No description available.

Thesis (MTech (Chemical Engineering))--Cape Peninsula University of Technology, 2011. / Lithium 7 (⁷Li⁺) is an isotope, which is used in the nuclear industry as lithium hydroxide (⁷LiOH) for the chemical control (pH control) of the high purity reactor coolant water process in order to prevent corrosion in the Pressurised Water Reactor (PWR). Furthermore, the ⁷Li⁺ isotope is used in an ionic form in the nuclear grade cation ion-exchange resin. This resin is used to purify the nuclear reactor coolant water by reducing cationic corrosion by-products such as Cesium and Cobalt, which are generated from nuclear fission reactions. In view of the fact that an inorganic salt of the isotope is used as an alkali sing agent in the PWR, the use of lithiated resin prevents the removal of the ⁷Li⁺ isotope in the coolant water. As most users of the nuclear grade resin purchase their resin in bulk, it follows that the resin has to be evaluated in order to determine its usability. In certain cases, the resin may be considered unusable as a result of the degradation caused by unsuitable transportation and storage conditions. These, in turn, perpetuate the release of leachates, which may further contribute to corrosion in the PWR. This necessitated the undertaking of this study, which was to evaluate whether it is possible to recover the high value ⁷Li⁺ isotope from a degraded nuclear grade resin in such a way that the isotope may be used in the PWR.

No description available.

The eastern margin of the Proterozoic Athabasca Basin in northern Saskatchewan is host to several of the highest-grade unconformity-related (U/C-related) uranium deposits in the world. Many researchers agree that uranium deposition occurred due to oxidized basinal brines transporting uranium mixing with reducing fluids or interacting with reduced rock causing uranium to precipitate, although the source of the uranium is still an unresolved and highly debated subject. Boron isotopic signatures, preserved in refractory minerals such as tourmaline, can aid in determining the source of fluids and P-T conditions during crystallization whereas lithium isotopic fractionation is indicative of weathering, hydrothermal alteration, and/or igneous and metamorphic processes. For this study a suite of fresh to strongly altered basement samples were selected from multiple sites below the eastern Athabasca Basin to measure the bulk delta7Li, delta11B and Pb-Pb isotopic signatures. Kinetic modelling of the Li and B isotopic systems suggest that both systems are slightly conservative of their original fluid reservoir, and by calculating the Damkohler numbers (ND) it is predicted that delta11B will be more indicative of the fluid source whereas lithium isotopes will equilibrate over shorter distance. However, both isotopic systems will fractionate with large concentration changes. Significant variations were observed for both delta7Li and delta11B, delta7Li values ranged from 0 to 14 ‰, the range in delta7Li was interpreted to be representative of both partial melting of metasediments to form granitic pegmatites and hydrothermal fluids. In comparison the range for delta11B was much larger from -16 to +17‰, within the dataset there appeared to be regional isotopic differences but unfortunately this dataset was too small to determine regional isotopic patterns. For each region the delta11B for the pegmatites was often heavier than the metasedimentary samples suggesting a metasedimentary source for the granitic pegmatites. Elevated U concentrations and decreasing 207Pb/206Pb ratios in both altered and unaltered samples suggest radiogenic Pb and U are present both in the basement and in fluids transporting U through the basement. Partial digestion 207Pb/206Pb ratios range from the common 207Pb/206Pb ratios of 0.7 to radiogenic 207Pb/206Pb ratios of 0.1. The radiogenic 207Pb/206Pb are indicative of either resetting of residual material during fluid migration or radiogenic fluids sources interacting with the rocks of this study.

Mass spectrometers are analytical instruments that convert neutral atoms and molecules into gaseous ions and separate those ions according to the ratio of their mass to charge, m/z. The measurement is reported as a mass spectrum: a plot of relative intensity vs. m/z that can be used to deduce the chemical structure and composition of materials and compounds. Initially, the use of mass spectrometers was restricted to the analysis of volatile compounds. Recent advances in the development of ionisation techniques to produce intact molecules directly from samples in the liquid or solid phase, has extended the powerful use of mass spectrometry to compounds of increasingly higher molecular mass. The aim of this study was twofold: develop diagnostic techniques for the in-situ measurement of isotope ratios in laser isotope separation experiments; and to correlate it with the measured isotope ratios on the collected product. The outcome is a thesis that can be divided into two distinct fields of application: Firstly; the Atomic Vapour Laser Isotope Separation (AVLIS) of lithium, and secondly the Molecular Laser Isotope Separation (MLIS) of uranium, In both AVLIS and MLIS pulsed laser systems were used to ionise and/or dissociate atomic or molecular beams. The pulsed nature of the lasers is ideally suited to in-situ time-of-flight detection of the produced ions. Different types of inter-changeable ion sources are common to the same TOF mass spectrometer. Each of these sources is selected according to its application. For instance, applications vary from photo- and multiphoton ionisation (laser ionisation) to surface analysis (laser desorption or particle bombardment) to chromatography (electron impact ionisation). Four different source configurations were considered in this study: (i) Atomic Laser Isotope Separation (AVLIS) of lithium; (ii) Multiphoton Ionisation (MPl) of UF6 gas; (iii) Non-resonant ionisation during Laser Desorption (LDI) of solids; and (iv) Matrix-Assisted Laser Desorption (MALD) of biopolymers. The design of each of these sources will be discussed in detail in chapters to follow. Bulk analysis of harvested laser-produced products needs to be in correlation with in-situ analysis. Three different characterisation methods were used in this study: (i) Laser Desorption Time-of-Flight Mass Spectrometry (LD-TOF-MS) (ii) Quadrupole-based Secondary Ion Mass Spectrometry (SIMS); and (iii) TOF-MS-based Secondary Ion Mass Spectrometry (TOF-SIMS). Chapter I describes the principles of time-of-flight mass spectrometry, design parameters, as well as the instrumentation that were designed and constructed for the purposes of this study. Chapter II describes the principles of Secondary Ion Mass Spectrometry (SIMS). In particular, research done on the establishment of tools to the non-expert user of SIMS to select analyses conditions, is described. Chapter III reports on the application of TOF-MS and SIMS during the AVLIS of lithium. Chapter IV reports on the application of the different combinations of TOF-MS, LD-TOF-MS, SIMS, and TOF-SIMS during the MLIS of uranium. / Thesis (Ph.D.)-University of Natal, Durban, 1999.

This dissertation combines mineralogical data and petrographic and field observations with geochemical analysis (major, trace and isotope) to provide new insights into the hydrology and geochemistry of mid-ocean ridge hydrothermal systems. Two study areas were chosen to study two different aspects of hydrothermal circulation: high-temperature on-axis hydrothermal systems were studied using samples from the Hess Deep Rift (Cocos Plate, Equatorial Pacific) and low-temperature off-axis hydrothermal systems were studied at the Troodos Ophiolite in Cyprus. Significant findings include the documentation of a previously unknown warm fluid that pervades the lavas leaching Li from newly formed crust. This finding corroborates a model of broad hydrothermal discharge in the sheeted dikes. In the off-axis low-temperature regime, lateral flow of warm fluid is documented in the lavas, advecting heat from the oceanic lithosphere, with minor geochemical changes to the lavas. The sedimentary cover was found to influence alteration in two ways. The longer an area remains unsedimented allowing the free ingress and egress of seawater, the deeper the enrichment of alkali metals is observed. The maximum enrichment in alkali metals (K, Rb, Cs) however, is similar in both locations. The sedimentary cover can also modify the seawater before it becomes impermeable to fluid flow; early metaliferrous oxide sediments react with seawater, creating a fluid that mobilizes and fractionates the REEs and Y. The fractionation results in negative Ce anomalies, positive Eu anomalies, and negative Y anomalies. Basalts altered under these conditions also lack the ubiquitous Fe-oxides and Fe-oxyhydroxides that are commonly associated with alkali metal uptake. In situ trace element analysis of alteration minerals formed at low-temperature confirmed that secondary phyllosilicates are strongly enriched in alkali metals (K, Rb, Cs and Li), Ba is found in adularia and zeolites, Sr is hosted in carbonates, and no phases were found to be enriched in U. The concentrations of K2O, Rb, Cs (as well as B) are highest in celadonites, whereas Li concentrations are highest in smectites (saponite, Al-saponite, beidellite) and smectite-chlorite mixtures, and much higher than previously reported. Alkalis are also taken up into palagonite, with Li having the highest concentrations, over 1000 ppm in one analysis. Crystal chemical factors were found to be the dominant control on trace element uptake, and for the phyllosilicates no correlation was found between the temperature, age of the crust, texture of the phyllosilicates. In phyllosilicates the K, Rb and Cs are adsorbed as exchange cations, with enrichment (Cs > Rb > K) increasing with decreasing hydration energy, whereas the uptake of Li and B does not correlate with the hydration energy. Lithium concentrations also do not correlate with the Mg content, suggesting substitution of Li for Mg is not the only mechanism of Li uptake into phyllosilicates as has been suggested. / Graduate

In this article, we document a detailed analytical characterisation of zircon M127, a homogeneous 12.7 carat gemstone from Ratnapura, Sri Lanka. Zircon M127 has TIMS-determined mean U-Pb radiogenic isotopic ratios of 0.084743 +/- 0.000027 for Pb-206/U-238 and 0.67676 +/- 0.00023 for Pb-207/U-235 (weighted means, 2s uncertainties). Its Pb-206/U-238 age of 524.36 +/- 0.16 Ma (95% confidence uncertainty) is concordant within the uncertainties of decay constants. The delta O-18 value (determined by laser fluorination) is 8.26 +/- 0.06 parts per thousand VSMOW (2s), and the mean Hf-176/Hf-177 ratio (determined by solution ICP-MS) is 0.282396 +/- 0.000004 (2s). The SIMS-determined delta Li-7 value is -0.6 +/- 0.9 parts per thousand (2s), with a mean mass fraction of 1.0 +/- 0.1 mu g g(-1) Li (2s). Zircon M127 contains similar to 923 mu g g(-1) U. The moderate degree of radiation damage corresponds well with the time-integrated self-irradiation dose of 1.82 x 10(18) alpha events per gram. This observation, and the (U-Th)/He age of 426 +/- 7 Ma (2s), which is typical of unheated Sri Lankan zircon, enable us to exclude any thermal treatment. Zircon M127 is proposed as a reference material for the determination of zircon U-Pb ages by means of SIMS in combination with hafnium and stable isotope (oxygen and potentially also lithium) determination.

Chemical weathering of silicate rock consumes atmospheric CO2 and supplies the oceans with cations, thereby controlling both seawater chemistry and climate. The rate of CO2 consumption is closely linked to the rate of CO2 outgassing from the planetary interior, providing a negative feedback loop essential to maintaining an equable climate on Earth. Reconstruction of past global temperatures indicates that a pronounced episode of global cooling began ~50 million years ago, coincident with the collision of India and Asia, and the subsequent exhumation of the Himalayas and Tibet. This has drawn attention to the possible links between exhumation, erosion, changes in silicate weathering rates, and climate. However, many of the present-day weathering processes operating on the continents remain debated and poorly constrained, hampering our interpretations of marine geochemical archives and past climatic shifts. To constrain the controls on silicate weathering, this thesis investigates the lithium (Li) isotopic composition of river waters, suspended sediments and bed load sediments in the Alaknanda river basin, forming the headwaters of the Ganges. Due to the large fractionation of Li isotopes in the Earth’s surface environment, Li is sensitive to small changes in silicate weathering processes. As a consequence of the pronounced gradients in climate (rainfall and temperature) and erosion across the basin, the river waters show large variations in their Li isotopic composition (δ7Li), ranging from +7.4 to +35.4‰, covering much of the observed global variation. This allows a detailed investigation of the controls on Li isotope fractionation, and by extension silicate weathering. The Li isotopic composition is modelled using a one-dimensional reactive transport model. The model incorporates the continuous input of Li from rock dissolution, removal due to secondary mineral formation, and hydrology along subsurface flow paths. Modelling shows that the Li isotopic variations can be described by two dimensionless variables; (1) the Damköhler number, ND, which relates the silicate dissolution rate to the fluid transit time, and (2) the net partition coefficient of Li during weathering, kp, describing the partitioning of Li between secondary clay minerals and water, which is primarily controlled by the stoichiometry of the weathering reactions. The derived values of the controlling parameters ND and kp, are investigated over a range of climatic conditions and on a seasonal basis, shedding light onto variations in the silicate weathering cycle. In a kinetically limited weathering regime such as the Himalayan Mountains, both climate and erosion exert critical controls the weathering intensity (the fraction of eroded rock which is dissolved) and the weathering progression (which minerals that are being weathered), and consequently the fractionation of Li isotopes and silicate weathering in general. Modelling of the Li isotopic composition provides an independent estimate of the parameters which control silicate weathering. These estimates are then used to constrain variables such as subsurface fluid flux, silicate dissolution rates, fluid transit times and the fraction of rock which is weathered to form secondary clay minerals. The simple one-dimensional reactive transport model therefore provides a powerful tool to investigate the minimum controls on silicate weathering on the continents.

No description available.

Pour mieux comprendre le processus géodynamique qui a permis la destruction du craton Nord Chinois (NCC), le rôle des fluides mantelliques a été examiné. Pour cela, les distributions des teneurs en eau et des compositions isotopiques du Lithium dans le manteau lithosphérique NCC ont été déterminées à partir des xénolites de péridotite entrainés par les basaltes mésozoïques et cénozoïques. Une variation temporelle des teneurs en eau est observée. Le manteau lithosphérique cénozoïque est appauvri en eau, sans doute suite à l'amincissement crustal et au réchauffement du manteau résiduel par un flux ascendant asthénosphérique. Le manteau lithosphérique mésozoïque montre des teneurs en eau intermédiaire entre les teneurs élevées du Crétacé et les teneurs basses cénozoïques, indiquant une déshydratation du manteau commençant dès le début de sa destruction. Cette déshydratation, facilitée par la destruction du manteau lithosphérique profond, permet de renforcer la rigidité de la lithosphère et lui permet de résister à la convection mantellique. Les distributions élémentaire et isotopique du Li montrent une grande hétérogénéité, aux échelles intra et inter-cristallines. Par simulation numérique, nous démontrons que deux enrichissements successifs ont affecté le manteau, un enrichissement limité (<5ppm) avec une signature pauvre en 7Li ([delta]7Li ~ -20 [pour mille]), suivi d'un enrichissement important (> 100 ppm) avec une signature riche ([delta]7Li ~ +20 [pour mille]), précédent de peu l'exhumation des xénolites. La formation des liquides métasomatiques responsables de ces enrichissements nécessite une distribution hétérogène dans le manteau NCC d'éléments recyclés lors de la subduction à l'est du NCC / In order to investigate the geodynamic cause for destruction of the North China Craton (NCC), the role of mantle fluids is examined. The aim of the PHD work is to clarify H2O contents and lithium isotopic compositions of the NCC lithospheric mantle by studying peridotite xenoliths hosted by Mesozoic-Cenozoic basalts across eastern NCC. A temporal variation of H2O content has been revealed, and it has deep implications for processes of craton destruction. The Cenozoic lithospheric mantle was featured by low H2O content, interpreted to be the relict mantle that survived the lithospheric thinning and has been dewatered by reheating from upwelling asthenospheric flow. The late-Mesozoic lithospheric mantle showed relatively high H2O content, a hydrous status intermediate between the Cretaceous hydration and the Cenozoic dryness, indicating the dehydration of the NCC mantle with time during NCC destruction. The dehydration, facilitated by thinning of weak mantle pieces at bottom, is one way by which the lithosphere strengthens itself to survive in the convecting mantle. Extreme Li and isotopic disequilibria were observed intra- and inter-mineral in the peridotites. With numerical simulations, we demonstrate two superimposed Li enrichment events occurring at the mantle: a limited Li enrichment (< 5 ppm) and large delta7Li depletion (-20~-10[per 1000]) of the mantle domain, followed by a recent and transient infiltration of high Li and delta7Li (up to +20 [per 1000]) melts/fluids. The anomalous Li isotopic compositions of mantle metasomatic agents call upon the same of their mantle sources, and we assume recycled components, both Li isotopically heavy and light, in the mantle beneath the eastern NCC