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Radioactive decay of U, Th and K contributes to noble gas radiogenic ingrowth in different geological reservoirs, which distinguish mass origin and reveal its transport pathway. Compared with minerals and fluid inclusions, porewater is more relevant in revealing the mobile mass origin and transport in the porous, deep subsurface environment. Hence, the approaches for porewater noble gas extraction and analysis are of great meaning to geochemistry and hydrogeology. However, all five stable noble gases in rock porewater are difficult to acquire because of possible air contamination during storage and difficulty of noble gas separation. This dissertation is dedicated to exploring novel noble gas extraction and analysis methods from rock porewater. Two porewater gas extraction methods were developed for crystalline and sedimentary rocks, respectively. Temperature-controlled heating was applied to crystalline rocks. Out-diffusion in Al-foil bags was used for Ordovician sedimentary rocks. Regarding noble gas methodology, a newly designed pneumatic processing line was built to explore an iterative polished stainless steel wool trapping method to separate Kr from Ar. The iterative trapping method yields > 95% trapping efficiency for Kr and > 99% trapping efficiency for Xe. Simultaneously, comparable and steady noble gas sensitivities and noble gas isotope ratios were attained from air standard aliquots. From heating experiments on crystalline rock porewater, the consistency of noble gas ratios between headspace gas and rock porewater illustrates that this extraction method is valid for crystalline rock. This work provides a benchmark for noble gas extraction from crystalline rock porewater. With room-temperature out-diffusion method in Al-bag, noble gas ratios and concentrations of Ordovician sedimentary rocks reveal crustal features. The measured noble gas ratios in Ordovician sedimentary cores agree with measurements previously made in the Ordovician brine samples from the western flank of the Michigan Basin. The Ordovician porewater residence time is quantitatively estimated with both He and Xe radiogenic ingrowth, yielding an average of 251 million years (m.y.), which is comparable with the previous He accumulation time estimate at the same study site that yielded 260 m.y.. The remarkable preservation of gases in Al-foil bags provides an economic and efficient possibility for noble gas out-diffusion sampling. In summary, the exploration of porewater noble gas extraction and all five noble gas analysis methodology gives satisfying noble gas results and geological information. These original developments are of great meaning to the future work of the noble gas laboratory at the University of Ottawa.

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Distributions of water transit times (TTDs), and related storage-selection (SAS) distributions, are spatially integrated metrics of hydrological transport within landscapes. Recent works confirm that the form of TTDs and SAS distributions should be considered time variant-possibly depending, in predictable ways, on the dynamic storage of water within the landscape. We report on a 28 day periodic-steady-state-tracer experiment performed on a model hillslope contained within a 1 m3 sloping lysimeter. Using experimental data, we calibrate physically based, spatially distributed flow and transport models, and use the calibrated models to generate time-variable SAS distributions, which are subsequently compared to those directly observed from the actual experiment. The objective is to use the spatially distributed estimates of storage and flux from the model to characterize how temporal variation in water storage influences temporal variation in flow path configurations, and resulting SAS distributions. The simulated SAS distributions mimicked well the shape of observed distributions, once the model domain reflected the spatial heterogeneity of the lysimeter soil. The spatially distributed flux vectors illustrate how the magnitude and directionality of water flux changes as the water table surface rises and falls, yielding greater contributions of younger water when the water table surface rises nearer to the soil surface. The illustrated mechanism is compliant with conclusions drawn from other recent studies and supports the notion of an inverse-storage effect, whereby the probability of younger water exiting the system increases with storage. This mechanism may be prevalent in hillslopes and headwater catchments where discharge dynamics are controlled by vertical fluctuations in the water table surface of an unconfined aquifer. Plain Language Summary Volumes of water reside within landscapes for varying amounts of time before they are discharged to a stream. That length of time determines how long the water has to interact chemically with soil and rock, and therefore influences the chemistry of water that ends up in stream channels. Quantifying the full range and variability of those travel times remains a challenge. We built an experimental hillslope, which allows us to keep track of all the water that enters and exits the soilsomething that is difficult to accomplish in open environmental systems. We introduced chemically distinct water into the hillslope at specific points in time and followed the movement of that water within, and upon exit from the soil. We discovered that the water being discharged from the hillslope tends to have resided in the landscape for shorter lengths of time when the hillslope is very wet (like a wetted sponge) than when it is very dry (like a dry sponge). This insight helps us understand how different rainfall regimes, and the associated wetness of the landscape, can potentially influence water transit times through the landscape, and their relationship with stream chemistry.

The photoionization cross sections of small fullerenes (C28, C32, C40, C44, and C50), and the outer and near-outer shells of atoms (noble gases, alkaline earth) confined endohedrally inside a C60 molecule are calculated employing a time-dependent local density approximation formulation. Plasmon and confinement resonances are found to be a general feature of these cross sections, and dramatic interchannel coupling effects, significantly increasing the atomic cross sections, are exhibited in all cases in the vicinity of the C60 plasmons. Hybridization effects, the mixing of the atomic and cage bound state wave functions, are also found, but no systematics of the hybridization present themselves. Also, in the case of Ar@C60, Inter-atomic Columbic decay (ICD) has been found and studied.

Iceland possesses numerous subglacial volcanoes (tuyas and tindars) that act as geological records of the thick ice sheets that once spanned across the country. Flat topped volcanic summits, which were able to penetrate through the covering ice, provide an estimate of the ice sheet's minimum thickness at the time the volcano was in its final eruptive stage. Iceland not only provides a large number of potential subglacial edifices to sample but is geologically interesting as it sits above a magmatic hotspot and spreading ridge, providing a long term record of volcanism during considerable climate variability. However, it is unknown exactly in which glacial cycle these volcanic edifices formed, due to the lack of accurate and reliable eruption ages. Helium isotopes are valuable tracers of the mantle source for the origin of volcanic rocks. Helium isotopes are comprised of a mixture of magmatic helium trapped whilst in the mantle, cosmogenic helium built up by interaction with cosmic rays during surface exposure and radiogenic helium produced from the in situ decay of U and Th. These helium components yield invaluable information on the mantle source, time of eruption and length of exposure respectively. The principle aim of this study is to determine whether reliable and accurate eruption ages of basaltic subglacial volcanoes in Iceland are possible, by applying a relatively new geochronological tool: U-Th/He dating. These eruption ages combined with cosmogenic derived 3He surface exposure ages of the summits helps to establish ice surface elevation and thickness fluctuations over time. Olivine bearing basalt samples were acquired from 14 tuyas, 4 tindars and 1 shield volcano across the Western and Northern Volcanic Zones in Iceland (WVZ and NVZ). Samples were collected from the base of each edifice for U-Th/He dating and the summits of 3 tuyas for cosmogenic 3He surface exposure dating. Olivine phenocrysts were hand-picked and analysed on two noble gas mass spectrometers (VG5400 and Helix-MC instruments). As part of the analytical procedure for these techniques, magmatic helium trapped in the olivine grains is also analysed. The mantle helium isotope ratios indicate that nearly all edifices sampled obtain a MORB-like source (1-18RA) except for an OIB-like (24RA) centrally located tuya, Bláfell. The helium ratios acquired in the NVZ are lower (4-11RA) than those in the WVZ (8-20RA). There are no significant differences seen in the mantle components between the different types of edifice sampled. Mantle helium isotope ratios confirm the heterogeneity of the mantle beneath Iceland. The cosmogenic 3He exposure ages of Hlöđufell and Bláfell in the WVZ and Gaesafjöll in the NVZ are determined as 0.5±7.4ka, 67±0.7ka and 108±46ka respectively. This study presents the first 3He cosmogenic exposure age determined to be over 20ka in Iceland. The low concentrations of U and Th observed in Icelandic olivines (0.002-0.04 nmol/g and 0.01-0.1 nmol/g respectively) prevent any reliable disequilibrium ages to be established. Minimum secular equilibrium U-Th/He ages are determined and provide a range of erroneously large eruption ages (0.4 - 80.4 Ma), due to potential helium implantation and under-detection of 3He released during sample analysis. Progress can be made towards determining accurate eruption ages for Icelandic basalts if certain factors are adhered to and various sources of helium are separated effectively.

Abstract The present thesis deals with the nuclear magnetic resonance (NMR) spectroscopy of small solutes applied to the studies of liquid crystals and molecular sieves. In this method, changes induced by the investigated environment to the static spectral parameters (i.e. nuclear shielding, indirect and direct spin-spin coupling and quadrupole coupling) of the solute are measured. The nuclear shielding of dissolved noble gases is utilized for the studies of thermotropic liquid crystals. The relation between the symmetry properties of mesophases and the nuclear shielding is described. The different interaction mechanisms perturbing the observed noble gas nuclear shielding are discussed, particularly, the role of long-range attractive van der Waals interactions is brought out. The suitability of the noble gas NMR spectroscopy to the studies of lyotropic liquid crystals is investigated in terms of nuclear shielding and quadrupole coupling interactions. In molecular sieve systems, the effect of inter- and intracrystalline motions of solutes on their NMR spectra is discussed. A novel method for the measurement of the intracrystalline motions is developed. The distinctions in the 13C shielding of methane adsorbed in AlPO4-11 and SAPO-11, two structurally similar molecular sieves differing in composition, are indicated.

Noble gas and halogen data from a suite of Icelandic samples are presented. Iceland combines hotspot volcanism, a spreading ridge and abundant subglacially erupted samples. This combination allows for samples that erupted under high enough pressures to retain a measurable mantle volatile content, and also display signatures representing interaction between ocean island basalt (OIB) and mid-ocean ridge basalt (MORB) mantle sources.Erupted samples used to determine the mantle’s halogen and noble gas content have undergone a degassing process that can alter their volatile composition. An existing disequilibrium degassing model is developed with the modified model taking into account the evolution of the major volatiles over a multi-stage process and the different conditions present during magma ascent and quenching. The modified model allows substantially lower elemental noble gas ratios to be reached under disequilibrium conditions than allowed by the original model. Initial CO2 concentrations, pressure, diffusivity, ascent rate and degree of disequilibrium are shown to be critical parameters for this model. Final degassed noble gas concentrations are most affected by the surface quenching stage of an eruption, whereas noble gas elemental ratios can be primarily determined during magma ascent. In applying this model to MORB and OIB sample suites, the 3He/22Ne ratio of the MORB source mantle is constrained to be lower than 4.4, similar to estimates for the OIB source mantle. Additionally the most straightforward match between the degassing model and OIB helium and neon data suggest the OIB source mantle has 3He concentrations similar to or lower than the MORB source mantle. This finding requires a model for the OIB source mantle in which a high 3He/4He component is added to a helium-poor protolith.Noble gas studies are hampered by the large, isotopically atmospheric component typically found in Icelandic subglacial samples, which can swamp other signatures. Detailed analysis of a volatile rich sample from SW Iceland shows evidence for more than one ‘contaminant’ component and that two component fits used incorrectly can produce misleadingly precise source mantle noble gas ratios. Multi component best fits to noble gas elemental ratios find that four components are present in samples from this region. These components are unfractionated air, fractionated air and a mantle component which shows some variation due to degassing. Combining the disequilibrium degassing model with component resolution allows limits to be placed on the source mantle composition for this sample. The light noble gas source composition is compatible with mixing between a solar (‘direct nebula’) component and a MORB-like component. This direct nebula signature is at odds with an implanted signature seen in both Ne and Kr for the convecting mantle, and shows that both accretionary volatile origins must have contributed during the Earth’s formation. The heavy noble gases show an elemental abundance pattern which is distinct from air and solar patterns, and trends towards seawater. This confirms the presence of a recycled volatile signature in Iceland’s mantle but it is not possible to further constrain the origin of this signature.The Icelandic halogen data shows no evidence for significant fractionation during degassing or melt generation. Source estimates for the Br/Cl and I/Cl ratios for Iceland’s plume are found to be (1.56±0.03) x 10-3 and (3.1±0.3) x 10-5, compatible with estimates for the MORB source mantle. Halogen source concentrations in central Iceland are found to be approximately three times higher than estimates for the convecting mantle and correlate with the regions of Iceland that show high 3He/4He ratios and high source water contents. This may indicate a recycled halogen signature associated with Iceland’s proposed mantle plume.

Gas hydrates are molecular host-guest mixtures where guest gas species are encapsulated in host water networks. They play an important role in gas storage in aqueous environments at relatively low pressures, and their stabilities are determined by weak interactions of the guest species with their respective host water frameworks. Thus, the size and the amount of the guest species vary, depending on the size of the empty space provided by the host water structures. The systems studied here are noble gas (He, Ne, Ar) and diatomic (H2) hydrates. Because of the similarity of the guests' sizes between the noble gases and the di-atomic gases, the noble gas hydrates act as simple models for the di-atomic gas hydrates. For example, He, Ne and H2 have approximately the same size. Density functional theory calculations are used to obtain the ground state formation enthalpies of each gas hydrate, as a function of host network, guest stoichiometry, and pressure. Dispersion effects are investigated by comparing various dispersion corrections in the exchange-correlation functionals (semi-local PBE, semi-empirical D2 pair correction, and non-local density functionals i.e. vdW-DF family). Results show that the predicted stability ranges of various phases agree qualitatively, although having quantitative difference, irrespective of the methods of the dispersion corrections in the exchange-correlation functionals. Additionally, it is shown in gas-water dimer interaction calculations that all DFT dispersion-corrected functionals overbind significantly than the interaction acquired by the coupled-cluster calculations, at the CCSD(T) level, which is commonly accepted to provide the most accurate estimation of the actual interaction energy. This could lead to an overestimation of the stability of the hydrate mixtures. Further study in the gas-water cluster indicates that less overbinding effect is found in the cluster than in the dimer. This implies that the overbinding energy caused by DFT might become less pronounce in the solid phase. Graph invariant topology and a program based on a graph theory are used to assign protons based on the 'ice rule' to fulfill the incomplete experimental structural data such as unknown/unclear positions of protons in the host water lattices. These methods help constructing host water networks for computational calculations. Several configurations of the host water structures are tested. Those configurations having lowest enthalpies are used as the host water networks in this research. Furthermore, the enthalpic spread between the configurations having the highest and the lowest enthalpy in the pure water ice network is very small (about 10 meV per water molecule). Nevertheless, it is still unclear to conclude that this protonic effect is also trivial in the gas-water compound. Therefore, this study also calculates the enthalpies of the gas-water mixtures having various proton configurations in the host water networks. Results indicate that very small enthalpic distributions among the proton configurations are found in the compounds as well. Furthermore, the enthalpic spread is almost constant as pressure increases. This suggests there is no pressure effect in the enthalpy gap amoung the proton distributions in both pure water ice and the gas-water compounds. Predicted stable phases for the noble gas compound systems are based on four host water networks, namely, ice Ih, II and Ic, and the novel host water network S!. The He-water system adopts ice Ih, II and Ic network upon increasing pressure. In the Ne-water system, a phase sequence of Sx/ice-Ih, II and Ic with a competitive hydrate phase in the S! host network at very low pressure is found. This is similar to the phase evolution of the H2-water system. For the Ar-water mixture, only a partially occupied hydrate in the Sx host network is found stable. This Sx phase becomes metastable if taking the traditional clathrates (sI and sII) into account. This result agrees very well with the experiment suggesting only two-third filling is found the large guest gases i.e. CO2. For the diatomic guest gas compound systems, the traditional clathrate structure (sII) that found to be existed experimentally in the H2-H2O system is also included in this study together with those four host water networks. Predicted phase stability sequence as elevated pressure is as follows: Sx, ice-Ih, II and Ic. This computationally prediction agrees very well with experiment. Results in this work suggest that the compound based on the traditional clathrate structure II (sII) host water framework is found to be metastable with respect to the decomposition constituents - in this case, they are pure water ice and the S!. The metastability of the hydrogen hydrates based on the sII structure might due to zero-point motions or other dynamic/entropic mechanisms uncovered in this research. Dynamic studies concerning the transition states of the hydrogen guest molecules in three competitive phases at very low pressure (less than 10 kbar), based on Sx, ice-Ih, and ice-II host water network, are considered. The energy barriers required by the hydrogen guest molecules in those three host frameworks are calculated by using Nudged Elastic Band (NEB) method. Results suggest that the hydrogen molecules are more mobile in the Sx than the other two host structures significantly. In the S! host water network, the energy barrier is about 25 meV/hydrogen molecule. This energy is about the room temperature suggesting that the hydrogen guest molecules are easily mobile in the Sx host water network if there is an empty site adjacent to them.

On Site Inspection is the final measure for verifying compliance of Member States with the Comprehensive Nuclear-Test-Ban Treaty. In order to enable the use of ³⁷Ar as a radiotracer for On Site Inspection, the sources of radioargon background must be characterized and quantified. A radiation transport model of the University of Texas at Austin Nuclear Engineering Teaching Laboratory (NETL) TRIGA reactor was developed to simulate the neutron flux in various regions of the reactor. An activation and depletion code was written to calculate production of ³⁷Ar in the facility based on the results of the radiation transport model. Results showed ³⁷Ar production rates of (6.567±0.31)×10² Bq·kWh⁻¹ in the re- actor pool and the air-filled irradiation facilities, and (5.811±0.40)×10⁴ Bq·kWh⁻¹ in the biological shield. Although ⁴⁰Ca activation in the biological shield was found to dominate the total radioargon inventory, the contribution to the effluent release rate would be diminished by the immobility of Ar generated in the concrete matrix and the long diffusion path of mobile radioargon. Diffusion of radioargon out of the reactor pool was found to limit the release rate but would not significantly affect the integrated release activity. The integrated ³⁷Ar release for an 8 hour operation at 950 kW was calculated to be (1.05±0.8)×10⁷ Bq, with pool emissions continuing for days and biological shield emissions continuing for tens of days following the operation. Sensitivity analyses showed that estimates for the time-dependent concentrations of ³⁷Ar in the NETL TRIGA could be made with the calculated buildup coefficients or through analytical solution of the activation equations for only (n,[gamma]) reactions in stable argon or (n,[alpha]) reactions in ⁴⁰Ca. Analyses also indicated that, for a generalized system, the integrated thermal flux can be used to calculate the buildup due to air activation and the integrated fast flux can be used to calculate the buildup due to calcium activation. Based on the results of the NETL TRIGA, an estimate of the global research reactor source term for ³⁷Ar and an estimate of ground-level ³⁷Ar concentrations near a facility were produced. / text