No description available.

No description available.

No description available.

No description available.

Thesis (M.S.)--Ohio State University, 2009. / Title from first page of PDF file. Includes vita. Includes bibliographical references (p. 97-103).

The effects of geopressuring and kerogen decomposition on mineral-fluid equilibria were calculated in order to predict the diagenetic-alteration mineralogy produced in equilibrium with kerogen-rich, geopressured sediments. These calculations indicate that several processes specific to kerogen-rich geopressured sediments contribute to the development of a characteristic alteration mineralogy. These processes are: (1) the upward flow of fluids in geopressured sediments, in contrast to the generally downward flow of fluids in normally-pressured sediments; (2) the coincidence of the depths of geopressuring (2-3 km; Fertl et al., 1976), with the geothermal temperatures necessary for CO₂ release (100°-135°C; Hunt, 1979), and CH₄ release (>90°C; Hunt, 1979); and (3) the opposing rates of sediment burial and CO₂ and CH₄ transfer into the upward-flowing fluids, which result in the geopressured pore fluids becoming enriched, and in some cases saturated, with respect to CO₂ and CH₄. Three patterns of mineral deposition during diagenesis of kerogen-rich geopressured sediments are predicted. Quartz deposition should occur at the top of the geopressured zone and decrease rapidly with increased depth as a result of the decreased flux of upward fluid flow with increased depth. Carbonate deposition should occur above the zone of CO₂ release from kerogen degradation as a result of the upward flux of CO₂ saturated fluids and subsequent decreases in fluid temperature, pressure and CO₂ solubility. Kaolinite-carbonate could deposit within and above the zone of CO₂ release from kerogen as a result of silicate dissolution by CO₂-rich acid pore fluids, followed by the potential for albite-carbonate deposition upon CO₂ depletion. In contrast, laumontite and anhydrite should not deposit during diagenesis of kerogen-rich geopressured sediments, but could deposit during diagenesis of normally-pressured or kerogen-poor geopressured sediments. An additional difference between these diagenetic environments is that quartz deposition would not be expected in normally-pressured sediments in which fluids are expected to be flowing downward. These mineralogic relationships compare favorably with observed relationships in the kerogen-rich geopressured sandstones of the Frio formation from the Texas Gulf Coast.

No description available.

Organic matter which is insoluble in common solvents and non-oxidising acids often comprises the quantitatively most important fraction of organic matter in sediments. This operationally defined material is usually simply termed 'insoluble organic matter' (IOM) or 'kerogen' when it is isolated from ancient sediments. Indeed, kerogen is regarded as the most abundant form of carbon on the planet. The molecular character of this generic material has not been fully elucidated, principally because of its insolubility which limits instrumental methods of analysis to those applicable to solid substrates. This thesis describes the quantitative isolation of IOM from lacustrine and marine sediments and two species of methanogenic bacteria using a sequential isolation procedure. A range of synthetic IOMs (melanoidins) was also prepared. The dissolution of IOM and melanoidins obtained in this manner was then attempted using the acidic ionic liquid l-ethyl-3- methylimidazolium chloride-aluminium (III) chloride. Two synthetic dendrimers containing similar functional groups to those observed in sedimentary IOM were used to try and assess the mode of action of the ionic liquid. Ionic liquid treatment of the DCM soluble dendrimers resulted in the formation of 7 - 62 % of material that was no longer soluble in DCM, whilst the soluble components had been substantially altered. The ionic liquid was found to non-quantitatively promote ether cleavage, protonation and rearrangement reactions. IOM was isolated from lacustrine Rostherne Mere, UK, sediments (7 - 3 0 % dry weight), Kimmeridge Clay, Dorset (11 - 12 %) and methanogenic bacteria (Methanococcus jannaschii, 3 %; Methanobacterium thermoaiitotrophicum, 0.1 %) using a time-consuming isolation procedure involving over forty separate chemical manipulations. Monitoring of the sequential isolation of IOM and characterisation of the final isolates was carried out using solid-state NMR, IR, elemental analysis, pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS), scanning electron microscopy, and the newer surface sensitive technique of time of flight-secondary ion mass spectrometry (ToF-SIMS). Less than 1 % of sedimentary IOM and 5 % of Kimmeridge Clay IOM was soluble in DCM following ionic liquid treatment, whilst alkyl chains were lost from the insoluble portion which also increased in aromaticity. The poor yield recovered following ionic liquid treatment of M. jannaschii IOM (5 %) was attributed to loss of volatile material during hydrolysis. Following ionic liquid treatment 93 - 96 % of the melanoidins remained insoluble in DCM although their character had been altered, becoming more condensed. This ionic liquid dissolution procedure has not provided the substantial progress in elucidating the molecular character of IOM promised by earlier reports.

This work had the objective of determining both the kinetic parameters for the pyrolysis of oil shale and kerogen as well as using analytical techniques coupled with pyrolysis to shed light on the structure of a specific Green River oil shale. Because of the problems with linearized methods and disagreement among literature values and methods, a new method was developed tofit kinetic parameters to non linearized data. The method was demonstrated to determine the "correct" answer for mathematically generated data within a few percent error and was shown to have a lower sum squared error than the linearized methods. The curve-fitting methodology was then applied to pyrolysis kinetic data for kerogen and oil shale. Crushed samples were pyrolyzed at heating rates from 1 to 10 K/min and at pressures of 1 and 40 bar. The transient pyrolysis data were fit with a first-order model and a progressive Distributed Activation Energy Model (DAEM). An F-test was used to determine confidence regions and compare the kinetic parameters among the samples. The activation energies determined ranged from 173 to 226 kJ/mol, with most values around 200-220 kJ/mol. The kinetic coefficients determined for oil shale and the demineralized samples were statistically the same. Only small differences in kinetic coefficients were seen in the size-graded samples. The first-order and DAEM were shown to be statistically different, but a visual inspection of a graph of the model predictions and the data revealed that both models performed well. The largest effect on the kinetic parameters was between samples collected from different geographic allocations. The pyrolysis products (and the parent kerogen sample) were analyzed by several chemical techniques to determine chemical structure information about the parent sample. TheGC/MS data for the tars collected showed a distribution of alkenes/alkanes with 11 to 12 carbonsin length being the most frequent. XPS analysis demonstrated that any chemical model must have pyridinic and pyrrolic nitrogens as well as carbonyls and carboxyl groups. Therefore a chemical structure model of kerogen should have heteroatoms of nitrogen in the aromatic region(i.e., the portions of the kerogen that are stable at moderate temperatures).

No description available.