Thesis (Ph. D.)--University of Alberta, 2009. / Title from pdf file main screen (viewed on Nov. 25, 2009). "A thesis submitted to the Faculty of Graduate Studies and Research in partial fulfillment of the requirements for the degree of Doctor of Philosophy, [Department of] Chemistry, University of Alberta." Includes bibliographical references.

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published_or_final_version / Physics / Doctoral / Doctor of Philosophy

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Attenuation of uranium (U) and rare earth elements (REEs) has been observed in stream and wetland sediments, but the geochemical and mineralogical processes involved in sequestering these elements in natural systems are not well understood. The decommissioned Bicroft Uranium Mine near Bancroft, ON uses a modified stream and wetland system to reduce the concentrations of U and other metals in tailings pond effluent to levels below the Provincial Water Quality Objectives. The Bicroft Mine was operated from 1957 to 1963, and processed low-grade (~0.17 wt% U3O8), disseminated U hosted by pegmatite dykes in amphibolite gneiss, forming 2,284,421 tonnes of tailings, deposited into two tailings impoundments. The Bicroft site has since operated as a passively attenuating stream and wetland remediation system for 55 years, demonstrating the potential longevity and viability for long-term sequestration of U and REEs through natural attenuation. To identify U and REE hosts and their stability in the natural environment, colloids, tailings, stream and wetland sediments were analyzed using various methods, including tangential flow filtration (TFF), ICP-ES/MS, scanning electron microscopy, and synchrotron techniques (bulk and µXANES, µXRF, and µXRD). The results show that Fe- and Mn-oxyhydroxides, goethite, and birnessite are the main mineral hosts for U and REEs in both the colloids and sediments. In addition, detrital grains of U- and REE-bearing minerals were found >200 m downstream in colloids and wetland sediments, showing the potential for long range transport of colloids and particulates in the stream system. Seasonal influences on the stability of trace metals in sediments were observed, and may demonstrate the limitations of passively attenuating remediation systems as a viable method for attenuation. Changes in the redox state of the stream system were observed to influence the attenuation of U and REEs, however, changes in the redox state with depth in the wetland sediments were not observed, and showed no direct influence on the attenuation of U and REEs. The results of this study will help to develop better monitoring strategies for U tailings sites and should reduce the impacts of future U mining operations. / Thesis (Master, Geological Sciences & Geological Engineering) -- Queen's University, 2013-05-06 07:44:03.327

The 'RMnO3': R = La, Nd, Pr, phases have been synthesised and characterised by a combination of electron probe microanalysis (EPMA), H2-reduction thermogravimetry (TG), x-ray (XRD) and neutron diffraction (ND). RMnO3 forms, at" 1400C, over the ranges: NdMn0, 95Oz to Nd0 88MnOz PrMn0.97O2 to Pr0 88MnOz LaMno 0.90Oz to La0.97MnOz Oxygen contents vary in air over the range 700 to 1400 C and can be varied further, either by high pressure Oz treatment or by reduction in H2. The structure of 'RMnO3' R = Nd, Pr is based on the GdFe03 structure with a Jahn-Teller distortion associated with the high proportion of Mn3+ ions present. The oxygen deficient 'LaMnOz' compositions also exhibit this structure consistent with earlier reports. By combining EPMA, TG, XRD and ND results various defect models describing the stoichiometry and structure of Mn-rich and R-rich, R = Nd, Pr compositions have been summarised. Both R = Nd and Pr systems exhibit very varied defect structures; depending on composition and heat treatment, vacancies can form on any one or any two of the three sublattices, R, Mn and O and the overall Mn oxidation state can include 2+, 3+ and 4+ contributions. For 'RMn03': R = La, Nd, Pr, data on their compositional ranges and defect crystal structures are presented in the form of novel phase diagram-defect structure maps from which the principal defect structure for a given stoichiometry can be easily obtained. The majority of the Pr-Sr-Mn-O pseudotemary phase diagram has been determined. EPMA was used to follow the progress of reaction and the conditions to achieve complete reaction established. Several solid solutions were evidenced, some previously unreported (3 - 6): 1) Pr1.xSrxMnO3 0[Special character omitted]x[Special character omitted]1.0 2) Pr1+xSr2.xMn2O7 0 [Special character omitted]x [Special character omitted] 0.4 3) SrxPr1-xO2 0[Special character omitted]x[Special character omitted]0.16 4) Sr1-xPrO3 0[Special character omitted]x[Special character omitted]0.15 5) Sr2.xMnxO4 6) Sr2.xPrxMnO4 The perovskite-like Pr1-xSrxMnO3 solid solution extends from PrMnOz to SrMnOz. The unit cell symmetry changes from orthorhombic to rhombohedral to tetragonal to cubic and finally to hexagonal as the Sr content increases. The limits of the Ruddlesden Popper (RP) n=2 Pr1+xSr2_xMn2O7 solid solution were determined: 0 [Special character omitted] x [Special character omitted] 0.4 and a tetragonal unit cell observed consistent with the literature. Synthesis of the RP compositions by solid state methods requires long heating times (up to 36 days) to produce homogeneous samples; qualitative EPMA of younger samples indicated an inhomogeneous distribution of Pr and Sr. Contrary to EPMA results, XRD of younger samples indicated that complete reaction had occurred and single phase compositions produced. It is suggested that the SrxPr1-.xO2 solid solution extends over the range 0 [Special character omitted] x [Special character omitted] 0.16 where similarly to the polymorphism of praseodymium oxides, compositions 0.03 [Special character omitted] x [Special character omitted]0.16 exhibit the cubic fluorite-type structure of Pr6O11 and x [Special character omitted] 0.03 is a mixture of cubic SrxPr1-xO2 and hexagonal SrxPr2.xO3. Perovskite-like SrPrO3 exhibits variable cation ratios; the Pr-rich boundary is Sr0.85PrOz. The lower Sr-rich boundary is yet to be identified. Similarly to 'RMnO3': R = La, Nd, Pr, the oxygen content of 'SrPrOz' is expected to vary. Therefore, various possible defect structures describing vacancies on the three sublattices, Sr, Pr and O could exist and charge compensation would be an interesting example of ionic and electronic mechanisms where Pr adopts the +4 and +3 oxidation states. Four layer hexagonal SrMnO3 exhibits variable Sr:Mn ratios but the solid solution limits are not yet known. The unreported Sr2-xPrxMnO4 solid solution has been observed but the solid solution limits are not yet known. The K2NiF4-type structure of Sr2Mn04 is retained at x = 0.75 and is expected to contain Mn3+ as Mn4+ is reduced to compensate Sr24 substitution by Pr3+.

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