Raman spectroscopic measurements of various hydrogen bearing clathrate hydrates have been performed under high (< 1cm-1) and low resolution (>2 cm-1) conditions. Raman bands for hydrogen in most common clathrate hydrate cavities have been assigned. Unlike most clathrate hydrate guests, the general observation is no longer valid that the larger the clathrate cavity in which a guest resides, the lower the vibrational frequency. This is rationalized by the multiple hydrogen occupancies in larger clathrate cavities. Both the roton and vibron bands for hydrogen clathrates illuminate interesting quantum dynamics of the enclathrated hydrogen molecules. At 77K, the progression from ortho to para H2 occurs over a relatively slow time period (days). The para contribution to the roton region of the spectrum exhibits the triplet splitting also observed in solid para H2. The complex vibron region of the Raman spectrum has been interpreted by observing the change in population of these bands with temperature and with isotopic substitution by deuterium. Raman spectra from H2 and D2 hydrates suggest that the occupancy patterns between the two hydrates are analogous. The Raman measurements demonstrate that this is an effective and convenient method to determine the relative occupancy of hydrogen molecules in different clathrate cavities.

Solid-state NMR spectroscopy is used to investigate strong hydrogen bonds in a variety of solids. NMR measurements of the 2H nuclear quadrupole coupling (CQ) and nuclear magnetic shielding tensors are performed on samples of trimethylammonium chloride (TMAC), protonated 1,8-bis(dimethylamino)napthalene (DMANH+), and potassium and sodium bifluoride. 2H CPMAS is used to obtain high quality spectra while reducing experimental time. From spectral simulations, values of 127, 36, 59 and 58 kHz are determined for the 2H CQ of TMAC, DMANH+ CF3SO3-, NaHF2 and KHF2, respectively. The 2H CPMAS spectrum of TMAC shows a minor secondary component resulting from a solid phase in which the trimethylammonium cation is experiencing precessional motion. At high temperature the 2H CPMAS spectrum of DMANH+ shows unexpected spinning sideband lineshapes because of residual dipolar coupling to 14N. The experimental 2H CQ values are corroborated by ab-initio and DFT calculations; for DMAN and the bifluorides the 2H CQ values are averaged over the potential energy surface to improve the computational quality. Large values of the isotropic chemical shift (>10 ppm) are observed for all of the hydrogen-bonded deuterons. To complement the 2H NMR work, other nuclei in the compounds of interest are investigated, for TMAC these include: 35Cl, 37Cl, 1H, 14N, 15N. The 35Cl CQ shows a small, but observable deuterium/proton isotope effect. Quadrupolar and chemical shift parameters for assorted nuclei in TMAC are calculated at various N-H distances, demonstrating the strong dependence of the chlorine and hydrogen parameters on the proton position. For DMANH+ the 15N CPMAS spectrum of a static sample of DMANH+-d1 provides a value for the average dipolar 15N-D coupling constant of 870±30 Hz, corresponding to a distance of 1.29 A. Spectra of the counterions in the bifluoride salts are obtained, providing CQ values of 123 kHz and 1.141 MHz for 39K and 23Na, respectively.

Polarized Raman spectroscopy has been used to measure the deuterium isotope effect, (delta)pK = pKD2O – pKH2O, for the second ionization constant of sulfuric acid in the temperature range of 25 °C to 200 °C at saturation pressure. Results for pK in light water agree with the literature within ± 0.034 pK units at alltemperatures under study, confirming the reliability of the method. The ionization constant of deuterated bisulfate, DSO4-, differs significantly from previous literature results at elevated temperatures. This results in an almost constant (delta)pK ≈ 0.425 ± 0.076 over the temperature range under study. Differences in (delta)pK values between the literature and current results can be attributed to the effect of dissolved silica from cell components. The new results are consistent with (delta)pK models that treat the temperature dependence of (delta)pK by considering differences in the zero-point energy of hydrogen bonds in the hydrated product and reactant species. The phosphate hydrolysis equilibrium was measured between the temperatures of 5 °C and 80 °C and the borate/boric acid equilibrium between the temperatures of 25 °C and 200 °C. The high alkalinity and temperatures experienced by these two systems had a significant impact on the glass dissolution and equilibrium. / Raman spectroscopy was used to measure the small differences in ionization constants for weak acids/bases as a function of temperature. / University of Guelph, Atomic Energy of Canada Limited (AECL), Bruce Power, University Network of Excellence in Nuclear Engineering (UNENE), National Sciences and Engineering Research Council of Canada (NSERC), Natural Resources Canada, Ontario Power Generation (OPG), Canada Foundation for Innovation

This research takes a multidisciplinary approach to comprehensively investigate the material and mechanical properties as well as pore water chemistry of the Bearpaw shale. This made it possible to characterize how these properties relate to the mechanical strength of this material. The results of this research challenge our ideas of the hydrogeology and of the geological history of the region. Core samples of the Bearpaw Formation and the overlying glacial till were collected from a field site in southern Saskatchewan, Canada. A combination of laboratory tests including multi-staged oedometer tests, constant rate of strain oedometer tests, specialized triaxial swell tests, along with pore water chemistry and finite element modelling were used to meet the following objectives: (1) To investigate the material properties and compression behaviour of the Bearpaw in addition to assessing disturbance due to specimen size; (2) Examine the time dependent behaviour of the Bearpaw and the transferability of time rate models developed for soft soils to stiff soils; (3) Examine the swelling potential and behaviour of the Bearpaw Formation and the influence of boundary conditions on this behaviour, while assessing the applicability of the swell concepts developed for compacted materials to a naturally swelling clay material; and (4) Constrain the depositional age of the till overlying the Bearpaw Shale. Contrary to what is seen in soft soils, smaller sized specimens were found to reduce disturbance, and produce more accurate and consistent results. Creep was found to follow the same laws as it does in soft soils, calling into question whether the use of preconsolidation pressure to predict geological history in stiff clays is appropriate. There was significant variation in the observed swell pressures of samples of the same size and depth. Finally, the glacial till at site was found to belong uniquely to the Battleford Formation and ranges in age from 22,500 to 27,500 years which is much younger (over 100,000 years younger) than previously believed. / Thesis (Ph.D, Geological Sciences & Geological Engineering) -- Queen's University, 2010-01-29 01:34:14.071

No description available.

Surface mining of oil sands results in extensive land disturbance, earth movement and water usage. After mining, the disturbed landscapes must be reconstructed and reclaimed as natural landforms. There are numerous challenges associated with understanding the responses of these landforms over time, including a need to track and characterize water movement through closure landforms to understand the hydrological responses of these landforms over time. This study attempted to use natural stable isotopes of water (δD and δ18O) to identify and characterize source waters from various closure landforms at an oil sands mine site. The study area is Syncrude‟s Mildred Lake mine, an open pit oil sands mine located in northern Alberta. A variety of groundwater, surface water and soil samples from a variety of landforms (overburden dumps, composite and mature fine tailings areas, tailings sand structures and freshwater reservoirs) were collected in an attempt to fully represent the isotopic distribution of waters across the mine site. Laboratory analysis of δD and δ18O was done on all samples. The local meteoric water line first established by Hilderman (2011) was redeveloped with additional precipitation data and calculated to be δD=7.0(δ18O) -18.6‰. A natural evaporation line having a slope of 5.3 was calculated for the mine site with samples collected from three surface water ponds on the mine site. Five primary source waters were identified on the mine site: process affected water/tailings, rainfall, snow, interstitial shale water and Mildred Lake water. It was found that these sources of water generally have unique natural stable water isotope signatures. Process affected water at the site generally had an enriched signature compared to other mine waters. The enrichment was attributed to fractionation from the recycle water circuit and natural evaporation. The characterizations of these source waters were then used in several hydrogeological examples to demonstrate that natural stable water isotopes can be applied to water balance estimates and to identify water movement processes related to closure landforms.

No description available.

The electric charge distribution of molecules such as H₂ and D₂ is inversion-symmetric so that permanent dipole moments do not exist: such molecules are infrared-inactive. It is therefore interesting that gaseous, liquid, and solid hydrogen and its isotopes actually absorb infrared radiation, for example if gas densities are sufficiently high. The observed absorption arises from electric dipole moments induced by intermolecular interactions. It is of a supermolecular origin, due to binary (or higher-order) molecular complexes that may be transient (i.e., in a collisional encounter) or relatively stable (van-der-Waals molecule). Interaction-induced electric dipoles arise from the same mechanisms that generate the intermolecular forces: exchange forces, dispersion forces, and multipolar induction. Recently the induced dipole and potential energy surfaces of H₂ pairs have been obtained by advanced quantum-chemical calculations. Interaction-induced absorption, more commonly called collision-induced absorption (CIA), by H₂ pairs is an important opacity source in the atmospheres of various types of planets and cool stars, such as late stars, low-mass stars, brown dwarfs, certain white dwarfs, etc., and therefore of special astronomical interest. The emission spectra of cool white dwarf stars differ significantly from the expected blackbody spectra of their cores, mainly due to collision-induced absorption by collisional complexes of hydrogen and helium in the stellar atmospheres. Before proceeding to the frequencies and temperatures of interest it is good to check the new potential energy surface and induced dipole surface in all possible ways by comparison with existing isotopic laboratory measurements. Furthermore, the new potential energy surface is directly compared with previously available, well established intermolecular potential energy surfaces. The electric charge distributions of deuterium and hydrogen are very similar. The new potential energy and induced dipole surfaces were originally obtained to facilitate the computation of the collision-induced absorption of hydrogen. However, by replacing the rotovibrational wavefunctions of H₂ with those of D₂ the surfaces can also be used to calculate the collision-induced absorption of deuterium pairs, thereby probing them further. At the temperature of 298K existing measurements of the collision-induced absorption of D₂--D₂ gas are compared with our quantum scattering calculations in the D₂ fundamental band (approximately 2,500cm⁻¹ to 4,500cm⁻¹). Furthermore, measurements of the collision-induced absorption of deuterium (D₂) in the D₂ first overtone band (about 5,250cm⁻¹ to 7,250cm⁻¹) at 201K are reported. These measurements are compared with ab initio calculations of the absorption spectra. Close agreement of measured and calculated spectra is seen.

Mass, solute (chloride), isotope (deuterium) and thermal balances were completed at Perry Lakes, two semi-permanent 'water table' lakes near Perth, Western Australia. All balance components except groundwater discharge/recharge were measured independently. These difficult to measure groundwater components of lake-aquifer interaction were estimated by integrating mass, solute and chloride data in sequential 4 day balances spanning two years. Before urbanisation, such wetlands functioned predominantly as flow-through lakes. Now, large winter storm water inputs (and summer artificial level maintenance pumped locally from groundwater) dominate. In East Lake these inputs together comprise 42% of the annual water budget; groundwater discharge is reduced to just 2%. Even under flow-through conditions, these 'non natural' inputs are so large East Lake always tends towards a recharge state and commonly becomes a local groundwater mound. Flow-through is established in both lakes over winter. Initially each lake functions separately however as winter progresses shared capture and release zones are established. Maintenance of lake levels in early summer forces East Lake back to recharge status. Sediment heat flux (Qse) is significant in these very shallow lakes. Over summer Qse was negative, with a net movement of heat from the water into the sediments which act as a seasonal heat sink. In winter Qse was positive and stored summer heat was returned to the water column. This flux at times exceeded 40 W m-2. Evaporation was determined independently by floating pan, leaving Qse as the thermal balance residual. Ignoring Qse, annual evaporation determined by thermal balance was over estimated by 7%. Over and under estimates of individual 12 day balance period evaporation exceeded 50%. Monthly Class A (Perth airport) pan coefficients varied from 0.54 (January) to 0.86 (September). Ten empirical equations for evaporation were calibrated and compared with the East Lake floating pan. Best performer was the Makkink which tracked the floating pan closely throughout all seasons. Poorest were the Penman, DeBruin-Keijman, Priestly-Taylor and Brutsaert-Stricker which grossly over estimated late winter evaporation. Transpiration from Typha orientalis, estimated using hydrograph techniques was 43% of open water evaporation in summer and 28% annually. Temperature controlled evaporation pans (tracking lake temperature) experimentally determined the local deuterium content of lake evaporate ƒÔE, required for isotopic balances. Techniques employing pans evaporated to dryness and pans evaporated at constant volume were run in tandem continuously for two years. This study singularly integrates mass, solute and isotope balances thereby allowing groundwater components to be accurately quantified. The isotope balances are unique, being the only such balances incorporating experimentally derived local deuterium values of lake evaporate. This study represents the only thermal balance, the only accurate determination of pan-lake coefficients and the first calibration of commonly used empirical evaporation equations for Swan Coastal Plain wetlands. Groundwater levels in the western suburbs of Perth have declined over 40 years and a disproportionate larger decline now seriously threatens Perry Lakes. Modelling suggests regional groundwater extraction exceeds recharge. Wetland managers can no longer maintain East Lake via local groundwater extraction. Artificial recharge using imported surface and waste water are possible future management options.

Thesis (Ph.D.); Submitted to New Mexico State Univ., Las Cruces, NM (US); 1 May 2003. / Published through the Information Bridge: DOE Scientific and Technical Information. "JLAB-PHY-03-22" "DOE/ER/40150-2731" David McKee. 05/01/2003. Report is also available in paper and microfiche from NTIS.