Zinc (Zn) and cadmium (Cd) have nutrient-type vertical distributions reflecting control driven by biological uptake in surface waters and remineralization of sinking biogenic particles at depth. Both metals show strong correlations with major algal nutrients (Cd with phosphate (PO43-) and Zn with silicic acid (Si)) in the world ocean. Through their roles as micronutrients and toxins to marine phytoplankton, Zn and Cd can influence surface biological community composition. Preserved Zn and Cd records have been employed as proxies to gain insight into nutrient distributions, circulation, and organic carbon export in the paleocean. A thorough and mechanistic understanding of the biogeochemical cycling of Zn and Cd is necessary for accurate paleoceanographic reconstructions as well as predicting alterations in metal supply to the modern surface ocean and its impacts on primary productivity due to oceanic changes. My dissertation aims to further this understanding through an investigation of Zn and Cd distributions in the subarctic northeast Pacific through samples collected along the Line P transect. A major focus of this dissertation was identifying and characterizing depletions of metals in O2-depleted waters relative to global and basin scale metal:macronutrient correlations. Dissolved Cd profiles from the subarctic northeast Pacific and the eastern North Atlantic show a deficit of Cd relative to regional Cd:PO43- relationships. Particulate Cd and Cd stable isotopes (ε112/110Cd) from low-O2 North Atlantic waters and published sedimentary data from the subarctic northeast Pacific point to a previously undocumented water-column metal removal process acting in O2-depleted waters. Metal sulphide formation, likely in association with particulate microenvironments, can explain the observed deficits. Other metals with similar sulphide coordination chemistry should also form metal sulphides if this process is occurring. Dissolved Zn from Line P showed distributions and Zn:Si relationships that are consistent with the removal of metal in O2-depleted waters through sulphide formation. A first order approximation of the Cd deficit suggests that sulphide formation may be an important sink term in the global Cd cycle. Surface and upper nutricline Zn:Si and Cd:PO43- relationships in the chronically iron (Fe)-limited subarctic northeast Pacific showed distinct trends, which differ from those seen in Fe-replete regions. Distributions suggest the formation of surface biogenic particles with high Cd:PO43- and Zn:Si, leaving surface waters depleted in metals relative to macronutrients and resulting in high metal:macronutrient ratios in the nutricline as these particles sink and are remineralized. This is consistent with understandings of phytoplankton physiology and uptake of divalent metals under Fe-limitation, and corresponds well with global data for dissolved Cd:PO43- patterns in Fe-limited regions. Subsurface high Cd:PO43- and Zn:Si may also be influenced by the advection of water enriched in trace metals. The distinct shallow remineralization horizon observed for Zn compared to Si in the subarctic northeast Pacific by this and previous work presents a fundamentally different distribution than observed in global Zn:Si compilations. Directed sampling in the subarctic northeast Pacific should help elucidate the mechanism behind the oceanographically distinct distributions in this basin. Dissolved ε112/110Cd from Line P demonstrates a remarkably uniform subarctic northeast Pacific deepwater reflecting an advected source signal. Particulate ε112/110Cd samples show an active Cd cycle, which is not imprinted upon the dissolved phase. Particulate ε112/110Cd from 200-600 m depth is among the lightest ε112/110Cd ever reported for natural telluric samples. This may be an important sink for light Cd in the global ocean, which at present is heavy with respect to known sources. Line P surface waters with very low Cd concentrations are not accurately represented by a closed-system Rayleigh model, which can describe ε112/110Cd in the Southern Ocean. This suggests spatially and/or temporally variable surface ε112/110Cd fractionation. A large difference is observed in reported dissolved ε112/110Cd at very low Cd concentrations between different instrumentations. An intercalibration is necessary to determine if this is an analytical artefact or reflects real oceanic variability. / Graduate

This research compares LC50 and LD50 of earthworms, Lumbricus terrestris and Eisenia foetida exposed to cadmium nitrate and chlordane using 48-h contact filter paper (FP) and 14-d artificial soil (AS) protocols. Both LC50 and LD50 showed that chlordane was more toxic than cadmium in both species regardless of the exposure. The reference toxicant 2-chloroacetamide using the standardized 48-h FP exposure was used to assess the general response of the earthworm prior to toxicity experiments. A glucose test was developed as an internal standard to assess homogeneity of mixtures among both replicates and dilutions. Accuracy of dilutions is assessed by the slope of a regression line relating nominal dilution to observed internal standard concentration. Precision of replicate preparation is assessed by among replicate variance.

La baie de Marennes Oléron, premier site ostréicole français, est influencée par la pollution polymétallique historique de l’estuaire de la Gironde avec des concentrations en cadmium dans les huîtres proches de la limite de consommation européenne (RNO 2006; 5 μg.g-1 ps, ECNo.466/2001). Ces travaux de recherche pluridisciplinaires ont pour objectif de caractériser le comportement des ETM en zone côtière et les mécanismes de contamination en ETM des huîtres, spécifiquement en Cd, dans la baie de Marennes Oléron. Pour cela, sept missions océanographiques en période contrastée ont permis de caractériser la spéciation des ETM à l’embouchure des estuaires de la Charente et de la Gironde ainsi qu’au Pertuis de Maumusson.Une étude spatio-temporelle complémentaire des sédiments de surface de la baie de Marennes Oléron a montré un enrichissement des sédiments de surface en Cd dans la zone sud baie,confirmant la connexion des eaux girondines et l’apport en Cd particulaire à la baie par le Pertuis de Maumusson. Cette zone sud a ainsi été choisie pour mener une transplantation d’huîtres pendant trois mois. L’hydrodynamique régionale, observée par imagerie satellite, a présenté unrôle important dans la distribution et la variation temporelle des concentrations en Cd dissous et particulaires minérales de la baie. La bioaccumulation en Cd des différents organes d’huîtres cultivées sur table a été plus importante que celle des huîtres cultivées directement sur le sol,suggérant le faible rôle de la diffusion de Cd par la remise en suspension des sédiments de surface et du microphytobenthos sur la bioaccumulation. De plus, le temps d’immersion étant relativement proche entre les deux conditions, nous suggérons que la voie trophique via le plankton pélagique participe à la contamination des huîtres en plus de la voie directe. Cette contribution de la voie trophique a été confirmée lors d’expérimentations en conditions contrôlées en laboratoire par le développement d’une méthode de traçage simultané des voies de contamination directe et trophique par ajouts d’isotopes stables de Cd, conduites pour des concentrations 10 fois supérieures à l’environnement et des concentrations réalistes observées en baie de Marennes Oléron (40 ng.l-1 et ~0.7 mg.kg-1). / The Marennes-Oléron Bay, hosting the largest oyster production in France, is influenced by thehistoric polymetallic pollution of the Gironde Estuary, with cadmium levels in oysters close tothe consumption limit level (5 μg.g-1 dw, EC No.466/2001). The aim of this pluridisciplinarywork was to characterize the behaviour of trace metals in the coastal zone and the mechanisms ofCd contamination in oysters in the Marennes Oléron Bay. Seven oceanographic cruises wereconducted during contrasting season to characterize trace metals behaviour and speciation in theGironde and Charente estuaries and the coastal zone. Then, a spatial and temporal study of tracemetals in the surface sediments of the Marennes-Oléron Bay showed punctual Cd-enrichedsediments in the southern part, reflecting the connexion with the Gironde waters and theparticulate Cd inputs via the Maumusson inlet. Thus, this area was chosen to study Cdbioaccumulation in oysters over a three months transplantation. The regional hydrodynamic,observed by satellite images, played an important role on Cd speciation and the temporalvariability of dissolved and particulate Cd concentrations. Cadmium bioaccumulation in organsof oysters reared on tables at 60 cm height was more important than in oysters reared near thesediment, suggesting the absence of Cd released during tidal suspension from sediment andmicrophytobenthos. Furthermore, as the immersion time was closed between the two rearingconditions, we suggested Cd bioaccumulation via the direct pathway and also via trophicpathway of contamination by pelagic plankton ingestion. This trophic pathway of Cdcontamination was validated during laboratory experiments using a simultaneous tracing of Cddirect and trophic pathways in oysters by stable isotope spikes at concencentrations 10-foldhigher than the Gironde Estuary and at realistic concentrations observed in the Marennes-OléronBay.

La polyarthrite rhumatoïde (PR) est une maladie inflammatoire chronique caractérisée par des atteintes articulaires. Les synoviocytes, cellules qui tapissent la membrane synoviale, deviennent réfractaires à l‘apoptose et, en produisant la cytokine inflammatoire Interleukin 6 (IL-6), participent à la chronicité de l‘inflammation qui est à l‘origine de la perte osseuse dans la PR.Le zinc (Zn) et le cadmium (Cd) partagent leurs propriétés physico-chimiques et leurs mécanismes de transport cellulaire. Le Zn régule des fonctions du système immunitaire, contrairement au Cd avec des propriétés sur le système immunitaire peu décrites dans la littérature.Notre travail vise à identifier les mécanismes impliqués dans la modification de l‘homéostasie des métaux dans les synoviocytes par l‘inflammation et les conséquences de cette altération.L‘inflammation induit l‘accumulation des métaux dans les synoviocytes en augmentant l‘expression de l‘importeur ZIP-8. En revanche, l‘expression de l‘exporteur ZnT1 et des metallothionéines (MTs, régulateurs de l‘homéostasie des métaux) est dépendante de la présence des métaux. L‘affinité Cd-MTs permet une accumulation irréversible du Cd dans les cellules qui réduit leur prolifération et la production d‘IL-6.Les effets antiprolifératif et anti-inflammatoire du Cd ont été testés dans le modèle d‘arthrite chez le rat où une seule injection intra-articulaire de Cd à faible dose prévient la perte osseuse et réduit les scores cliniques d‘arthrite. Cela pourrait représenter une nouvelle approche thérapeutique pour le traitement de la PR et d'autres pathologies caractérisées par une hyperplasie et une inflammation localisées / Rheumatoid arthritis (RA) is a chronic inflammatory disease. Synoviocytes, cells forming the inner layer the synovium, become refractory to apoptosis and participate in the chronicity of inflammation through the production of IL-6. The perpetuation of inflammation causes an important induction of bone loss in joints.Zinc (Zn) and Cadmium (Cd) share many physico-chemical properties and cell transport mechanism. Zn is known as a regulator of the normal function of the immune system, while Cd properties on the immune system are not well defined.Our aim was to provide information on the metal homeostasis mechanisms in synoviocytes during chronic inflammation and on the consequences of metal homeostasis changes. After studying the differential effect of Zn and Cd at the cellular level, we could provide an innovative tool to control synoviocyte contribution to rheumatoid arthritis, which was tested on an in vivo model of arthritis.Results show that IL-17/TNF-a combination drives the accumulation of metals inside synoviocytes through the enhancing of ZIP-8 importer expression and regardless of the concentration of metals in the culture medium. In contrast, the expression of the metal exporter ZnT1 and of the homeostasis regulators metallothioneins (MTs) was primarily dependent on metal levels.Addition of Zn stimulated the inflammatory response, while addition of Cd can reduce both viability and inflammation.The anti-proliferative and anti-inflammatory properties of Cd were used in the rat model of arthritis as intra-articular treatment to reduce local inflammation and joint destruction and it may represent a new local therapeutic approach for RA treatment

Anhydrous monophenylphosphinates of manganese(II), Mn[H(C₆H₅)PO₂]₂ (Form I, Form II and Form 1(B)) and cadmium(II), Cd[H(C₆H₅)PO₂]₂ (Form I and Form II) were synthesized and characterized by solubility tests, Differential Scanning Calorimetry (DSC), Infrared Spectroscopy, X-ray Powder Diffractometry, Electron Spin Resonance (ESR) spectroscopy, magnetic susceptibility measurements and Electron Spectroscopy for Chemical Analysis (ESCA). These materials are considered to be polymeric with metal ions connected in chains by double bridging phosphinate groups with cross-linkage forming sheets and octahedral metal centers. Magnetic susceptibility studies showed that Mn[H(C₆H₅)PO₂]₂ (Form I) exhibits relatively strong antiferromagnetic exchange interactions (J is about -4.50 cm⁻¹) and the effects on this magnetic exchange of doping diamagnetic cadmium ions into the material have been investigated. A series of mixed metal phosphinates of the form Mn₁₋x Cdx [H(C₆H₅)PO₂]₂ (Form I) where x=0 to 1.00 were prepared and investigated. The effect of doping with cadmium is to break the infinite manganese(II) monophenylphosphinate chain into finite segments and to generate monomer impurities in odd numbered segments. As the extent of doping is increased the average chain length decreases and the fraction of monomer increases. In addition, the exchange coupling constant, J, was found to decrease (from -4.50 to -2.70 cm⁻¹) as the average chain length decreases. Mn[H(C₆H₅)PO₂]₂ (Form 1(B)), which is precipitated from concentrated solutions, contains much shorter chain fragments than the pure Form I material. Mn[H(C₆H₅)PO₂]₂ (Form II) has a distinct infrared spectrum and X-ray powder diffraction pattern and shows much weaker antiferromagnetic behavior (J is about -2.40 cm⁻¹) than the Form I compound. Magnetic studies suggest that in this compound the average chain length is significantly smaller than in Mn[H(C₆H₅)PO₂]₂ (Form I). The hydrated monophenylphosphinates of manganese(II), Mn[H(C₆H₅)PO₂]₂•H₂0 and Mn[H(C₆H₅)PO₂]₂•2H₂0, were synthesized and characterized in this work. The structures of these compounds are considered to be similar to those of the anhydrous materials except in the hydrated compounds one or two of the metal coordination sites are occupied by water molecules. The dihydrate shows only very weak antiferromagnetic properties (J is about -0.50 cm⁻¹). The diphenylphosphinates of manganese(II) and cadmium(II) were also prepared and characterized. The infrared spectra and X-ray powder diffraction patterns for these materials are distinct from each other,which indicates the compounds are not isomorphous. Only rather weak magnetic exchange was observed in the manganese compound. Zn[H(C₆H₅)PO₂]₂ has also been synthesized and partially characterized in this work. The infrared spectrum and X-ray powder diffraction pattern obtained for this compound are unique among all the metal phosphinates studied in this work. / Science, Faculty of / Chemistry, Department of / Graduate

No description available.

Cadmium (Cd) is a highly toxic metallic element to the human body such that prolonged occupational or environmental exposure produces renal, hepatic, pneumonic, and neurological disorders. Thus, as a consequence it is important to have a way of monitoring cadmium exposure as it has the potential to become an occupational health hazard. The primary uses of this element are in the mining and smelting industry in the manufacture of cadmium alloys and the manufacture of alkaline accumulators. Since the discovery of X-rays in 1895 by Wilhelm Conrad Roentgen, the science of X-ray analysis has become a cardinal tool in all domains of chemical identification and classification. X-ray fluorescence (XRF) has been shown to be an effectual technique for measuring trace quantities of heavy metals such as lead in various tissues within the body. This thesis stud:r elucidates a means of measuring Cadmium in bone. The study assesses the feasibility and practicality of the polarised XRF and source excited techniques. In the polarised cadmium concentration measurements, a gain in sensitivity due to improved background characteristics was perused by increasing the x-ray tube operating voltage of the system. It was found that an operating voltage of 175 kV, and a copper filter resulted in a significant gain in sensitivity for which a minimum detection limit (MDL) of 3.5 ± 1.4 ppm was determined with 3 mm of tissue equivalent overlay. Using the source-based technique, a MDL of 3.5 ± 0.2 ppm was estimated for the corresponding tissue equivalent overlay. / Thesis / Master of Science (MS)

Call number: LD2668 .T4 1958 W49

No description available.

No description available.