Gas hydrate investigation at the Amsterdam mud volcano

We investigated gas hydrate in situ inventories as well as the composition and principal transport mechanisms of fluids expelled at the Amsterdam mud volcano (AMV; 2,025 m water depth) in the Eastern Mediterranean Sea. Pressure coring (the only technique preventing hydrates from decomposition during recovery) was used for the quantification of light hydrocarbons in near-surface deposits. The cores (up to 2.5 m in length) were retrieved with an autoclave piston corer, and served for analyses of gas quantities and compositions, and pore-water chemistry. For comparison, gravity cores from sites at the summit and beyond the AMV were analyzed. A prevalence of thermogenic light hydrocarbons was inferred from average C1/C2+ ratios <35 and d13C-CH4 values of -50.6 per mil. Gas venting from the seafloor indicated methane oversaturation, and volumetric gas-sediment ratios of up to 17.0 in pressure cores taken from the center demonstrated hydrate presence at the time of sampling. Relative enrichments in ethane, propane, and iso-butane in gas released from pressure cores, and from an intact hydrate piece compared to venting gas suggest incipient crystallization of hydrate structure II (sII). Nonetheless, the co-existence of sI hydrate can not be excluded from our dataset. Hydrates fill up to 16.7% of pore volume within the sediment interval between the base of the sulfate zone and the maximum sampling depth at the summit. The concave-down shapes of pore-water concentration profiles recorded in the center indicate the influence of upward-directed advection of low-salinity fluids/fluidized mud. Furthermore, the SO42- and Ba2+ pore-water profiles in the central part of the AMV demonstrate that sulfate reduction driven by the anaerobic oxidation of methane is complete at depths between 30 cm and 70 cm below seafloor. Our results indicate that methane oversaturation, high hydrostatic pressure, and elevated pore-water activity caused by low salinity promote fixing of considerable proportions of light hydrocarbons in shallow hydrates even at the summit of the AMV, and possibly also of other MVs in the region. Depending on their crystallographic structure, however, hydrates will already decompose and release hydrocarbon masses if sediment temperatures exceed ca. 19.3°C and 21.0°C, respectively. Based on observations from other mud volcanoes, the common occurrence of such temperatures induced by heat flux from below into the immediate subsurface appears likely for the AMV.

(Table 3) Geochemistry of borehole fluids of ODP Hole 137-504B

Circulation of seawater through basaltic basement for several million years after crustal emplacement has been inferred from studies of surface heat flow, and may play a significant role in the exchange of elements between the oceanic crust and seawater. Without direct observation of the fluid chemistry, interpretations regarding the extent and timing of this exchange must be based on the integrated signal of alteration found in sampled basalts. Much interest has thus been expressed in obtaining and analyzing fluids directly from basaltic formations. It has been proposed that open oceanic boreholes can be used as oceanic groundwater wells to obtain fluids that are circulating within the formation. Water samples were collected from the open borehole in Hole 504B prior to drilling operations on Leg 137, with the original intention of collecting formation fluids from the surrounding basaltic rocks. Past results have yielded ambiguous conclusions as to the origin of the fluids recovered-specifically, whether or not the fluids were true formation fluids or merely the result of reaction of seawater in the borehole environment. The chemistry of eight borehole fluid samples collected during Leg 137 is discussed in this paper. Large changes in major, minor, and isotopic compositions relative to unaltered seawater were observed in the borehole fluids. Compositional changes increased with depth in the borehole. The samples exhibit the effect of simple mixing of seawater, throughout the borehole, with a single reacted fluid component. Analysis and interpretation of the results from Leg 137 in light of past results suggest that the chemical signals observed may originate predominantly from reaction with basaltic rubble residing at the bottom of the hole during the interim between drilling legs. Although this endeavor apparently did not recover formation waters, information on the nature of reaction between seawater and basalt at the prevalent temperatures in Hole 504B (>160°C) has been gained that can be related to reconstruction of the alteration history of the oceanic crust. Isotopic analyses allow calculation of element-specific water/rock mass ratios (Li and Sr) and are related to the extent of chemical exchange between the borehole fluids and basalt.

Tight-Binding Approximations in 1D and 2D Coupled-Cavity Photonic Crystal Structures

Light confinement and controlling an optical field has numerous applications in the field of telecommunications for optical signals processing. When the wavelength of the electromagnetic field is on the order of the period of a photonic microstructure, the field undergoes reflection, refraction, and coherent scattering. This produces photonic bandgaps, forbidden frequency regions or spectral stop bands where light cannot exist. Dielectric perturbations that break the perfect periodicity of these structures produce what is analogous to an impurity state in the bandgap of a semiconductor. The defect modes that exist at discrete frequencies within the photonic bandgap are spatially localized about the cavity-defects in the photonic crystal. In this thesis the properties of two tight-binding approximations (TBAs) are investigated in one-dimensional and two-dimensional coupled-cavity photonic crystal structures We require an efficient and simple approach that ensures the continuity of the electromagnetic field across dielectric interfaces in complex structures. In this thesis we develop \textrm{E} -- and \textrm{D} --TBAs to calculate the modes in finite 1D and 2D two-defect coupled-cavity photonic crystal structures. In the \textrm{E} -- and \textrm{D} --TBAs we expand the coupled-cavity \overrightarrow{E} --modes in terms of the individual \overrightarrow{E} -- and \overrightarrow{D} --modes, respectively. We investigate the dependence of the defect modes, their frequencies and quality factors on the relative placement of the defects in the photonic crystal structures. We then elucidate the differences between the two TBA formulations, and describe the conditions under which these formulations may be more robust when encountering a dielectric perturbation. Our 1D analysis showed that the 1D modes were sensitive to the structure geometry. The antisymmetric \textrm{D} mode amplitudes show that the \textrm{D} --TBA did not capture the correct (tangential \overrightarrow{E} --field) boundary conditions. However, the \textrm{D} --TBA did not yield significantly poorer results compared to the \textrm{E} --TBA. Our 2D analysis reveals that the \textrm{E} -- and \textrm{D} --TBAs produced nearly identical mode profiles for every structure. Plots of the relative difference between the \textrm{E} and \textrm{D} mode amplitudes show that the \textrm{D} --TBA did capture the correct (normal \overrightarrow{E} --field) boundary conditions. We found that the 2D TBA CC mode calculations were 125-150 times faster than an FDTD calculation for the same two-defect PCS. Notwithstanding this efficiency, the appropriateness of either TBA was found to depend on the geometry of the structure and the mode(s), i.e. whether or not the mode has a large normal or tangential component.

ULTRAVIOLET EMISSION LINES of Si II in QUASARS - INVESTIGATING the Si II DISASTER

The observed line intensity ratios of the Si ii λ1263 and λ1307 multiplets to that of Si ii λ1814 in the broad-line region (BLR) of quasars are both an order of magnitude larger than the theoretical values. This was first pointed out by Baldwin et al., who termed it the "Si ii disaster," and it has remained unresolved. We investigate the problem in the light of newly published atomic data for Si ii. Specifically, we perform BLR calculations using several different atomic data sets within the CLOUDY modeling code under optically thick quasar cloud conditions. In addition, we test for selective pumping by the source photons or intrinsic galactic reddening as possible causes for the discrepancy, and we also consider blending with other species. However, we find that none of the options investigated resolve the Si ii disaster, with the potential exception of microturbulent velocity broadening and line blending. We find that a larger microturbulent velocity () may solve the Si ii disaster through continuum pumping and other effects. The CLOUDY models indicate strong blending of the Si ii λ1307 multiplet with emission lines of O i, although the predicted degree of blending is incompatible with the observed λ1263/λ1307 intensity ratios. Clearly, more work is required on the quasar modeling of not just the Si ii lines but also nearby transitions (in particular those of O i) to fully investigate whether blending may be responsible for the Si ii disaster.

Stable carbon isotope ratios and accumulation rates of organic carbon and nutrients of DSDP Hole 79-545 (Appendix A)

Future warming is predicted to shift the Earth system into a mode with progressive increase and vigour of extreme climate events possibly stimulating other mechanisms that invigorate global warming. This study provides new data and modelling investigating climatic consequences and biogeochemical feedbacks that happened in a warmer world ~112 Myr ago. Our study focuses on the Cretaceous Oceanic Anoxic Event (OAE) 1b and explores how the Earth system responded to a moderate ~25,000 yr lasting climate perturbation that is modelled to be less than 1 °C in global average temperature. Using a new chronological model for OAE 1b we present high-resolution elemental and bulk carbon isotope records from DSDP Site 545 from Mazagan Plateau off NW Africa and combine this information with a coupled atmosphere-land-ocean model. The simulations suggest that a perturbation at the onset of OAE 1b caused almost instantaneous warming of the atmosphere on the order of 0.3 °C followed by a longer (~45,000 yr) period of ~0.8 °C cooling. The marine records from DSDP Site 545 support that these moderate swings in global climate had immediate consequences for African continental supply of mineral matter and nutrients (phosphorous), subsequent oxygen availability, and organic carbon burial in the eastern subtropical Atlantic, however, without turning the ocean anoxic. The match between modelling results and stratigraphic isotopic data support previous studies [summarized in Jenkyns 2003, doi:10.1098/rsta.2003.1240] in that methane emission from marine hydrates, albeit moderate in dimension, may have been the trigger for OAE 1b, though we can not finally rule out alternative mechanisms. Following the hydrate mechanism a total of 1.15 * 10**18 g methane carbon (delta13C=-60 ?), equivalent to about 10% to the total modern gas hydrate inventory, generated the delta13Ccarb profile recorded in the section. Modelling suggests a combination of moderate-scale methane pulses supplemented by continuous methane emission at elevated levels over ~25,000 yr. The proposed mechanism, though difficult to finally confirm in the geological past, is arguably more likely to occur in a warmer world and apparently perturbs global climate and ocean chemistry almost instantaneously. This study shows that, once set-off, this mechanism can maintain Earth's climate in a perturbed mode over geological time leading to pronounced changes in regional climate.

Pulling Back the Veil: The Characterization and Habitability of Enshrouded Worlds

Thesis (Ph.D.)--University of Washington, 2016-08

A Study on the liquefaction risk in seismic design of foundations

A fully coupled non-linear effective stress response finite difference (FD) model is built to survey the counter-intuitive recent findings on the reliance of pore water pressure ratio on foundation contact pressure. Two alternative design scenarios for a benchmark problem are explored and contrasted in the light of construction emission rates using the EFFC-DFI methodology. A strain-hardening effective stress plasticity model is adopted to simulate the dynamic loading. A combination of input motions, contact pressure, initial vertical total pressure and distance to foundation centreline are employed, as model variables, to further investigate the control of permanent and variable actions on the residual pore pressure ratio. The model is verified against the Ghosh and Madabhushi high acceleration field test database. The outputs of this work is aimed to improve the current computer-aided seismic foundation design that relies on ground’s packing state and consistency. The results confirm that on seismic excitation of shallow foundations, the likelihood of effective stress loss is greater in deeper depths and across free field. For the benchmark problem, adopting a shallow foundation system instead of piled foundation benefitted in a 75% less emission rate, a marked proportion of which is owed to reduced materials and haulage carbon cost.

Understanding near Fermi-level electronic structure through x-ray emission spectroscopy

Thesis (Ph.D.)--University of Washington, 2016-08

Role of substrate quality on the performance of semipolar (11 2 - 2) InGaN light-emitting diodes

We compare the optical properties and device performance of unpackaged InGaN/GaN multiple-quantum-well light-emitting diodes (LEDs) emitting at ∼430 nm grown simultaneously on a high-cost small-size bulk semipolar (11 2 - 2) GaN substrate (Bulk-GaN) and a low-cost large-size (11 2 - 2) GaN template created on patterned (10 1 - 2) r-plane sapphire substrate (PSS-GaN). The Bulk-GaN substrate has the threading dislocation density (TDD) of ∼ and basal-plane stacking fault (BSF) density of 0 cm-1, while the PSS-GaN substrate has the TDD of ∼2 × 108cm-2 and BSF density of ∼1 × 103cm-1. Despite an enhanced light extraction efficiency, the LED grown on PSS-GaN has two-times lower internal quantum efficiency than the LED grown on Bulk-GaN as determined by photoluminescence measurements. The LED grown on PSS-GaN substrate also has about two-times lower output power compared to the LED grown on Bulk-GaN substrate. This lower output power was attributed to the higher TDD and BSF density.

Exploring redox-driven self-assembly of mixed metal polyoxometalates

How can we control the experimental conditions towards the isolation of specific structures? Why do particular architectures form? These are some challenging questions that synthetic chemists try to answer, specifically within polyoxometalate (POM) chemistry, where there is still much unknown regarding the synthesis of novel molecular structures in a controlled and predictive manner. This work covers a wide range of POM chemistry, exploring the redox self-assembly of polyoxometalate clusters, using both “one-pot”, flow and hydrothermal conditions. For this purpose, different vanadium, molybdenum and tungsten reagents, heteroatoms, inorganic salts and reducing agents have been used. The template effect of lone-pair containing pyramidal heteroatoms has been investigated. Efforts to synthesize new POM clusters displaying pyramidal heteroanions (XO32-, where X= S, Se, Te, P) are reported. The reaction of molybdenum with vanadium in the presence of XO32- heteroatoms is explored, showing how via the cation and experimental control it is possible to direct the self-assembly process and to isolate isostructural compounds. A series of four isostructural (two new, namely {Mo11V7P} and {Mo11V7Te} and two already known, namely {Mo11V7Se} and {Mo11V7S} disordered egg-shaped Polyoxometalates have been reported. The compounds were characterized by X-ray structural analysis, TGA, UV-Vis, FT-IR, Elemental and Flame Atomic Absorption Spectroscopy (FAAS) analysis and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Cyclic Voltammetry measurements have been carried out in all four compounds showing the effect of the ionic density of the heteroatom on the potential. High-Resolution ESI-MS studies have revealed that the structures retain their integrity in solution. Efforts to synthesize new mixed-metal compounds led to isolation, structural, and electronic characterization of the theoretically predicted, but experimentally elusive δ-isomer of the Keggin polyoxometalate cluster anion, {H2W4V9O33(C6H13NO3)}, by the reaction of tungstate(VI) and vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to the surface of the cluster. Control experiments (in the absence of the organic compound) have proven that the tripodal ligand plays crucial role on the formation of the isomer. The six vanadium metal centres, which consist the upper part of the cluster, are bonded to the “capping” TEA tripodal ligand. This metal-ligand bonding directs and stabilises the formation of the final product. The δ-Keggin species was characterized by single-crystal X-ray diffraction, FT-IR, UV-vis, NMR and ESI-MS spectrometry. Electronic structure and structure-stability correlations were evaluated by means of DFT calculations. The compounds exhibited photochromic properties by undergoing single-crystal-to-single-crystal (SC-SC) transformations and changing colour under light. Non-conventional synthetic approaches are also used for the synthesis of the POM clusters comparing the classical “one-pot” reaction conditions and exploring the synthetic parameters of the synthesis of POM compounds. Reactions under hydrothermal and flow conditions, where single crystals that depend on the solubility of the minerals under hot water and high pressure can be synthesized, resulted in the isolation of two isostructural compounds, namely, {Mo12V3Te5}. The compound isolated from a continuous processing method, crystallizes in a hexagonal crystal system, forming a 2D porous plane net, while the compound isolated using hard experimental conditions (high temperature and pressure) crystallizes in monoclinic system, resulting in a different packing configuration. Utilizing these alternative synthetic approaches, the most kinetically and thermodynamically compounds would possibly be isolated. These compounds were characterised by single-crystal X-ray diffraction, FT-IR and UV-vis spectroscopy. Finally, the redox-controlled driven oscillatory template exchange between phosphate (P) and vanadate (V) anions enclosed in an {M18O54(XO4)2} cluster is further investigated using UV-vis spectroscopy as a function of reaction time, showed that more than six complete oscillations interconverting the capsule species present in solution from {P2M18} to {V2M18} were possible, provided that a sufficient concentration of the TEA reducing agent was present in solution. In an effort to investigate the periodicity of the exchange of the phosphate and vanadate anions, time dependent Uv-vis measurements were performed for a period at a range of 170-550 hours. Different experimental conditions were also applied in order to investigate the role of the reducing agent, as well as the effect of other experimental variables on the oscillatory system.

Al-based anodic oxide films structure observation using field emission gun scanning electron microscopy

In the present work, the anodic oxide films of Al, Al-Cu 4.5% and Al-Si 6.5% alloys are formed using direct and pulse current. In the case of Al-Cu and Al-Si alloys, the electrolyte used contains sulfuric acid and oxalic acid, meanwhile for Al the electrolyte contains sulfuric acid only. Al-Cu alloy was submitted to a heat treatment in order to decrease the effect of inter metallic phase theta upon the anodic film structure. Fractured samples were observed using a field emission gun scanning electron microscope JSM-6330F at (LME)/Brazilian Synchrotron Light Laboratory (LNLS), Campinas, SP, Brazil. The oxide film images enable evaluation of the pore size and form with a resolution similar to the transmission electron microscope (TEM) resolution. It is also observed that the anodizing process using pulse current produces an irregular structure of pore walls, and by direct cur-rent it is produced a rectilinear pore wall. (c) 2005 Elsevier B.V. All rights reserved.

Investigating the peculiar emission from the new VHE gamma-ray source H1722+119

The MAGIC (Major Atmospheric Gamma-ray Imaging Cherenkov) telescopes observed the BL Lac object H1722+119 (redshift unknown) for six consecutive nights between 2013 May 17 and 22, for a total of 12.5 h. The observations were triggered by high activity in the optical band measured by the KVA (Kungliga Vetenskapsakademien) telescope. The source was for the first time detected in the very high energy (VHE, E > 100 GeV) γ-ray band with a statistical significance of 5.9 σ. The integral flux above 150 GeV is estimated to be (2.0 ± 0.5) per cent of the Crab Nebula flux. We used contemporaneous high energy (HE, 100MeV < E < 100 GeV) γ-ray observations from Fermi-LAT (Large Area Telescope) to estimate the redshift of the source. Within the framework of the current extragalactic background light models, we estimate the redshift to be z = 0.34±0.15. Additionally, we used contemporaneous X-ray to radio data collected by the instruments on board the Swift satellite, the KVA, and the OVRO (Owens Valley Radio Observatory) telescope to study multifrequency characteristics of the source. We found no significant temporal variability of the flux in the HE and VHE bands. The flux in the optical and radio wavebands, on the other hand, did vary with different patterns. The spectral energy distribution (SED) of H1722+119 shows surprising behaviour in the ∼ 3×1014 −1018 Hz frequency range. It can be modelled using an inhomogeneous helical jet synchrotron self-Compton model.

Elementos de apoio ao dimensionamento de secções compostas em light steel framing

Dissertação de Mestrado, Engenharia Civil, Especialização em Estruturas, Instituto Superior de Engenharia, Universidade do Algarve, 2016