the conductive attributes of the catalyst support for accelerated transfer of photo-induced electrons. The Ag/AgBr activated carbon catalysts using pinecone- derived activated carbon also exhibited better performance on tetracycline removal when compared to photocatalysts reported in literature. Two catalyst preparation methods, thermal polyol and deposition precipitation, were compared. The thermal polyol method yielded a more active catalyst for the degradation of the tetracycline in comparison to the deposition precipitation method. The degradation reaction conditions such as pH, light intensity and degradation temperature influenced the rate of the reaction. The highest rate of degradation was obtained at a pH of seven, white light and 40 ºC temperature. The intermediate products formed because of hydroxylation, deamination, demethylation and dehydration during the photocatalytic degradation of tetracycline antibiotics were identified using liquid chromatography mass spectrometer. Quenching experiments with hydroxyl, hole, and superoxide anion species showed that the most important radical responsible for the tetracycline degradation was the superoxide anion radical.

This thesis focuses on the synthesis and characterisation of organoclays. X-ray diffraction has been used to study the changes in the basal spacings of montmorillonite clay and surfactant-intercalated organoclays. Variation in the d-spacing was found to be a step function of the surfactant concentration. Three different molecular environments for surfactant octadecyltrimethylammonium bromide (ODTMA) within the surface-modified montmorillonite are proposed upon the basis of their different decomposition temperatures. High-resolution thermogravimetric analysis (HRTG) shows that the thermal decomposition of montmorillonite modified with ODTMA takes place in four steps attributing to dehydration of adsorbed water, dehydration of water hydrating metal cations, loss of surfactant and the loss of OH units respectively. In addition, it has shown that the decomposition procedure of DODMA and TOMA modified clays are very different from that of ODTMA modified ones. The surfactant decomposition takes place in several steps in the DODMA and TOMA modified clays while for ODTMA modified clays, it shows only one step for the decomposition of surfactant. Also TG was proved to be a useful tool to estimate the amount of surfactant within the organoclays. A model is proposed in which, up to 0.4 CEC, a surfactant monolayer is formed between the montmorillonite clay layers; up to 0.8 CEC, a lateral-bilayer arrangement is formed; and above 1.5 CEC, a pseudotrimolecular layer is formed, with excess surfactant adsorbed on the clay surface. While for dimethyldioctadecylammonium bromide (DODMA) and trioctadecylmethylammonium bromide (TOMA) modified clays, since the larger sizes of the surfactants, some layers of montmorillonite are kept unaltered because of steric effects. The configurations of surfactant within these organoclays usually take paraffin type layers. Thermal analysis also provides an indication of the thermal stability of the organoclay as shown by different starting decomposition temperatures. FTIR was used as a guide to determine the phase state of the organoclay interlayers as determined from the CH asymmetric stretching vibration of the surfactants to provide more information on surfactant configurations. It was used to study the changes in the spectra of the surfactant ODTMA upon intercalation into a sodium montmorillonite. Surfaces of montmorillonites were modified using ultrasonic and hydrothermal methods through the intercalation and adsorption of the cationic surfactant ODTMA. Changes in the surfaces and structure were characterized using electron microscopy. The ultrasonic preparation method results in a higher surfactant concentration within the montmorillonite interlayer when compared with that from the hydrothermal method. Both XRD patterns and TEM images demonstrate that SWy-2-Namontmorillonite contains superlayers. TEM images of organoclays prepared at high surfactant concentrations show alternate basal spacings between neighboring layers. SEM images show that modification with surfactant will reduce the clay particle aggregation. Organoclays prepared at low surfactant concentration display curved flakes, whereas they become flat with increasing intercalated surfactant. Fundamentally this thesis has increased the knowledge base of the structural and morphological properties of organo-montmorillonite clays. The configurations of surfactant in the organoclays have been further investigated and three different molecular environments for surfactant ODTMA within the surface-modified montmorillonite are proposed upon the basis of their different decomposition temperatures. Changes in the spectra of the surfactant upon intercalation into clay have been investigated in details. Novel surfactant-modified montmorillonite results in the formation of new nanophases with the potential for the removal of organic contaminants from aqueous media and for the removal of hydrocarbon spills on roads.

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.