<p> Phase equilibrium relations were determined in the system NaAlSiO8-NaAlSiO4-H2O on a P-T projection in the P-T range 0.5-10Kb and 150°-900°C, and on three isobaric (2Kb, 5.15Kb and 7. 32Kb) T-X projections. The T-X stability field of analcite determined in this study has a relatively large distorted pentagonal shape. The petrogenetic problem of analcite is fully discussed. On the composition join NaAlSiO4-H2O, the phase relation is not binary for the transition: nepheline hydrate I = nepheline + H2O; there exists a narrow three-phase zone for the transition. The true P-T curve was determined in terms of a ternary univariant reaction: nepheline hydrate I+ analcite = nepheline + H2O. Another univariant reaction (zeolite species P. = analcite + nepheline hydrate I+ H2O) was found at 2Kb/215°C and 5.15Kb/235°C and determined on a P-T projection. In the system NaAlSi3O8-SiO2-H2O, albite contains a maximum of about 5 Wt.% silica in solid solution at 5.15Kb/670°C.</p> <p> The equilibrium compositions of various univariant phases were determined essentially by phase boundary-location on several isobaric T-X projections. Three singular points were determined: two of them are approximately located at 0.8Kb/390°C and 9.4Kb/475°C on a univariant curve (N-h I+ Anl =Ne+ H2O). The other one is approximately located at 6Kb/655°C on the (Ab) univariant curve.</p> </p> A simple method for determining H2O-solubility in melts was developed and applied to the study of the system NaAlSi3O8-NaAlSiO4-H2O. Using this method, solubility data are simply obtained as by-products of the experimental runs made for the investigation of the phase equilibria. The amount of water required to make an H2O-saturated melt (from the total amount of water in the original charge) is taken as the dissolved water in the melt; the solubility value is corrected by determining the amount of moisture originally absorbed in the starting powder. The method is generally applicable to the determination of H2O-content in any hydrous phase. The H2O-solubility in a melt is not too sensitive to a variation in anhydrous composition of the melt (~ 6±1 Wt.% H2O at 2Kb and ~11±1 Wt.% H2O at ~5Kb in the range of compositions Ab100Ne0-An40Ne60). H2O-solubility in the (Anl) and (Ne) univariant melts was determined up to l0Kb (H2O contents: 4.7 Wt.%/1.1Kb and 850°C, 6.2 Wt. %/2Kb and 804°C, 10.8 Wt. %/5.2Kb and 672°C, l2.2 Wt.% /6.6Kb and 655°C, 13.2 Wt. %/7.3Kb and 652°C and 14(?) Wt.% /10Kb and 632°C ). The origin of water bubbles in quenched hydrous glasses is essentially attributed to the exsolution of the dissolved water in melts upon quenching.</p> <p> The sequence of P-T curves around a quaternary invariant point (~5Kb and ~635°C) in the system NaAlSiO4-KAlSiO4-SiO2-H2O was theoretically discussed. The most probable four P-T diagram types are proposed, one of which is expected to be the real one.</p> <p> Phase relations in the system NaAlSi3O3-NaAlSiO4-H2O are theoretically discussed up to ~15Kb. The discussion is largely based on the equilibrium compositions of invariant phases approximately estimated from data presented in Parts 1 and 2. Six invariant points are examined. Two of them, I5 and I6, have been predicted to occur; I5 is inferred to be located at ~13Kb/~500°C where five phases Jd, N-h I, Anl, Ne and V coexist, and I6 to be located at ~0.5Kb/-375°C where Ab, Ne, Anl, N-h I and V coexist. The phase relations around the other four are partly modified. The maximum P-T stability field of analcite is deduced. The stability field of solidus analcite is extremely large whereas that of liquidus analcite is very much limited. The maximum stability field of liquidus analcite is a small triangular area defined by three invariant points I1 (5.15Kb/657°C), I2 (11Kb/650°C) and I4 (12.5Kb/575°C).</p> / Thesis / Doctor of Philosophy (PhD)

<p> This is a study of the groundwaters and their associated rocks and minerals from the Lac du Bonnet batholith at the Underground Research Laboratory (URL), Pinawa, Manitoba, to assess the water-rock interaction in crystalline rocks by using Sr, O and U-series isotopes. Emphasis is also placed on the development of the analytical techniques.</p> <p> A high precision analytical technique of U-series isotopes has been developed in this study by using solid-source mass spectrometry. A precision of better than 1% (2σ) is achieved in determining the 234U/238U and 230Th/234U ratios using 10^-8 g of U and 10^-11 g of 230Th. The potential applications of this method is demonstrated by dating small speleothem samples and the results agree well with those of α-spectrometry. This method also applies well to precise determination of the 234U/238U ratios in groundwaters and igneous rocks and minerals using small quantities of samples. However, precise measurements of 230Th in igneous rocks and minerals are limited by the large 232Th tail in the Th mass spectrum. Even better precision is achievable if pure Th spike is used.</p> <p> An ICP-MS isotope dilution method is also developed for fast and precise determination of Sr concentrations in groundwater samples. A precision of 1% is routinely achieved by taking into account the dead-time effect of the Channel Electron Multiplier (CEM) and the sample-to-spike ratios.</p> <p> The isotope results of both the groundwaters and the host rocks and minerals have revealed the processes of water-rock interaction and water mixing through the history of the batholith. Strontium isotope systematics of the rocks and their constituent minerals have shown that Sr loss occurred on whole-rock scale during both the high-temperature alteration (about 2300 Ma ago) and the low-temperature alteration which lasted at least 450 Ma. The Sr loss is most pronounced in plagioclase of altered samples. Uranium-series results indicate the disequilibrium of both whole-rock samples and minerals, and migration of U on whole-rock scale in, at least, the last million years.</p> <p> The Sr and O isotopic results have shown that the groundwaters from the three sub-horizontal, successively deeper fracture zones (FZ) have distinct isotopic signature: 87Sr/86Sr= 0.715 to 0.719 and 𝛿18O=-13o/oo for FZ-3; 87Sr/86Sr= 0.720 to 0.729 and 𝛿18O=-13 to -20o/oo for FZ-2; 87Sr/86Sr= 0.730 to 0.738 and 𝛿18O=-13 to -17o/oo for FZ-1. Uranium-series results show that all the groundwaters are highly enriched in 234U and the 234U/238U activity ratios range from 2.6 to 7.7. Mixing of three groundwaters is indicated by the Sr and O isotopes and the elemental chemistry. The three end-members are fresh surface water, the deep fresh (possibly glacial melt) groundwater and the deep saline groundwater.</p> <p> Comparison between the rocks and associated groundwaters shows that Sr isotopic equilibrium exists between plagioclase of altered samples and the groundwaters. This similarity indicates the vulnerable mineral phase control, such as plagioclase in this case, of the isotopic signatures, hence, chemistry of the groundwaters.</p> / Thesis / Master of Science (MSc)

<p> The North Quarry (north of Ontario Highway 4) is located in Flamborough Ontario. In it, rocks of the Guelph formation are well exposed. The Guelph formation consists of dolomite and at the North Quarry has an average thickness of 30m. These rocks are cut by three predominant joint sets which have no indication of shear motion. The 030° set was formed as a result of compaction and loading; It appears to represent an upward joint propagation mirroring the Algonquin Arch trend. Joint sets 120° and 160° are a north western analogue to the conjugate pair described by Nickelson and Hough (1967) in the north eastern United States.</p> <p> Vein data and sampled minerals, using techniques such as cathodoluminescence, photoluminescence, and isotope analysis enable paragenesis of joint propagation and crystallization relationships to be inferred. Possible stress field configurations have been deduced from these data. The joint set 030° was the first to open. Next, a minor east-west trending set opened. Joint sets 120° and 160° are the last to open. The joints were infilled by cement in the order of Organics > Calcite > Sulphides > Iron Oxides. Buckle heaves in the quarry were unreliable indicators of neotectonic stress.</p> / Thesis / Bachelor of Science (BSc)

This dissertation is comprised of three independent but interconnected studies with the scope of further understanding uranium and iodine partitioning between apatite and fluid. The studies herein presented investigated: 1) brushite to apatite crystallization method; 2) the degree of uranium incorporation into apatite; 3) the degree of iodine incorporation into apatite. The importance of this work is assessing the role of apatite in immobilizing these elements, where uranium is a major component of spent nuclear fuel and iodine is a chemical analog of its radioactive isotope (129I). Once we understand the incorporation mechanisms, we will provide data that can be used in development of engineering barrier systems via add-on of phosphate minerals. In the first chapter we evaluate a method for the crystallization of apatite (Ca10(PO4)6(OH, F, Cl)2) using brushite (CaHPO4·2H2O) as initial material. The solutions evaluated for this transformation were NaCl, NaF, and KOH. Result yielded 100% apatite transformation from brushite when pH is 3.5 or greater. At a pH lower than 3.5, transformation yields monetite-apatite mixtures. Crystal size is reduced during the transformation from ~10 micrometer to ~1 micrometer. In the second chapter, degree of uranium uptake by apatite was evaluated. Phosphate minerals were crystallized from U-bearing NaCl solutions at 25-350°C. After experimental runs uranium concentrations in experimental solids and fluids were analyzed using Inductively Coupled Plasma – Mass Spectrometry. Additionally, characterization of the solids was performed via X-Ray Diffraction, Scanning Electron Microscopy and Electron Microprobe to confirm the brushite to apatite conversion. Results show that >90% of uranium was extracted from solution. Moreover, that the partitioning of uranium between apatite and fluid decreases with increasing temperature. In the third chapter apatite was crystallized from iodine-bearing solutions. The crystallization was evaluated at 39 and 200°C. Iodine concentration in solids were acquired via Electron Microprobe Analysis (EMPA) whereas iodine concentration in fluids were acquired via UV-Visible Spectrophotometry. Iodine concentrations in fluids yielded minimum depletion (0.1M) from initial iodine added to the system (0.1M). Partitioning data suggest that iodate (the oxidized form of iodine) is more compatible with apatite compared to iodide (the reduced state of iodine).

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To compare the effect of a standard commercial trace mineral dietary program to low levels of organic minerals on turkey performance, mineral excretion, bone strength, and carcass yield, day-old Hybrid poults (n=1,224) were randomly distributed to one of four treatments with 9 replicates. Experimental treatments consisted of: standard inorganic (SI) with a commercial supplementation program (Mn, Zn, Cu, Se), reduced inorganic (RI) with 10% level of SI, and two organic regimens of Bioplex®/Sel-Plex® (at the same level of RI during period 1 and 2 and at 2/3 of RI for period 3, 4, 5, and 6, or at the same level of RI for entire trial). Body weight (BW), body weight gain (BWG), feed conversion ratio (FCR), and feed intake (FI) were evaluated and fresh excreta were collected at d 28, 49, 70, 84, 105 and 133. Tibias and femurs were collected at d 49, 84 and 133. Trace mineral concentration in litter and carcass yield were determined at d 133. Overall, there was no significant effect on BW, cumulative BWG, FCR, or FI due to treatments (P < 0.05). The contents of Mn and Zn in excreta and litter were significantly reduced (P < 0.05) in Bioplex®/Sel-Plex® or RI diet compared to SI during the study. Cu excretion was significantly reduced at d 84 and 133. Tibias from the SI treatment had increased bone strength at d 49. Carcass yield at processing was significantly improved (P < 0.05) by feeding Bioplex®/Sel-Plex® treatments compared to the SI diet. To investigate the effect of organic or inorganic Zn combined with other trace minerals on turkey performance, immune response, and intestinal development, a 2 by 4 factorial design was utilized with coccidia vaccinated and non-vaccinated and 4 dietary treatments varying in level and source of Zn with Mn, Cu, and Se. A total of 2,376 day-old Hybrid turkeys were assigned to one of the combinations with 9 replicates of each. Dietary treatments consisted of: 1) standard inorganic (SI), Zn (150 ppm) with Mn (165 ppm), Cu (10 ppm), and Se (0.2 ppm); 2) reduced inorganic (RI), Zn, Mn, and Cu at 10% of SI, and Se at 0.2ppm; 3) organic 1 (O1), at the same level of RI; 4) organic 2 (O2), Zn (30 ppm) with the same level of Mn, Cu, and Se as O1. Body weight, BWG, FI and FCR were determined weekly. Bursa, thymus, and spleen were weighed, and duodenum and jejunum were collected at d 7, 14, 28, and 42. Peripheral blood was collected for T-lymphocyte populations on d 21, 28, and 42. Cumulative FI was influenced by vaccination (P=0.003). Cumulative BWG and BW were significantly decreased by vaccination except on d 14. Cumulative BWG increased in poults fed RI compared with those fed O2 (P=0.03). Poults fed O2 had significantly decreased BW when compared with RI after d 28. Cumulative FCR was not affected by diet and vaccination. Vaccination increased spleen weight on d 7 and thymus weight on d 42 (P < 0.05). The birds fed O2 had increased thymus weight when compared with those fed SI at d 7 (P < 0.05). The vaccinated poults had higher numbers of CD4+ T-cells than non-vaccinated birds on d 28 and d 42 (P < 0.05), and an interaction between diet and vaccination was observed (P < 0.05). Compared to non-vaccinated poults, CD4+/CD8+ ratio was significantly increased in vaccinated poults on d 42 (P = 0.0475). The villus height in vaccinated birds was significantly increased in the jejunum (P = 0.0012), but diets did not affect intestinal morphology. In summary, using low levels of organic or inorganic trace minerals is adequate to maintain turkey performance and immune response and decreased trace minerals excretion. / Ph. D.

Recently it has been concluded that the SiO₄ silicate tetrahedra in crystals behave as rigid bodies. This conclusion is based on analyses of the atomic displacement factors of Si and O atoms obtained from single crystal diffraction experiments wherein the amplitudes of atomic vibrations are ascribed to translational, librational and screw-correlated modes of motion for the entire SiO₄ group. If the displacement ellipsoids are considered to represent time averaged quadratic surfaces of equal configurational potential energy about the mean position of an atom, then an analysis of the these displacements should provide detailed information about the SiO₄ group and the crystal. The apparent SiO bond lengths recorded for silicates over a range of temperatures are typically either invariant or exhibit a contraction with increasing temperature. A rigid-body thermal analysis was completed for the tetrahedra in nine silicates whose structures have been determined over a range of temperatures from 15 K to 1250 K and whose tetrahedra seem to behave as rigid units. The coordinates provided by the analysis yield bond lengths and polyhedral volumes corrected for the librational motion of each silicate tetrahedron. The bond lengths and volumes estimated for tetrahedra with four bridging oxygens seem to increase with temperature at a faster rate than those with four nonbridging oxygen atoms. Those for tetrahedra with two or three nonbridging oxygen atoms tend to increase at an intermediate rate. An analysis of the rigid-body motion of coordinated polyhedra yields a simple but accurate expression for correcting bond lengths for thermal vibrations. Observed anisotropic displacement parameters for Si and O atoms indicate that the SiO₄ tetrahedra in quartz behave as rigid bodies. A configurational potential energy curve, constructed from the librational components of the rigid body motion of the tetrahedra, shows a double well for α quartz and a single well for β quartz when plotted as a function of the displacement of the O atom with temperature. The configurational energetics of α and β quartz are examined with a theoretical potential energy function based on parameters obtained from molecular orbital calculations. The calculations indicate that the temperature behavior of a quartz is governed by the energetics of the SiOSi angle, in contrast to β quartz which is governed by the energetics of the SiO bond. The mechanism of the α ⇌ β transition is examined in terms of the experimental and modeled configurational potential energy curves. Evidence for the proposal that π bonding is the driving mechanism for the transition is lacking. Structural and volume compressibility data for α-cristobalite were determined by single crystal X-ray diffraction methods for pressures up to ~1.6 GPa, where cristobalite undergoes a reversible phase transition. The bulk modulus was determined to be 11.5(7) GPa with a pressure derivative of 9(2). The SiOSi angle shows a greater decrease than observed for quartz and coesite while the SiO bond lengths and the OSiO angles remain essentially unchanged. The responses of V/V₀ and SiOSi angle to pressure for the silica polymorphs are compared and it is found that the percentage decrease in the volume is linearly correlated with the percentage decrease in the SiOSi angle, regardless of the framework structure type. A mathematical modeling of the energies of the structural changes that are induced by pressure suggests that the contribution to the total energy ascribed to Si0Si angle bending terms is the same in quartz and cristobalite. / Ph. D.