Nuclear fusion from Coulomb explosions of deuterated methane clusters subjected to ultraintense femtosecond laser pulses

This paper reports that Coulomb explosions taken place in the experiment of heteronuclear deuterated methane clusters ((CD4)(n)) in a gas jet subjected to intense femtosecond laser pulses (170 mJ, 70 fs) have led to table-top laser driven DD nuclear fusion. The clusters produced in supersonic expansion had an average energies of deuterons produced in the laser-cluster interaction were 60 and 1.5 KeV, respectively. From DD collisons of energetic deuterons, a yield of 2.5(+/-0.4)x10(4) fusion neutrons of 2.45 MeV per shot was realized, giving rise to a neutron production efficiency of about 1.5 x 10(5) per joule of incident laser pulse energy. Theoretical calculations were performed and a fairly good agreement of the calculated neutron yield with that obtained from the present experiment was found.

Succinate:ubiquinone oxidoreductase from Paracoccus denitrificans and particulate methane monooxygenase from Methylococcus capsulatus (Bath): experimental and theoretical EPR studies of the metal cofactors

This thesis summarizes the application of conventional and modern electron paramagnetic resonance (EPR) techniques to establish proximity relationships between paramagnetic metal centers in metalloproteins and between metal centers and magnetic ligand nuclei in two important and timely membrane proteins: succinate:ubiquinone oxidoreductase (SQR) from Paracoccus denitrificans and particulate methane monooxygenase (pMMO) from Methylococcus capsulatus. Such proximity relationships are thought to be critical to the biological function and the associated biochemistry mediated by the metal centers in these proteins. A mechanistic understanding of biological function relies heavily on structure-function relationships and the knowledge of how molecular structure and electronic properties of the metal centers influence the reactivity in metalloenzymes. EPR spectroscopy has proven to be one of the most powerful techniques towards obtaining information about interactions between metal centers as well as defining ligand structures. SQR is an electron transport enzyme wherein the substrates, organic and metallic cofactors are held relatively far apart. Here, the proximity relationships of the metallic cofactors were studied through their weak spin-spin interactions by means of EPR power saturation and electron spin-lattice (T_1) measurements, when the enzyme was poised at designated reduction levels. Analysis of the electron T_1 measurements for the S-3 center when the b-heme is paramagnetic led to a detailed analysis of the dipolar interactions and distance determination between two interacting metal centers. Studies of ligand environment of the metal centers by electron spin echo envelope modulation (ESEEM) spectroscopy resulted in the identication of peptide nitrogens as coupled nuclei in the environment of the S-1 and S-3 centers.

Finally, an EPR model was developed to describe the ferromagnetically coupled trinuclear copper clusters in pMMO when the enzyme is oxidized. The Cu(II) ions in these clusters appear to be strongly exchange coupled, and the EPR is consistent with equilateral triangular arrangements of type 2 copper ions. These results offer the first glimpse of the magneto-structural correlations for a trinuclear copper cluster of this type, which, until the work on pMMO, has had no precedent in the metalloprotein literature. Such trinuclear copper clusters are even rare in synthetic models.

New insights into the formation and modification of carbonate-bearing minerals and methane gas in geological systems using multiply substituted isotopologues

This thesis describes the use of multiply-substituted stable isotopologues of carbonate minerals and methane gas to better understand how these environmentally significant minerals and gases form and are modified throughout their geological histories. Stable isotopes have a long tradition in earth science as a tool for providing quantitative constraints on how molecules, in or on the earth, formed in both the present and past. Nearly all studies, until recently, have only measured the bulk concentrations of stable isotopes in a phase or species. However, the abundance of various isotopologues within a phase, for example the concentration of isotopologues with multiple rare isotopes (multiply substituted or 'clumped' isotopologues) also carries potentially useful information. Specifically, the abundances of clumped isotopologues in an equilibrated system are a function of temperature and thus knowledge of their abundances can be used to calculate a sample’s formation temperature. In this thesis, measurements of clumped isotopologues are made on both carbonate-bearing minerals and methane gas in order to better constrain the environmental and geological histories of various samples.

Clumped-isotope-based measurements of ancient carbonate-bearing minerals, including apatites, have opened up paleotemperature reconstructions to a variety of systems and time periods. However, a critical issue when using clumped-isotope based measurements to reconstruct ancient mineral formation temperatures is whether the samples being measured have faithfully recorded their original internal isotopic distributions. These original distributions can be altered, for example, by diffusion of atoms in the mineral lattice or through diagenetic reactions. Understanding these processes quantitatively is critical for the use of clumped isotopes to reconstruct past temperatures, quantify diagenesis, and calculate time-temperature burial histories of carbonate minerals. In order to help orient this part of the thesis, Chapter 2 provides a broad overview and history of clumped-isotope based measurements in carbonate minerals.

In Chapter 3, the effects of elevated temperatures on a sample’s clumped-isotope composition are probed in both natural and experimental apatites (which contain structural carbonate groups) and calcites. A quantitative model is created that is calibrated by the experiments and consistent with the natural samples. The model allows for calculations of the change in a sample’s clumped isotope abundances as a function of any time-temperature history.

In Chapter 4, the effects of diagenesis on the stable isotopic compositions of apatites are explored on samples from a variety of sedimentary phosphorite deposits. Clumped isotope temperatures and bulk isotopic measurements from carbonate and phosphate groups are compared for all samples. These results demonstrate that samples have experienced isotopic exchange of oxygen atoms in both the carbonate and phosphate groups. A kinetic model is developed that allows for the calculation of the amount of diagenesis each sample has experienced and yields insight into the physical and chemical processes of diagenesis.

The thesis then switches gear and turns its attention to clumped isotope measurements of methane. Methane is critical greenhouse gas, energy resource, and microbial metabolic product and substrate. Despite its importance both environmentally and economically, much about methane’s formational mechanisms and the relative sources of methane to various environments remains poorly constrained. In order to add new constraints to our understanding of the formation of methane in nature, I describe the development and application of methane clumped isotope measurements to environmental deposits of methane. To help orient the reader, a brief overview of the formation of methane in both high and low temperature settings is given in Chapter 5.

In Chapter 6, a method for the measurement of methane clumped isotopologues via mass spectrometry is described. This chapter demonstrates that the measurement is precise and accurate. Additionally, the measurement is calibrated experimentally such that measurements of methane clumped isotope abundances can be converted into equivalent formational temperatures. This study represents the first time that methane clumped isotope abundances have been measured at useful precisions.

In Chapter 7, the methane clumped isotope method is applied to natural samples from a variety of settings. These settings include thermogenic gases formed and reservoired in shales, migrated thermogenic gases, biogenic gases, mixed biogenic and thermogenic gas deposits, and experimentally generated gases. In all cases, calculated clumped isotope temperatures make geological sense as formation temperatures or mixtures of high and low temperature gases. Based on these observations, we propose that the clumped isotope temperature of an unmixed gas represents its formation temperature — this was neither an obvious nor expected result and has important implications for how methane forms in nature. Additionally, these results demonstrate that methane-clumped isotope compositions provided valuable additional constraints to studying natural methane deposits.

Deposition of diamond-like carbon films by photon-enhanced chemical vapour deposition of methane using a windowless hydrogen lamp

Thin films of diamond-like carbon (DLC) have been deposited using a novel photon-enhanced chemical vapour deposition (photo-CVD) method. This low energy method may be a way to produce better interfaces in electronic devices by reducing damage due to ion bombardment. Methane requires high energy photons for photolysis to take place and these are not transmitted in most photo-CVD methods owing to the presence of a window between the lamp and the deposition environment. In our photo-CVD system there is no window and all the high energy photons are transmitted into the reaction gas. Initial work has proved promising and this paper presents recent results. Films have been characterized by measuring electron energy loss spectra, by ellipsometry and by fabricating and testing diode structures. Results indicate that the films are of a largely amorphous nature and are semiconducting. Diode structures have on/off current ratios of up to 106.

The structure of turbulent stratified and premixed methane/air flames I: Non-swirling flows

A series of flames in a turbulent methane/air stratified swirl burner is presented. The degree of stratification and swirl are systematically varied to generate a matrix of experimental conditions, allowing their separate and combined effects to be investigated. Non-swirling flows are considered in the present paper, and the effects of swirl are considered in a companion paper (Part II). A mean equivalence ratio of φ=0.75 is used, with φ for the highest level of stratification spanning 0.375-1.125. The burner features a central bluff-body to aid flame stabilization, and the influence of the induced recirculation zone is also considered. The current work focuses on non-swirling flows where two-component particle image velocimetry (PIV) measurements are sufficient to characterize the main features of the flow field. Scalar data obtained from Rayleigh/Raman/CO laser induced fluorescence (CO-LIF) line measurements at 103μm resolution allow the behavior of key combustion species-CH 4, CO 2, CO, H 2, H 2O and O 2-to be probed within the instantaneous flame front. Simultaneous cross-planar OH-PLIF is used to determine the orientation of the instantaneous flame normal in the scalar measurement window, allowing gradients in temperature and progress variable to be angle corrected to their three dimensional values. The relationship between curvature and flame thickness is investigated using the OH-PLIF images, as well as the effect of stratification on curvature.The main findings are that the behavior of the key combustion species in temperature space is well captured on the mean by laminar flame calculations regardless of the level of stratification. H 2 and CO are significant exceptions, both appearing at elevated levels in the stratified flames. Values for surface density function and by extension thermal scalar dissipation rate are found to be substantially lower than laminar values, as the thickening of the flame due to turbulence dominates the effect of increased strain. These findings hold for both premixed and stratified flames. The current series of flames is proposed as an interesting if challenging set of test cases for existing and emerging turbulent flame models, and data are available on request. © 2012 The Combustion Institute.

The structure of turbulent stratified and premixed methane/air flames II: Swirling flows

Experimental results are presented from a series of turbulent methane/air stratified flames stabilized on a swirl burner. Nine operating conditions are considered, systematically varying the level of stratification and swirl while maintaining a lean global mean equivalence ratio of φ̄=0.75. Scalar data are obtained from Rayleigh/Raman/CO laser induced fluorescence (CO-LIF) line measurements at 103μm resolution, allowing the behavior of the major combustion species-CH 4, CO 2, CO, H 2, H 2O and O 2-to be probed within the instantaneous flame front. The corresponding three-dimensional surface density function and thermal scalar dissipation rate are investigated, along with geometric characteristics of the flame such as curvature and flame thickness. Hydrogen and carbon monoxide levels within the flame brush are raised by stratification, indicating models with laminar premixed flame chemistry may not be suitable for stratified flames. However, flame surface density, scalar dissipation and curvature all appear insensitive to the degree of stratification in the flames surveyed. © 2012 The Combustion Institute.

Flow field measurements of a series of turbulent premixed and stratified methane/air flames

This paper presents flow field measurements for the turbulent stratified burner introduced in two previous publications in which high resolution scalar measurements were made by Sweeney et al. [1,2] for model validation. The flow fields of the series of premixed and stratified methane/air flames are investigated under turbulent, globally lean conditions (φg=0.75). Velocity data acquired with laser Doppler anemometry (LDA) and particle image velocimetry (PIV) are presented and discussed. Pairwise 2-component LDA measurements provide profiles of axial velocity, radial velocity, tangential velocity and corresponding fluctuating velocities. The LDA measurements of axial and tangential velocities enable the swirl number to be evaluated and the degree of swirl characterized. Power spectral density and autocorrelation functions derived from the LDA data acquired at 10kHz are optimized to calculate the integral time scales. Flow patterns are obtained using a 2-component PIV system operated at 7Hz. Velocity profiles and spatial correlations derived from the PIV and LDA measurements are shown to be in very good agreement, thus offering 3D mapping of the velocities. A strong correlation was observed between the shape of the recirculation zones above the central bluff body and the effects of heat release, stoichiometry and swirl. Detailed analyses of the LDA data further demonstrate that the flow behavior changes significantly with the levels of swirl and stratification, which combines the contributions of dilatation, recirculation and swirl. Key turbulence parameters are derived from the total velocity components, combining axial, radial and tangential velocities. © 2013 The Combustion Institute.

Methane and carbon dioxide fluxes from a shallow hypereutrophic subtropical Lake in China

Up to now, there have been few studies in the annual fluxes of greenhouse gases in lakes of subtropical regions. The fluxes of methane (CH4) and carbon dioxide (CO2) across air-water interface were measured in a shallow, hypereutrophic, subtropical Lake Donghu (China) over a year cycle, using a static chamber technique. During the year, Lake Donghu emitted CH4 and CO2; the average flux of CH4 and CO2 was 23.3 +/- 18.6 and 332.3 +/- 160.1 mg m(-2) d(-1), respectively. The fluxes of CH4 and CO2 showed strong seasonal dynamics: CH4 emission rate was highest in summer, remaining low in other seasons, whereas CO2 was adsorbed from the atmosphere in spring and summer, but exhibited a large emission in winter. Annual carbon (C) budget across air-water interface in Lake Donghu was estimated to be 7.52 +/- 4.07 x 10(8) g. CH4 emission was correlated positively with net primary production (NPP) and temperature, whereas CO2 flux correlated negatively with NPP and temperature; however, there were no significant relationships between the fluxes of CH4 and CO2 and dissolved organic carbon, a significant difference from boreal lakes, indicating that phytoplankton rather than allochthonous matter regulated C dynamics across air-water interface of subtropical lake enriched nutrient content. (c) 2005 Elsevier Ltd. All rights reserved.

Diel variation of methane fluxes in summer in a eutrophic subtropical lake in China

The summer diel variation of methane (CH4) flux was investigated in a eutrophic, subtropical lake in China. The CH4 concentration was always supersaturated, and the emission rate ranged from 0.24 to 45.51 mg m(-2) h(-1). The diel variations of CH4 flux in June and August showed a single peak in early afternoon and a minimum in the morning, while the pattern varied irregularly in May. There was a moderate relationship between water and sediment temperature and CH4 emission rate in some months.

Influence of A-type Zeolite on Methane Hydrate Formation

The porous medium has an important effect on hydrate formation. In this paper, the formation process and the gas storage capacity of the methane hydrate were investigated with A-type zeolite and Sodium Dodecyl Sulfate (SDS) existing in the system. The results show that A-type zeolite can influence methane hydrate formation. At the temperature of 273.5 K and pressure of 8.3 MPa, the distilled water with A-type zeolite can form methane hydrate with gaseous methane in 12 hours. The formation process of the system with A-type zeolite was quite steady and the amount of A-type zeolite can influence the gas storage capacity significantly. The adding of A-type zeolite with 0.067 g.(g water)(-1) into 2 x 10(-3) g.g(-1) SDS-water solution can increase the gas storage capacity, and the maximum increase rate was 31%. Simultaneously the promotion effect on hydrate formation of 3A-type zeolite is much more obvious than that of 5A-type zeolite when the water adding amounts are 0.033 g.g(-1) and 0.067 g.g(-1) at the experimental conditions.

The methane hydrate formation and the resource estimate resulting from free gas migration in seeping seafloor hydrate stability zone

It is a typical multiphase flow process for hydrate formation in seeping seafloor sediments. Free gas can not only be present but also take part in formation of hydrate. The volume fraction of free gas in local pore of hydrate stable zone (HSZ) influences the formation of hydrate in seeping seafloor area, and methane flux determines the abundance and resource of hydrate-bearing reservoirs. In this paper, a multiphase flow model including water (dissolved methane and salt)-free gas hydrate has been established to describe this kind of flow-transfer-reaction process where there exists a large scale of free gas migration and transform in seafloor pore. In the order of three different scenarios, the conversions among permeability, capillary pressure, phase saturations and salinity along with the formation of hydrate have been deducted. Furthermore, the influence of four sorts of free gas saturations and three classes of methane fluxes on hydrate formation and the resource has also been analyzed and compared. Based on the rules drawn from the simulation, and combined information gotten from drills in field, the methane hydrate(MH) formation in Shenhu area of South China Sea has been forecasted. It has been speculated that there may breed a moderate methane flux below this seafloor HSZ. If the flux is about 0.5 kg m-2 a-1, then it will go on to evolve about 2700 ka until the hydrate saturation in pore will arrive its peak (about 75%). Approximately 1.47 109 m3 MH has been reckoned in this marine basin finally, is about 13 times over preliminary estimate.

Methane hydrate growth velocity in seepage system of Qiongdongnan Basin, South China Sea

The occurrences of diapirs, gas-filled zones and gas plumes in seawater in Qiongdongnan Basin of South China Sea indicate that there may exist seepage system gas-hydrate reservoirs. Assuming there has a methane venting zone of 1500 m in diameter, and the methane flux is 1000 kmol/a, and the temperature of methane hydrate-bearing sediments ranges from 3 degrees C to 20 degrees C, then according to the hydrate film growth theory, by numerical simulation, this paper computes the temperatures and velocities in 0 mbsf, 100 mbsf, 200 mbsf, 425 mbsf over discrete length, and gives the change charts. The results show that the cementation velocity in sediments matrix of methane hydrate is about 0.2 nm/s, and the seepage system will evolve into diffusion system over probably 35000 years. Meanwhile, the methane hydrate growth velocity in leakage system is 20 similar to 40 times faster than in diffusion system.