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The clay mineral composition of sediments deposited in the last six oxygen isotope stages in the Gulf of Mexico continental slope was characterized. Smectite and illite were found to be the two major clay minerals of the clay fraction while kaolinite, chlorite and quartz were present in the clay fraction but in less proportions. Variations in clay mineral abundances, especially in the relative abundances of smectite and illite, were identified in relation to climate changes. Smectite was the most abundant mineral in sediments of the current (stage 1) and last interglacial maxima (stage 5) while illite dominates the clay min-eralogy of sediments from the last glacial maximum (stage 2). Relationships between clay mineralogy and physical properties were investigated as well. Significant positive correla-tions were found between Atterberg limits with the smectite content of the bulk sediment and with clay content. However, the relationship with smectite yielded a significantly higher correlation coefficient. Smectite and clay content also affect the natural water con-tent of sediments and its changes with depth.

The clay mineral composition of sediments deposited in the last six oxygen isotope stages in the Gulf of Mexico continental slope was characterized. Smectite and illite were found to be the two major clay minerals of the clay fraction while kaolinite, chlorite and quartz were present in the clay fraction but in less proportions. Variations in clay mineral abundances, especially in the relative abundances of smectite and illite, were identified in relation to climate changes. Smectite was the most abundant mineral in sediments of the current (stage 1) and last interglacial maxima (stage 5) while illite dominates the clay min-eralogy of sediments from the last glacial maximum (stage 2). Relationships between clay mineralogy and physical properties were investigated as well. Significant positive correla-tions were found between Atterberg limits with the smectite content of the bulk sediment and with clay content. However, the relationship with smectite yielded a significantly higher correlation coefficient. Smectite and clay content also affect the natural water con-tent of sediments and its changes with depth.

Authigenic clays are potential proxies for paleoclimate change when formed under saline conditions. Between 1.9 -1.7 mya, Olduvai was a closed-hydrologic basin into which Al- and Fe- rich detrital clays were transported from surrounding soils. Authigenic Mg-rich smectite formed within the basin due to chemical alteration in alkaline and saline conditions. 40 samples were chosen from a stratigraphic section in the center of the paleolake and analyzed to characterize the geochemical facies of the material using XRD, EMPA, and FTIR. ~70% of samples were Mg-rich with clay d060 XRD peaks between 1.506-1.523Å. EMPA indicated (Al2O3 + Fe2O3)/MgO ratios ranged from 0.2-4.8, 21 had ratios >1.0, indicating higher (Al2O3 + Fe2O3) content. These clay data correlated with bulk XRF data, indicating diagenetic controls on bulk composition. Therefore, bulk geochemistry can potentially indicate paleoclimate change when influenced by Mg-rich phyllosilicate formation.

Unconformity-related uranium deposits in the Athabasca Basin represent a significant global resource of uranium. One such deposit, the Phoenix Deposit, discovered in 2007 on Denison Mine’s Wheeler River property, shares similarities with other deposits in the Basin. The Phoenix Deposit is located at the apex between a basement shear structure, and the unconformity between the crystalline basement and overlying sandstones. The shear structure extends into the sandstones, this structure controls the distribution of alteration minerals in the basement and early alteration phases in sandstones. The shear structure extending to sandstones is not spatially associated with late alteration phases associated with the uranium deposit, suggesting that the structure was not important for uranium mineralisation. Bulk rock compositions of sandstones show chimney-like distribution of elements above the uranium deposit. The most notable ones are the distribution of yttrium, and boron. Rare earth elements and yttrium are not soluble in aqueous fluids at low temperatures and they are enriched in uranium ore. Therefore, the chimney-like distribution of elements are attributed to uraniferous hydrothermal activity in sandstones. Petrographic and chemical analysis of alteration associated with the Phoenix Deposit shows two types of tourmaline, a pre-ore (Tur 1) in the basement, which is likely a metamorphic product (Tur1) and a syn-ore magnesiofoitite (Tur 2) in the basement and the sandstones. Three generations of chlorite are identified within the alteration halo of the Phoenix Deposit; an early Fe-rich clinochlore (C1) in the basement and sandstones, the second generation, Mg-rich sudoitic chlorite (C2) in the basement, and a late, sudoitic chlorite (C3) in the basement and sandstones. Illite shows three types; an early and late M1 and a late M2. M1 is found as two polytypes, 1Mc and 1Mt, in the basement and sandstones, with the 1Mt having a spatial relationship with the uranium deposit. Late M2 illite is coarse-grained and occurs in the basement and sandstones. Near Infrared (NIR) spectra of sandstones overlying the deposit shows absorption features between 600 and 700 nm. It is considered that these absorption features appear to have been produced during late hydrothermal activity and may have a temporal as well as spatial relationship with uranium mineralisation.

Many chemical and physical factors govern the mobility of metal contaminants in soils and clay systems; some of these chemical factors include mineralogical composition, cation exchange capacity, organic matter content, pH and the ionic strength of soil water. This makes understanding and therefore predicting the fate of metal contaminants in soils a complex undertaking. There were two broad objectives in this study. The first was to investigate binary and ternary sorption systems, with the aim to understand the effects that factors such as pH, ionic strength, organic matter and metal concentrations, have on sorption of simple clay minerals (bentonite and kaolinite) with metals (cadmium, caesium, nickel and strontium). The second was to investigate the retention of heavy metals and radionuclides by well characterised organic-rich and organic-poor clay soils, breaking them down to their individual components to help understand the effects of each component separately, the study also tested to see if the additivity principle holds for these heavy metals and radionuclides, the additivity principle presumes that the overall sorption behaviour of a complex mixture is a summation of the weighted individual sorption behaviours of its constituents. The study also determined the relationship between the natural organic matter (NOM) content and cation exchange capacity (CEC) of the soils and how these affect the mobility of the metals, while also considering the relative importance of the speciation of the metals. Two British clay soils (Mercia Mudstone and London Clay) and two Nigerian soils (an organic-rich Ikeja Loam and the other organic-poor Magodo Laterite) were characterised by X-ray diffraction (XRD) analysis. Batch techniques were employed for the sorption studies, and radiometric techniques, ICP-OES and ICP-MS were used to quantify metal distribution between phases. The sorption of dissolved organic matter to clay minerals is very dependent on pH; this dependence is greater with increasing concentration of organic matter. The formation of metal-humate complexes is dependent on the nature of the metal and pH. Caesium exhibits no discernible sorption to humic acid, cadmium sorption is enhanced by increasing alkalinity but this enhancement is slightly reduced in higher concentrations of humic acid, nickel sorption is mostly unaffected by pH except in higher concentrations of humic acid and enhanced only under very low concentrations of humic acid, while strontium sorption to humic acid is reduced with increasing alkalinity. The nature and preference of humic acid sorption for these metals are vital to understanding the role played by humic acid in the ternary sorption studies of metals, humic acid and clay minerals. Strongly acidic conditions dominate other factors affecting sorption such as ionic strength in sorption of metals to clay minerals. Caesium sorption to bentonite at pH 4 is poor and almost unaffected by ionic strength of the electrolyte solution; saturation of sorption sites is reached with low amounts of adsorbed caesium. Strontium also binds poorly to bentonite at pH 4, more so than caesium, but an ionic strength effect on sorption still exists and is discernible even under these conditions. Increasing alkalinity has the expected effect of increasing sorption capacity of bentonite for both metals. Bentonite has poor sorption properties, having low affinity for caesium and strontium, but has greater affinity for caesium than strontium. The presence of humic acid can enhance or suppresses sorption, this varies from metal to metal and from solid to solid, the degree of enhancement or suppression also depends on humic acid concentration. Kaolinite has better sorption properties than bentonie. Cadmium has greater sorption affinity for kaolinite in the absence of humic acid, but nickel sorption is more enhanced in the presence of humic acid. Although the presence of humic acid enhances cadmium and nickel sorption to kaolinite, low humic acid concentration provides the best conditions for maximum sorption of both metals. High concentrations of humic acid lead to colloid formation which block access of metals with larger hydration radii to sorption sites while also encouraging the formation of humic acid-metal complexes. As with bentonite, caesium and strontium are both poorly sorbed by kaolinite. Unlike with cadmium and nickel however, the enhancement of strontium sorption is supported by higher concentrations of humic acid, these confirm a greater preference for the formation of S-HA-Sr ternary and lower preference for the formation HA-Sr binary complexes. The presence of humic acid inhibits caesium binding, and retention but this reduces with increasing alkalinity, while the reverse is the case with strontium whose retention is very poor and improved in the presence of humic acid and increasing alkalinity. Both caesium and strontium are poorly sorbed and retained by kaolinite but their retention improves with increasing humic acid concentration and pH. Cadmium and nickel also exhibit poor retention to kaolinite but their retentions are more improved under alkaline conditions and higher humic acid concentrations, nickel more so than cadmium. Similar sorption affinities were exhibited by the British (London Clay and Mercia Mudstone) and Nigerian soils (Magodo Laterite and Ikeja Loam) for the metals studied, showing the significance of soil constituent contribution to sorption behaviour. Both British clay matrices have affinity for the metals in the order Cs >> Cd ≈ Ni >> Sr, London Clay has the greater sorption capacity for all the metals, the clay mineral content of Mercia Mudstone is almost entirely made up of Illite while London Clay contains a mixture of smectite, illite and kaolinite with smectite being the most prevalent clay mineral phase. These confirm that smectite-rich clay systems will exhibit better sorption and retention capacities for metal contaminants. Both Nigerian soils showed the same order of affinity for all the metals Cd >> Ni >> Cs >> Sr, cadmium s preferential sorption to kaolinite was observed in its greater sorption and retention by the Nigerian soils which are kaolinite-rich. This preferential sorption of cadmium by kaolinite is confirmed by the Standard Addition experiment where its contribution to cadmium sorption is clearly evident, a trend not replicated with nickel as the sorbing metal. The presence of organic matter in soils or clay systems improves their metal sorption capacity significantly, especially true for insoluble organic matter, however its significance is reduced as pH increases. The contribution of organic matter also depends on the sorption affinity of the metal for organic matter; metals such like strontium are more affected by organic matter presence. The overall sorption behaviour of complex systems such as soils is difficult to attribute to their individual constituents. The laterite soils can be considered a relatively simple soil system containing only four constituents in significant quantities, yet it is difficult to replicate its sorption behaviour using a replicate proportioned mixture of its constituent phases. The additively calculated sorption profiles for the synthetic laterite were different from those obtained experimentally, the reason for this is that the existence of significant particle size differences between the natural and synthetic soils give rise to differences in the availability of sorption sites which is evident from the different CEC values measured for both systems.

Thesis (Ph. D.)--University of Missouri-Columbia, 1997. / Typescript. Vita. Includes bibliographical references (leaves 258-282). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 1997. / Typescript. Vita. Includes bibliographical references (leaves 258-282). Also available on the Internet.

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