Th. 3e cycle--Instrumentation phys.--Grenoble 1, 1981. N°: 134.

Th. doct.-ing.--Nancy, I.N.P.L., 1982.

Cadmium, one of the trace metals, has, in the last two to three decades, become increasingly important in both industrial and biological fields. The recognition of cadmium as a serious health hazard has led to a closer examination of its properties and biochemical effects. Cadmium, an element of ata:nic number 48, atomic weight 112.41 and valency 2, is a soft 'White lustrous metal belonging to the second sub-group of the Periodic Table. It has a boiling point of 768°c, melting point of 321°0, is remarkably volatile for a heavy metal, and exists naturaly as a mixture of eight isotopes, constituting 2 x 10-5% of the earth's crust. Extraction of cadmium is by distillation from zinc ores. The electron configuration of cadmium is 4d105s2, and it forms simple bipositive cations only. There are no ligand field stabilization effects in cadmium ions, and the stereochemistry is, therefore, determined solely by size and electrostatic and covalent bonding forces.s Cadmium chloride shows octahedral co-ordination.

Certain of these isotopes appear suitable for activation analysis by neutron or other type of bombardment, which, in the future, could provide a much more sensitive technique for determination of trace quantities of the element than the spectrographic or oolorimetrio methods currently employed. The metal tarnishes in air and burns when heated forming the oxide. It occurs naturally in small quantities associated with sine, and was discovered by Strongmeyer in 1817 as an impurity in zinc carbonate. Cadmium volatilizes before zinc during the course of preparation of the metal, and condenses as a brown oxide, which is then reduced with carbon. It forms a number of salts, the chloride and sulfate being readily available in high degree of purity.

Titanium dioxide (TiO2) photocatalysis, which can oxidise or reduce organic and inorganic pollutants, is a developing technology for water and wastewater treatment. The current work investigates the photocatalytic reduction of cadmium and selenium species as the presence of these elements in water are of environmental concern. Although TiO2 has been widely used for the photocatalytic process, its light absorption is limited to the UV region of the solar spectrum. Hence, the current project also explores the possibility to deposit cadmium selenide (CdSe) onto TiO2 to extend the photoresponse to the visible region. This study demonstrated that cadmium (Cd(II)) could be reduced to its metallic form by photocatalysis. The choice of hole scavengers and reaction pH are of importance in determining whether the photocatalytic reduction reaction will occur. It is also essential that both Cd(II) and organic additives are adsorbed on the surface of TiO2. A mechanism for cadmium photoreduction in the presence of formate as the hole scavenger was proposed. The current investigation elucidated the mechanism for the photoreduction of selenite (Se(IV)). Selenite was found to be photoreduced to its elemental form (Se(0)) as films, by direct photoreduction of Se(IV), and as discrete particles, by the reaction between Se(IV) and selenide (Se(2-)) ions. The Se(2-) ions are believed to have been generated from the 6 electron photoreduction of Se(IV) and/or the further photoreduction of the Se(0) deposits. Photocatalytic reduction reactions of Se(IV) and selenate (Se(VI)) using different commercial TiO2 materials was also studied. The current work also successfully deposited CdSe by photocatalysis using Se-TiO2 obtained from the photoreduction of Se(IV) and Se(VI). The mechanism for CdSe deposition was clarified and attributed to the reaction of Cd(II) present in the system and the Se(2-) released from the reduction of Se(0) upon further illumination. The Se??TiO2 photocatalysts obtained from the photoreduction of different selenium precursors (Se(IV) and Se(VI)) resulted in the dominance of different morphologies of the CdSe particles. This suggests a new approach to manipulate the properties of CdSe during its formation, and hence control over electrical and optical properties of this semiconductor.

Titanium dioxide (TiO2) photocatalysis, which can oxidise or reduce organic and inorganic pollutants, is a developing technology for water and wastewater treatment. The current work investigates the photocatalytic reduction of cadmium and selenium species as the presence of these elements in water are of environmental concern. Although TiO2 has been widely used for the photocatalytic process, its light absorption is limited to the UV region of the solar spectrum. Hence, the current project also explores the possibility to deposit cadmium selenide (CdSe) onto TiO2 to extend the photoresponse to the visible region. This study demonstrated that cadmium (Cd(II)) could be reduced to its metallic form by photocatalysis. The choice of hole scavengers and reaction pH are of importance in determining whether the photocatalytic reduction reaction will occur. It is also essential that both Cd(II) and organic additives are adsorbed on the surface of TiO2. A mechanism for cadmium photoreduction in the presence of formate as the hole scavenger was proposed. The current investigation elucidated the mechanism for the photoreduction of selenite (Se(IV)). Selenite was found to be photoreduced to its elemental form (Se(0)) as films, by direct photoreduction of Se(IV), and as discrete particles, by the reaction between Se(IV) and selenide (Se(2-)) ions. The Se(2-) ions are believed to have been generated from the 6 electron photoreduction of Se(IV) and/or the further photoreduction of the Se(0) deposits. Photocatalytic reduction reactions of Se(IV) and selenate (Se(VI)) using different commercial TiO2 materials was also studied. The current work also successfully deposited CdSe by photocatalysis using Se-TiO2 obtained from the photoreduction of Se(IV) and Se(VI). The mechanism for CdSe deposition was clarified and attributed to the reaction of Cd(II) present in the system and the Se(2-) released from the reduction of Se(0) upon further illumination. The Se??TiO2 photocatalysts obtained from the photoreduction of different selenium precursors (Se(IV) and Se(VI)) resulted in the dominance of different morphologies of the CdSe particles. This suggests a new approach to manipulate the properties of CdSe during its formation, and hence control over electrical and optical properties of this semiconductor.

Cadmium (Cd), a cancer-causing heavy metal ion, concentration in the environment has recently shown a rapid increase mainly as a result of human activity. Since many plants are used as medicine and food, it is crucial to investigate effects of Cd on plant growth and development. This study examines the time course and concentration-dependent effects of Cd on morphology, photosynthesis and protein profiles in hydroponically-grown bean plants (Phaseolus vulgaris). High concentrations of Cd (1000 and 100uM) induced leaf wilting and reduced both leaf growth and photosynthesis rate within 24 and 48 hours respectively. Lower concentration of 10 uM Cd showed the wilted morphology after 96 hours. In addition, the Cd-induced changes in protein profiles especially the photosynthesis and stress proteins will be discussed in relation to morphology, leaf growth and photosynthesis in bean plants.

Les activités humaines agricoles, urbaines et industrielles, sans cesse croissantes, sont à l'origine d'une contamination de notre environnement par les métaux lourds. Alors que de nombreuses molécules organiques peuvent être dégradées, les métaux lourds ne le peuvent pas et leur concentration augmente régulièrement dans les sols et les eaux. Ceci expose les plantes à des concentrations croissantes de métaux lourds. L'accumulation de métaux lourds dans les plantes présente un risque toxique pour l'Homme, car les plantes cultivées sont le point d'entrée dans la chaîne alimentaire. Par comparaison aux autres espèces, la laitue «Lactuca sativa» a tendance à présenter des teneurs élevées en cadmium, un métal lourd très toxique dont la concentration croît régulièrement dans les sols cultivés pour des raisons environnementales. En termes de sécurité alimentaire, il est donc important de produire des variétés accumulant des teneurs en cadmium réduites, et la laitue est un bon modèle pour débuter ce type d'approche. L'objectif de notre thèse était de caractériser aux niveaux physiologique, génétique, et moléculaire, les déterminants majeurs contrôlant l'accumulation du cadmium chez la laitue. Notre objectif a été décliné en différentes opérations. Tout d'abord une analyse de diversité nous a permis de décrire la capacité d'accumulation de cadmium de 18 génotypes de laitue et de sélectionner des génotypes présentant des performances extrêmes vis-à-vis du cadmium. Ainsi, des génotypes présentant des performances extrêmes du point de vue de la tolérance au cadmium, de l'accumulation de cadmium et de la capacité de translocation du cadmium des racines vers les parties aériennes ont été sélectionnés. Dans une deuxième étape, nos variétés extrêmes pour les caractères d'accumulation de cadmium et de translocation de cadmium des racines vers la partie aérienne ont été utilisées pour développer une approche physiologique. L'objectif de cette approche était de montrer l'origine de leur variabilité afin de comprendre les déterminants physiologiques contrôlant l'accumulation du cadmium chez la laitue. Dans le cadre de cette approche, des expériences d'efflux faites en utilisant du cadmium radioactif (109Cd) ont montré que la variété la moins accumulatrice de cadmium se caractérise par un efflux de cadmium marqué plus important par comparaison aux autres variétés. Cette variété possède vraisemblablement un mécanisme d'efflux plus efficace par comparaison aux autres variétés qui pourraient être le déterminant majeur permettant d'obtenir une plus faible accumulation de cadmium chez cette variété. Notre étude a permis de montrer une forte corrélation positive entre teneur en cadmium et teneur en zinc. Ce qui a permis d'émettre l'hypothèse d'un transport très associé entre le cadmium et le zinc. / Cadmium is an extremely toxic pollutant causing a great number of diseases. It is a widespread metal which concentration rises in cultivated soils, thus exposing food or feed crops to it and ultimately causing potential major sanitary problems as a consequence of its entry in the food chain. Among the vegetable species used for food, lettuce shows one of the highest capacities of accumulating cadmium. Our objectives are to characterize mechanisms controlling cadmium accumulation in this species and identify the corresponding genetic determinants, ultimately aiming at breeding lettuce for cadmium under-accumulation.A phenotypical analysis of cadmium accumulation was carried out on 18 lettuce genotypes representing the genetic diversity of the species, revealing a great variability of response, both with respect to cadmium accumulation and cadmium translocation from roots to shoot. The lettuce genotypes displayed independent variations for both traits, and also between these traits and cadmium tolerance. In contrast, a very strong positive correlation linked cadmium and zinc accumulation. Increasing calcium and iron concentration in the culture medium had a protective effect against cadmium accumulation, however this characteristic did not discriminate the lettuce genotypes presenting extreme cadmium accumulation phenotypes. Interestingly, experiments measuring 109Cd influx in roots, 109Cd efflux from roots and 109Cd translocation from roots to shoots revealed that the genotype displaying the least cadmium accumulation could be discriminated from the genotype displaying the highest one by its markedly increased ability to efflux cadmium from the roots to the culture medium. Progeny analysis from crosses between the genotypes displaying extreme performances for cadmium accumulation, cadmium translocation from roots to shoots and cadmium tolerance revealed that none of these traits was supported by a single genetic determinism. QTL mapping is under development. Surprisingly, the genetic analysis demonstrated that the ability to limit cadmium accumulation (and thus probably to increase cadmium efflux from the roots) was recessive.In conclusion, phenotypic analysis of cadmium accumulation in a large set of lettuce genotypes revealed that a major determinant limiting cadmium accumulation in these species is the ability to efflux cadmium from the root to the culture medium.

Thesis (M. Sc.)--University of Western Sydney, Hawkesbury, (1994). / Includes bibliographical references and index.

Cadmium sulfide and cadmium selenide are important materials for applications such as photoconductive cells, photovoltaic cells and other electrooptical devices. Generally, these devices use single crystals. However, reasonable efficiencies have been observed by using polycrystalline films on conducting substrates, which are easier to make and provide considerable savings on materials and energy. Polycrystalline CdS/CdSe films have been made by sputtering and solution spraying, compound evaporation, chemical vapor deposition, and many others. A recent technique involves the electrochemical deposition of CdS and CdSe from nonaqueous solvents. Preparation of these films is based upon the cathodic deposition from a nonaqueous solution of a cadmium salt and elemental sulfur and/or selenium. Although the technique is simple, no mechanistic information is known to optimize the conditions in which films of controlled stoichiometry, doping and crystallinity are made. This research has the purpose to understand the mechanism of the formation of polycrystalline films of CdS and CdSe by electrochemical deposition in dimethylsulfoxide. This approach to the problem makes use of electrochemical techniques such as rotating ring disc electrode, linear scan voltammetry, high pressure liquid chromatography coupled with ultraviolet and electrochemical detection. By the rotating ring disc electrode technique, we have studied the kinetic parameters for the reduction of sulfur, selenium, cadmium, and the electroChemical formation of CdS and CdSe for temperatures from 25 - lOO°C. The results show that rates of initie.l electron transfer for the reduction of these species are moderately rapid, and secondly, that the reverse reaction is irreversible and involves additional steps. Studies of solubility of selenium with temperature reveal that its solubility is enhanced by the addition of sulfur. Understanding the electrochemical behavior of sulfur-selenium mixtures is of great importance to produce mixed semiconductive films with more adequate bandgaps for use with solar spectrum. Electrochemistry of sulfur-selenium mixtures are no different from that of sulfur alone. High pressure liquid chromatography separations with spectroscopic and electrochemical detectors have shown that sulfur solutions contain 86 and 87 fractions which are not electrochemically active.