Spectral Reflectance Characteristics of Kimberlite Indicator Minerals and Other Selected Mineral Grains

High chromium content in kimberlite indicator minerals such as pyrope garnet and diopside is often correlated with the presence of diamonds. In this study, kimberlite indicator minerals were examined using visible light reflectance spectroscopy to determine if chromium content can be correlated with spectral absorption features. The depth of absorption features in the visible spectral region were correlated with the molecular percentage of chromium and other first series transition metal elements obtained by electron microprobe data. In the visible part of the spectrum, chromium is evident by 3 absorption features in the pyrope reflectance spectrum; one isolated and narrow feature at the wavelength 689 nm was used to correlate with the chromium mol %. The isolation of this feature in the pyrope spectra is advantageous since it is not directly affected by other proximal absorption bands that could be caused by other transition metals. Analysis of the feature indicates that as grain volume increases the depth of the absorption feature will also increase. Clustering grain volumes into fractions yields better correlation between absorption depth and mol % chromium. Other types of garnet (almandine, grossular, spessartine) and kimberlite indicator minerals (olivine, diopside, chromite, ilmenite) were analyzed to determine if other absorption features could be used to predict the proportion of specific transition metal elements. Diopside in particular illustrates the same isolated chromium absorption feature as pyrope and may indicate mol percent but needs further study with larger sample sets.

Étude de nouveaux complexes de type ansa-chromocène

Les complexes de la famille des ansa-chromocènes sont relativement peu nombreux, mais ils ont tout de même démontré des réactivités intéressantes comme la possibilité de coordonner une molécule de monoxyde de carbone au centre métallique sans être sous pression constante de gaz, ce qui n’est pas le cas pour l’homologue chromocène. L’ansa-chromocène le plus surprenant est sans doute le Me2Si(C5Me4)2Cr, car il est le seul qui ne comporte pas de ligand autre que celui de type ansa. Cependant, ce composé a été obtenu sans que le mécanisme de la réaction ne soit compris et prouvé, seul un mécanisme proposé a été publié. Au cours de cette étude, le mécanisme proposé a tout d’abord été infirmé grâce à de nombreuses expériences qui ont mené à l’élaboration d’un nouveau mécanisme. Par la suite, la réactivité du Me2Si(C5Me4)2Cr a été approfondie en le faisant réagir avec divers réactifs. Aucun produit d’addition oxydante n’a été isolé, mais la réaction avec l’isonitrile forme un complexe asymétrique avec deux isonitriles coordonnés. La détermination du moment magnétique du composé Me2Si(C5Me4)2Cr confirme la présence de deux électrons non-pairés à la température de la pièce et évoque la possibilité d’une transition à S=2 à température plus élevée. La synthèse de nouveaux complexes de type ansachromocène insaturé a été tentée avec d’autres ligands ansa, et la réaction avec [C2H4(C9H6)2]Li2 mène à un complexe dimérique avec des ligands indényles pontés.

Synthèse et caractérisation de complexes métalliques avec le ligand 2,2'-biimidazole et son dérivé 1,1'-diméthyl-2,2'-biimidazole

Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal

Relargage d’ions métalliques après l’arthroplastie de la hanche à grand diamètre avec couple de frottement métal sur métal

La dégénérescence articulaire sévère de la hanche est une pathologie fréquente et son traitement ultime est le remplacement prothétique. L’arthroplastie la plus répandue au monde est la prothèse totale de hanche (PTH) avec un couple de frottement métal-sur-polyéthylène (MPE). Cependant ce type d’intervention présente une longévité limitée à cause de l’usure de PE et ne convient pas aux patients actifs souffrant de coxarthrose sévère tôt dans leur vie. Afin de palier à ce problème, une nouvelle génération de surfaces de frottement métal-sur-métal (MM) est actuellement employée. Ces surfaces de frottement sont utilisées en PTH avec tête de 28 mm, en resurfaçage (RH) et avec la PTH à tête de grand diamètre. Alors qu’il y a beaucoup d’évidence à l’égard du bon fonctionnement des implants PTH 28 mm et du RH, les données quant aux performances in vivo des PTH MM à grand diamètre manquent. Malgré cela, ces implants sont utilisés à grande échelle. Dans un premier temps, l’objectif de ce travail de recherche était d’évaluer l’effet et de comparer les taux d’ions chrome (Cr) et cobalt (Co) chez des sujets porteurs de PTH MM à grand diamètre à ceux de 64 porteurs de RH, tous deux possédant des surfaces de frottement aux propriétés tribologiques identiques. Dans un deuxième temps, nous avons comparé les taux ioniques (Cr, Co et titane (Ti)) entre quatre PTH MM à grand diamètre provenant de fabricants différents (Zimmer, DePuy, Smith & Nephew et Biomet). Les mesures d’ions étaient effectuées dans le sang entier dans un laboratoire indépendant par la technique de spectrophotométrie de masse à haute résolution HR-ICP-MS, pour l’ensemble de ce travail de recherche. Les deux comparaisons ont démontré le rôle crucial joué par la modularité au niveau de la jonction tête-col des PTH MM à grand diamètre. En effet, des écarts considérables dans les concentrations ioniques de Co ont été retrouvés entre les RH et PTH Durom ayant un couple de frottement identique, ainsi qu’entre les 4 différents designs de PTH MM à grand diamètre comparés entre eux. La PTH MM à grand diamètre Durom était la moins favorable alors que celle de Biomet était la plus performante. Nos observations démontrent que des sources inattendues comme la jonction tête-col de certains implants PTH MM à grand diamètre peuvent contribuer au relargage ionique systémique. Une meilleure compréhension de ce phénomène est indispensable avant l’utilisation clinque de nouveaux implants de ce type.

Effet des macrophytes aquatiques sur le traitement d’eau contaminée à l’ACC et au PCP

L’objectif principal de ce projet est d’évaluer le potentiel d’un système de marais filtrants combinés pour le traitement d’un lixiviat contaminé aux agents de préservations du bois - l’arséniate de cuivre chromaté (ACC) et le pentachlorophénol (PCP) - en portant une attention particulière au rôle des plantes. Pour ce faire, une expérience en pot faisant varier la concentration d’exposition de quatre espèces de macrophyte (Typha angustifolia, Phalaris arundinacea, Phragmites australis americanus et Phragmites australis australis) a été effectuée. Le suivi de quatre marais filtrants à écoulement horizontal sous-surfacique, plantés d’une des quatre espèces de macrophyte et d’un bassin planté de saules (Salix Miyabeana SX67) a également été réalisé. La résistance des plantes au milieu contaminé, la capacité de bioaccumulation des macrophytes et les efficacités de traitement des différents systèmes ont été analysés. Nos résultats montrent que la concentration d’exposition n’influence pas la capacité des plantes à croître en milieu contaminé. Par contre, il existe une relation dose-réponse entre la concentration d’exposition et la capacité de bioaccumulation des macrophytes. Les quatre marais pilotes ont tous des efficacités de traitements supérieures à 55% en 2013 et 82% en 2014 pour les contaminants à l’étude. Le bassin de saule a la capacité théorique d’évapotranspirer jusqu’à 1200 L par jour. De plus, ses efficacités de traitements sont supérieures à 59% pour tous les composés à l’étude. L’utilisation de marais filtrants pour le traitement d’un lixiviat contaminé aux agents de préservations du bois est donc une alternative intéressante aux méthodes de traitement conventionnel.

INVESTIGATIONS ON THE RECOVERY OF TITANIUM VANADIUM AND IRON VALUES FROM THE WASTE CHILORIDE LIQUORS OF TITANIA INDUSTRY

The thesis entitled INVESTIDGATIONS ON THE RECOVERY OF TITANIUM VANADIUM AND IRON VALUES FROM THE WASTE CHILORIDE LIQUORS OF TITANIA INDUSTRY embodies the results of the investigations carried out on the solvent extraction separation of iron (III) vanadium(V) and titanium (IV) chlorides from the waste chloride liquors of titanium minerals processing industry by employing tributylphosphate (TBT) as an extractant. The objective of this study is to generate the knowledge base to achieve the recovery of iron, vanadium and titanium cvalues from multi- metal waste chloride liquors originating from ilmenite mineral beneficiation industries through selective separation and value added material development

Texture Mineralogy and Geochemistry Of Sediments From The Coastal Plains Between Kodungallur And Chellanam Central Kerala India

The present study addresses to understand the sedimentological properties of the coasts of kodungallur and chellanam, central Kerala to bring out the relationship between the textural, mineralogical and geochemical characters with that of the respective environment. The grain size study of the beach ridge sediments from different pits has been investigated at close intervals, which enables to understand the grain size variations with depth. The sediment samples from various pits of the beach ridges indicate that the sediments range primarily from medium to very fine sand, well to moderately sorted, fine to coarse skewed and leptokurtic to platykurtic. The study area is considered as a prograding coast. Variations in grain size down the pit give three phases of beach building activities i.e.; a coarsening upward sequence in the bottom layers, a fining upward in the middle and coarsening upward in the top. Beach ridges are formed by swash built sediments with cross bedding and setting lag type sediments with seaward dipping/horizontal units. Geochemical signatures in the study area have been brought out through the analysis of major and trace elements. Iron is significantly enriched and its control over many trace elements is evident. Copper, chromium, cobalt, lithium, lead and zinc show decreasing trend with depth, while sodium, potassium,strontium,nickel and organic carbon increases. The association of many trace elements with organic carbon has also been established. Dissolution of trace elements in anoxic environment, at depth and reprecipitation in the oxic layers, at near or subsurface, are the major mechanism that brought out the variation of certain environmentally sensitive elements

Surface acidity and catalytic activity of mixed Fe-Al and Cr-Al pillared montmorillonites

The incorporation of transition metal oxide pillars such as those of iron and chromium along with Al2O3, pillars within the interlayers of a montmorillonite clay is investigated. The surface acidity of these catalysts has been evaluated for the first time employing the equilibrium adsorption of an electron donor, perylene, and the results are compared with those obtained by temperature programmed desorption of ammonia. The principle is based on the ability of a catalyst surface site to accept a single electron from an electron donor like perylene to form charge transfer complexes and the amount of adsorbed species is measured quantitatively by UV-vis spectroscopy. Fina1ly, an attempt has been made to correlate the acidity determined by the two independcnt methods and the catalytic activity of present systems in the benzoylation of toluene with benzoyl chloride. Incorporation of Fe and Cr has changed the properties of AI pitlared montmorillonite. Fe pillared systems have been found to be vcry good catalysts for benzoylation reaction

Sulfated titania mediated regioselective nitration of phenol in solid state

Titania, sulfated titania and chromium loaded sulfated titania were prepared by sol–gel method and characterized using different technique. Phenol is nitrated regioselectively by nitric acid using chromium loaded sulfated titania catalysts. A remarkable ortho selectivity is observed in solid state nitration to yield exclusively ortho-nitrophenol. Compared to the conventional process, phenol nitration over solid acid catalyst is a clean and environment friendly process. Catalytic activity well correlates with the Brönsted acid sites of these catalysts.

Studies on the effect of selected metals on the productivity of two species of algae

The thesis embodies the results of a study on the variations in the parameters of productivity of two test species, a chlorophycean alga and a diatom. The chlorophycean alga Scenedesmus abundans was isolated from a fresh water pond whereas the diatom Nitzschia clausii was from the Cochin backwaters. Their growth parameters and their variations due to the effect of addition of some heavy metals have been studied. The growth parameters include biomass, production, respiration, photosynthetic pigments and end products of photosynthesis. The cell numbers were estimated by using a haemocytometer and production and respiration by oxygen light and dark technique. Spectrophotometric analysis for pigments, anthrone method for carbohydrate and heated biuret method for protein were the different methods employed in the present investigation. The present study is confined to nickel, cobalt, trivalent and hexavalent chromium. Different metals are discharged from various industries in and around Cochin. The effects of these metals individually and in combination are studied. Experiments to determine the effects of interaction of metals in combination enabled the assessment of the antagonistic and synergistic effect of metals on test species. The concentration or accumulation of metals on algae was determined by Atomic Absorption Spectrophotometry. The thesis has been divided into seven chapters. The introductory chapter explains the relevance of the present investigation. Chapter two presents the review of literature based on the work in relation to toxicity. Third chapter gives a detailed description of the material and specialized methods followed for the study. The effects of various metals selected for study - nickel, cobalt, trivalent and hexavalent chromium on the qualitative and quantitative aspects of productivity forms the subject of matter of the fourth chapter. The fifth chapter gives the impact of metals in combination on two species of algae. A general discussion and summary are included in the sixth and seventh chapters

Structural studies on some metal complexes of embelin

This thesis deals with the studies on the synthesis and characterisation of the complexes of embelin with manganese (II), cobalt(II), nickel (II), copper (II), zinc (II), cadmium (II), chromium (III), iron (III) lanthanum(III), praseodymium (III) neodymium (III) Samarium (III), gadolinium (III) dysprosium (III), yttrium (III) thorium (IV) and uranium (VI). Elemental analysis as well as spectral, thermal and magnetic data were used to ascertain the composition of the complexes and to establish the structures of the metal complexes. Wherever possible, the electronic spectra and magnetic data were used to predict the stereochemistry of the complexes.The thesis is divided into four chapters.

Waste Water Treatment Using Low Cost Natural Adsorbents

Heavy metals are major toxic pollutants with severe health effects on humans. They are released into the environment from a variety of industrial activities. Cadmium, lead, zinc, chromium and copper are the most toxic metals of widespread use in industries such as tanning, electroplating, electronic equipment manufacturing and chemical processing plants. Heavy metals contribute to a variety of adverse health environmental effects due to their acute and chronic exposure through air, water and food chain. Conventional treatment methods of metal removal are often limited by their cost and ineffectiveness at low concentrations. Adsorption, the use of inactivated biomass as adsorbents offers an attractive potential alternative to their conventional methods. Mango peel and Alisma plantago aquatica are naturally occurring and abundant biomass can offer an economical solution for metal removal.The Cd(II), Pb(II), Zn(II), Cr(III) and Cu(II) adsorption by milled adsorbents of mango peel and Alisma plantago aquatica were evaluated in batches.

“Catalysis by Nanocrystalline Ceria Modified with Transition Metals”

The objective of the present work is to improve the textural and structural properties of cerium oxide by the incorporation of transition metals as well as sulphate ions. We have incorporated tungsten, molybdenum and chromium oxide into pure as well as sulphated cerium oxide and the catalytic systems thus prepared were characterised using various techniques. lndustrially important reactions such as acetalization and deacetalization, oxidative dehydrogenation of ethylbenzene, MTBE synthesis and Beckmann rearrangement of cinnamaldoxime and salicylaldoxime have been selected for the measurement of the catalytic activity of the systems. The work is presented in eight chapters

Toxic Metal Distribution in the Core Sediment of Cochin Estuarine System (CES)

This article present the result from a study of two sediment cores collected from the environmentally distinct zones of CES. Accumulation status of five toxic metals: Cadmium (Cd), Chromium (Cr), Cobalt (Co), Copper (Cu) and Lead (Pb) were analyzed. Besides texture and CHNS were determined to understand the composition of the sediment. Enrichment Factor (EF) and Anthropogenic Factor (AF) were used to differentiate the typical metal sources. Metal enrichment in the cores revealed heavy load at the northern (NS1 ) region compared with the southern zone (SS1). Elevation of metal content in core NS1 showed the industrial input. Statistical analyses were employed to understand the origin of metals in the sediment samples. Principal Component Analysis (PCA) distinguishes the two zones with different metal accumulation capacity: highest at NS1 and lowest at SS1. Correlation analysis revealed positive significant relation only in core NS1, adhering to the exposition of the intensified industrial pollution

Studies on Landfill Leachate Transportation and Its Impact on Soil Characteristics

Leachate from an untreated landfill or landfill with damaged liners will cause the pollution of soil and ground water. Here an attempt was made to generate knowledge on concentrations of all relevant pollutants in soil due to municipal solid waste landfill leachate and its migration through soil and also to study the effect of leachate on the engineering properties of soil. To identify the pollutants in soil due to the leachate generated from municipal solid waste landfill site, a case study on an unlined municipal solid waste landfill at Kalamassery has been done. Soil samples as well as water samples were collected from the site and analysed to identify the pollutants and its effect on soil characteristics. The major chemicals in the soil were identified as Ammonia, Chloride, Nitrate, Iron, Nickel, Chromium, Cadmium etc.. Engineering properties of field soil samples show that the chemicals from the leachate of landfill may have effect on the engineering properties of soil. Laboratory experiments were formulated to model the field around an unlined MSW landfill using two different soils subjected to a synthetic leachate. The Maximum change in chemical concentration and engineering property was observed on soil samples at a radial distance of 0.2 m and at a depth of 0.3 m. The pollutant (chemicals) transport pattern through the soil was also studied using synthetic leachate. To establish the effect of pollutants (chemicals) on engineering properties of soil, experiments were conducted on two types soils treated with the synthetic chemicals at four different concentrations. Analyses were conducted after maturing periods of 7, 50, 100 and 150 days. Test soils treated with maximum chemical concentration and matured for 150 days were showing major change in the properties. To visualize the flow of pollutants through soil in a broader sense, the transportation of pollutants through soil was modeled using software ‘Visual MODFLOW’. The actual field data collected for the case study was used to calibrate the modelling and thus simulated the flow pattern of the pollutants through soil around Kalamassery municipal solid waste landfill for an extent of 4 km2. Flow was analysed for a time span of 30 years in which the landfill was closed after 20 years. The concentration of leachate beneath the landfill was observed to be reduced considerably within one year after closure of landfill and within 8 years, it gets lowered to a negligible level. As an environmensstal management measure to control the pollution through leachate, permeable reactive barriers are used as an emerging technology. Here the suitability of locally available materials like coir pith, rice husk and sugar cane bagasse were investigated as reactive media in permeable reactive barrier. The test results illustrates that, among these, coir pith was showing better performance with maximum percentage reduction in concentration of the filtrate. All these three agricultural wastes can be effectively utilized as a reactive material. This research establishes the influence of leachate of municipal solid waste landfill on the engineering properties of soil. The factors such as type of the soil, composition of leachate, infiltration rate, aquifers, ground water table etc., will have a major role on the area of influence zone of the pollutants in a landfill. Software models of the landfill area can be used to predict the extent and the time span of pollution of a landfill, by inputting the accurate field parameters and leachate characteristics. The present study throws light on the role of agro waste materials on the reduction of the pollution in leachate and thus prevents the groundwater and soil from contamination