Master of Science / Department of Geology / Matthew Totten / The Viola Limestone is a prominent petroleum reservoir in the Mid-Continent Region, particularly in Oklahoma and Kansas. Coral Coast Petroleum established production from the Viola Ls. in 2011 in their Stephens Ranch lease in Clark County, south-central Kansas. Development of this lease has been hindered by the unpredictable production rates encountered in each of the subsequent eleven development wells. Infield drilling locations to date were chosen by favorable structural position as determined by 3D seismic. The best reservoir conditions, however, do not necessarily coincide with structural position. It was the purpose of this study to determine whether the ideal porosity and permeability are controlled by depositional environment, diagenetic alterations, or a combination of these factors. Several approaches to solve this question were implemented and utilized, including well log analysis, petrographic inspection of well cuttings and thin sections, and the application of the Scanning Electron Microscope (SEM). An exploration model of the Viola Ls. in this field was developed, where the Viola A and B zones were dolomitized during during marine transgressions by mixing of sea water with other Mg-rich fluids. Reservoir conditions are found where these facies were preserved as paleotopographic highs during a subsequent sea level low-stand. These preserved dolomitized facies correspond to the seismic facies identified by seismic attributes in a 3D seismic study by Vohs (2016).

[pt] A avaliação da fonte e origem de hidrocarbonetos e isótopos estáveis em sedimentos dos Cânions Grussaí e Almirante Câmara fazem parte do projeto HABITATS, que visa a caracterização ambiental da Bacia de Campos e a melhor compreensão da dinâmica do ecossistema. Neste estudo foram avaliados diversos parâmetros orgânicos como hidrocarbonetos alifáticos, aromáticos, hopanos e esteranos assim como a razão isotópica de carbono e nitrogênio. A fração alifática indica ao longo dos cânions a contribuição de plantas vasculares terrestres, bem como resíduos produtos derivados de petróleo, possivelmente de fluídos de perfuração não-aquosos ou material semelhante. A distribuição da concentração de hopanos e esteranos é característico da presença de óleo recente em todas as estações, o que pode estar associado a exsudações naturais de petróleo. A avaliação das concentrações de HPAs, auxiliadas por razões diagnósticas sugerem fonte pirogênica de contribuição. Na campanha de inverno, observa-se no Cânion Almirante Câmara um forte predomínio da queima de biomassa, no entanto, a razão isotópica de carbono e nitrogênio indica um material orgânico de origem tipicamente marinha, não corroborando as informações obtidas pelas analises de hidrocarbonetos. O largo numero de estações e parametros empregados permitem uma visão amplificada para avaliação. / [en] The assessment of source and origin of hydrocarbons and stable isotopes in sediments from Grussaí and Almirante Câmara canyons is part of the HABITATS Project, which aim to characterize the environment of Campos Basin e a better understanding of the ecosystem dynamics. On this study several organic parameters were evaluate, such aliphatic and aromatic hydrocarbons, hopane, sterane and also the isotopic ratio of carbon and nitrogen. The aliphatic fraction over the canyons indicates the contribution of vascular land plants as well as residue oil products, possibly drilling non-aqueous fluids or similar material. The concentration distribution of hopanes or steranes is characteristic at all stations of recent presence of oil, which can be associated to natural oil seeps.The assessment of PAHs concentrations, assisted by diagnostic ratios suggests pyrogenic source contribution. In the winter campaign, is observed in Almirante Câmara canyon a predominance of biomass burning source, however, the isotopic ratio of carbon and nitrogen indicates marine source, which do not corroborate the information obtained by analysis of hydrocarbons. The large number of stations and parameters analyzed allow an amplified view for evaluation.

Polycyclic aromatic hydrocarbon (PAH) compounds, which are common to coal tar and coal-tar-based products, are ubiquitous environmental contaminates with carcinogenic effects to human health and aquatic life. Transport of PAHs via solid phase particulate motion, gaseous phase volatilization, and aqueous phase dissolution into urban waterbodies of PAH compounds from coal-tar-based pavement sealant products has been studied. Pavement rejuvenators are products applied to increase the usable life of pavement. Coal-tar-based rejuvenators contain a significantly larger mass fraction of coal-tar with respect to coal-tar-based sealants, but pavement rejuvenators have not been as extensively studied as pavement sealants. Chemical analysis of detached pavement material treated with coal-tar-bases, asphalt-based, and bio-based rejuvenators was conducted with gas chromatography – mass spectrometry (GC/MS) analysis for 16 PAH compounds and two aromatic heterocyclic organic compounds following extraction with methylene chloride. Detached pavement material was collected from 19 simulated asphalt surface abrasion experiments that used a model mobile load simulator (MMLS) test apparatus that replicated surface challenges from vehicular traffic. The MMLS test apparatus configuration allowed asphalt disc samples treated with different rejuvenation products, to be tested and for detached material to be collected and quantified prior to GC/MS analysis. Test cases evaluated the influence of rejuvenation product type and cure time, as well as the effect of sand application (simulating sand application during slippery winter storm conditions) had on detached particulate and ultimate PAH compound loading. The average mass of particulate detachment from samples following a 48 hour cure time, for the asphalt-based and coal-tar-based rejuvenator products were 0.347 g and 0.480 g, respectively. This mass of detached material was lower than that from pavement treated with bio-based rejuvenator and the control (not treated), which had 4.858 g and 2.567 g of detached particulate material, respectively. When the product cure time was increased to three weeks, which was significantly long enough to capture effects of compound volatilization, average particulate detachment increased to 0.882 g for the coal-tar-based rejuvenator and decreased for the bio-based rejuvenator to 2.600 g. Six tests performed with a single application of winter storm sand after a 48 hour product cure time showed an increase in average particulate detachment to 1.450 g and 0.617 g for pavement treated with the asphalt-based and coal-tar-based rejuvenators, respectively. Conversely, under the same conditions, a reduction in average detached particulate to 3.749 g was observed for the bio-based product. Detached particulate material quantities for each test case were used with the respective cumulative concentration of 16 PAH compounds quantified to make an assessment on the potential PAH compound contamination via solid phase particle transport. The average PAH compound concentration in particulate detached from pavement treated with a coal-tar-based rejuvenator was 3062.8 mg PAH per kg of particulate. This was an order of magnitude higher than the average PAH concentration measured in particulate detached from the two control pavement samples and the two asphalt-based samples after a 48 hour cure time, which were 322.1 and 508.1 mg PAH per kg detached particulate, respectively. PAH compound concentrations were also normalized by the surface area of pavement treated with a rejuvenator to determine the potential PAH compound contamination per unit area. Normalized results for each rejuvenator type were averaged to make an overall evaluation of the potential rejuvenator specific PAH compound loading. The coal-tar-based, bio-based, and asphalt-based rejuvenators had a normalized cumulative solid-phase PAH compound release of 2.35, 0.88, and 0.17 mg PAH per square foot of pavement rejuvenated, respectively. In addition, carbazole was quantified in all pavement samples treated with the coal-tar-based rejuvenator at an average concentration of 125.6 mg carbazole per kg detached particulate. Acridine was quantified in detached particulate from five of seven coal-tar-based test performed at an average concentration (excluding non-detection samples) of 42.1 mg acridine per kg detached particulate.

The current methods for identifying ignitable liquid residues in fire debris are heavily based on the holistic, qualitative interpretation of chromatographic patterns with the mass spectral identification of selected peaks. The identification of neat, unweathered ignitable liquids according to ASTM 1618 using these methods is relatively straightforward for the trained analyst. The challenges in fire debris analysis arise with phenomena such as evaporation, substrate interference, and biodegradation. These phenomena result in alterations of chromatographic patterns which can lead to misclassifications or false negatives. The biodegradation of ignitable liquids is generally known to be more complex than evaporation [20], and proceeds in a manner that is dependent on numerous factors such as: composition of the petroleum product/ignitable liquid, structure of the hydrocarbon compound, soil type, bacterial community, the type of microbial metabolism that is occurring, and the environmental conditions surrounding in the sample. While nothing can be done to prevent the biodegradation, continued research on biodegraded ignitable liquids and the characterization of the trends observed may be able to provide insight into how an analyst can identify a biodegraded ignitable liquid residue. This research utilized normalized abundance values of select ions from pre-existing gas chromatography-mass spectrometry (GC-MS) data on samples from three different gasoline and diesel biodegradation studies. A total of 18 ions were selected to indicate the presence of six hydrocarbon classes (three each for alkanes, aromatics, cycloalkanes, naphthalenes, indanes, and adamantanes) based on them being either base peaks or high abundance peaks within the electron impact mass spectra of compounds within that hydrocarbon class. The loss of ion abundance over the degradation periods was assessed by creating scatter plots and performing simple linear regression analyses. Coefficient of determination values, the standard error of the estimate, the slope, and the slope error of the best fit line were assessed to draw conclusions regarding which classes exhibited desirable characteristics, relative to the other classes, such as a linear degradation, low variation in abundance within the sampling days, and a slow rate of abundance loss over the degradation period. Additional analyses included two-way analysis of the variance (ANOVA), to assess the effects of time as well as different soil type on the degradation of the hydrocarbons, stepwise multinomial logistic regressions to identify which classes were the best predictors of the type of ignitable liquid, and one-way ANOVAs to determine where the differences in the ratios of hydrocarbon classes existed within each of the ignitable liquids, as well as between the two liquids. Hydrocarbon classes identified as exhibiting characteristics such as slow and/or reliable rates of abundance loss during biodegradation are thought of as desirable for future validation studies, where specific ranges of hydrocarbon class abundance(s) may be used to identify the presence of a biodegraded ignitable liquid. Classes of hydrocarbons that have experienced biodegradation that maintain an abundance close to that of a neat, non degraded counterpart, or that reliably degrade and have predictable abundance levels given a particular period of degradation, would be instrumental in determining whether or not an unknown sample contains an ignitable liquid residue. It is the hope that these assessments will not only provide helpful information to future researchers in the field of fire debris analysis, but that they will create interest in the quantitative, statistical assessment of ignitable liquid data for detection and identification purposes.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / O gÃs natural, cuja maior parte à constituÃda de metano, à um combustÃvel que vem se expandindo no mercado energÃtico global por possuir uma queima mais limpa que outros derivados petrolÃferos e por ser mais eficiente energeticamente. No entanto, ele possui como grande desvantagem frente a outros combustÃveis a dificuldade em ser armazenado devido a sua baixa densidade. Materiais microporosos vÃm sendo utilizados para aumentar tal densidade por meio da adsorÃÃo. No entanto, um dos problemas encontrados na utilizaÃÃo desses materiais se trata da diminuiÃÃo da capacidade adsortiva apÃs ciclos de carga e descarga de tanques de armazenamento. O estudo desse problema, porÃm, demanda um grande nÃmero de experimentos e uma aparelhagem relativamente sofisticada. Este trabalho propÃs a simulaÃÃo molecular como uma metodologia vÃlida a ser utilizada para o estudo da retenÃÃo de alcanos em carbono ativado e em oito estruturas metalorgÃnicas: IRMOF-1, ZIF-8, CuBTC, PCN-11, PCN-14, UiO-66, MIL-100 e MIL-101. Considerou-se o gÃs natural como uma mistura de metano (C1), etano (C2), propano (C3) e butano (C4) nas proporÃÃes de, respectivamente, 84,7:10:0,9:0,1. Para a validaÃÃo dos modelos utilizados nassimulaÃÃes, as isotermas simuladas de C1, C2, C3 e C4 foram ajustadas Ãs experimentais obtidas da literatura para cada um dos materiais. Foram entÃo realizadas isotermas multicomponentes e estudo de sÃtios de adsorÃÃo para o estudo da retenÃÃo de hidrocarbonetos e da influÃncia de fatores composicionais e estruturais nesse fenÃmeno. Observou-se que as MOFs MIL-100 e ZIF-8 sÃo as mais recomendadas para uso em tanques de GNA por critÃrios de capacidade, eficiÃncia adsortiva e estabilidade. Verificou-se ainda que MOFs que apresentam sÃtios de adsorÃÃo pouco dispersos apresentam uma maior tendÃncia à acumulaÃÃo de hidrocarbonetos. / Natural gas, which consists mostly of methane, is a fuel that has been expanding in the global energy market by having a cleaner burning than other petroleum derivatives and are more energy efficient. However, it has a great disadvantage compared to other fuels: it is difficult to be stored due to its low energy density. Microporous materials have been used to increase the energy density by adsorption. However, one of the problems encountered in using these materials it comes to the decrease in adsorption capacity after charge and discharge cycles of the storage tanks. The study of this problem, however, requires a large number of experiments and a relatively sophisticated equipment. This paper proposes themolecular simulation as a valid methodology to study the retention of alkanes in activated carbon, and eight metalorganic structures: IRMOF - 1, ZIF - 8, CuBTC, PCN- 11, PCN -14, UiO -66, MIL -100 and MIL- 101. We considered the natural gas as a mixture of methane (C1), ethane (C2), propane (C3) and butane (C4) in the proportions respectively 84,7:10:0,9:0,1. For the validation of the models used in the simulations, the simulated isotherms of C1, C2, C3 and C4 were adjusted to fit the experimental ones, obtained from the literature data for every material. Multicomponent isotherms were then performed, the retention of hydrocarbons were studied as well as the influence of compositional and structural factors to this phenomenon. We noticed that the MOFs MIL-100 and ZIF-8 are the most recommended to use in GNA tanks according to the criteria of capacity, adsorption efficiency and stability. We verified as well that MOFs that have adsorption sites too localized present a larger tendency to the accumulation of hydrocarbons.

In the next 20 years, the global demand for oil is forecast to grow by 0.7% every year, and the demand for natural gas will increase by 1.6% annually. But as we continue to produce oil and gas, the resources of our current oilfields are depleting. To meet the rising global energy demand, it is essential that we can keep discovering more petroleum resources in the future. The primary aim of this PhD project is to deepen our understanding of hydrocarbon reservoirs and enhance our ability to explore. The first project looked at the geological risks in hydrocarbon exploration. It reviewed and statistically analysed the data of 382 unsuccessful boreholes in the UK offshore area. The results suggest that the most significant risk for an exploration well is encountering a thin or absent target reservoir. This risk happened to 27 ± 4% of the past unsuccessful wells. The following most common risks are low-porosity reservoirs (22 ± 4% of all cases) and the lack of a closed trap (23 ± 4%). The probability of a target reservoir having a leaky caprock is 5 ± 2%. The study has calculated the probability of occurrence of all the geological risks in exploration, and this risk data can be applied to predict the potential geological risks in future exploration. One challenge in developing saline aquifers as CO2 storage reservoirs is the lack of subsurface data, unless a well has been drilled. Drawing on the experience of hydrocarbon exploration, a potential CO2 storage site identified on seismic profiles will be subject to many uncertainties, such as thin or low-porosity reservoirs, leaky seals, which are analogue to the geological risks of an undrilled hydrocarbon prospect. Since the workflow of locating CO2 storage reservoirs is similar to the exploration for hydrocarbon reservoirs, the risk data of hydrocarbon exploration wells can be applied to infer the geological risks of the exploration wells for CO2 storage reservoirs. Based on this assumption, the study of Chapter 3 estimated that the probability of a borehole encountering a reservoir suitable for CO2 storage is c. 41-57% (90% confidence interval). For reservoirs with stratigraphic traps within the UKCS, the probability of success is slightly lower, at 39 ± 10% (90% confidence). Chapter 4 studies the porosity and diagenetic process of the Middle Jurassic Pentland Formation in the North Sea. The analysis data come from 21 wells that drilled and cored the Pentland Formation. Petrographic data suggest the content of detrital illite is the most important factor affecting the porosity of the Pentland Sandstone - the porosities of the sandstones with more than 15% of illite (determined by point-count) are invariably low (< 10%). Quartz cement grows at an average rate of 2.3 %/km below the depth of 2km, and it is the main porosity occluding phase in the deep Pentland Sandstone. Petrographic data shows the clean, fine-grained sandstones contain the highest amount of quartz cement. Only 1-2 % of K-feldspar seems to have dissolved in the deep Pentland Sandstone (> 2 km), and petrographic data suggest that K-feldspar dissolution does not have any substantial influence on the sandstone porosity. There is no geochemical evidence for mass transfer between the sandstones and shales of the Pentland Formation. Chapter 5 investigates the high porosity of the Pentland Sandstone in the Kessog Field, Central North Sea. The upper part of the Kessog reservoir displays an anomalously high porosity (c. 25 %, helium porosity) that is 10 % higher than the porosity of other Pentland sandstones at the same depth (c. 15 %, 4.1 - 4.4 km). Petrographic data show these high porosities are predominantly primary porosity. The effects of sedimentary facies, grain coats, secondary porosity and overpressure on the formation of the high porosity are considered to be negligible in this case. Early hydrocarbon emplacement is the only explanation for the high porosity. In addition to less quartz cement, the high-porosity sandstones also contain more K-feldspar and less kaolin than the medium-porosity sandstones of the same field. This indicates that early hydrocarbon emplacement has also inhibited the replacement of K-feldspar. The last chapter studies the potential mass transfer of silica, aluminium, potassium, iron, magenesium and calcium at sandstone-shale contacts. The study samples include 18 groups of sandstones and shales that were collected from five oilfields in the North Sea. The interval space between the samples of each group varies from centimetres to meters. The research aim is to find evidence of mass transfer by studying the samples' variation of mineralogy and chemistry as a function of the distance to the nearest sandstone-shale contact. The sandstones are mostly turbidite sandstones, and the shales are Kimmeridge Clay shales. Petrographic, mineralogical and chemical data do not provide firm evidence for mass transfer within any group of the samples. The result indicates that the scale of mobility of silica, aluminium, potassium, iron, magenesium and calcium in the subsurface may be below the scale of detection of the study method, i.e. < 5 cm.

>Magister Scientiae - MSc / The reservoir quality of the Orange Basin, offshore South Africa is known to be immensely impaired by the presence of authigenic minerals. The collective effects of burial, bioturbation, compaction and chemical reactions between rocks, fluid and organic matter conclusively determined the quality of reservoirs within the Orange basin. The aim of this study was to provide information on the quality of reservoirs within the Orange Basin. Data used to conduct this study include wireline logs (LAS format), well completion reports and core samples from potential reservoir zones of wells K-A2, K-A3 and K-E1. To accomplish the aim, petrophysical parameters were calculated, such as porosity, permeability and water saturation. Besides, depositional environments were identified using gamma ray log and core logging techniques. Thirdly, petrographic studies were supporting techniques in understanding how various minerals and diagenetic processes play a role in reservoir characterisation. Geophysical wireline logs (Gamma ray, Resistivity, Bulk density and Caliper) allowed for the estimation of the three main reservoir properties; namely: porosity, water saturation and permeability. The porosity calculations revealed a range of 3-18% for well K-A2, 2%-13% for well K-A3 and 3%-16% for well K-E1. The permeability’s ranged from 0.08-0.1 mD and 0.001-1.30 mD for K-A3 and K-E1, respectively. Thus, the findings of the petrophysical evaluation of the wells in Interactive Petrophysics indicated that the reservoir intervals of wells K-A2, K-A3 and K-E1 are of poor to good quality. Based on the core analyses, the depositional environment is mostly shallow marine, specifically tide dominated for well K-A2, sandstone channel for well K-A3 and intertidal environment for well K-E1. These environments were confirmed by XRD, revealing glauconite as the prominent mineral.

Hydrogen production from reforming bio-fuels is considered as one of the major ways of utilizing renewable energy sources. Conventionally, most reforming catalysts are noble metal catalysts with high operation temperature above 1000 °C, which result in low thermal efficiency, long start-up time and use of high grade materials. These reasons hinder the development of hydrogen production technology. Novel self-sustained electrochemical promotion (SSEP) catalysts were developed and evaluated for heavy hydrocarbon reforming at relatively low temperatures, 450 to 650 °C. Typically, the SSEP catalysts contain NiO/Ni/CuO/Cu/CeO2 as a selective anodic phase, La0.9Sr0.1MnO3 (LSM) as a selective cathodic phase, yttria stabilized zirconia (YSZ) as an oxygen ion conduction phase, and Ni/Cu also as an electronic conduction phase. The reforming performance of the SSEP catalysts was evaluated using a fixed bed reforming reactor for n-pentadecane. A commercially available noble metal containing catalyst, 2.4 %Pt on CeO2 support, was evaluated using exactly the same method. The following conclusions can be drawn as a consequence of this study: 1) The fuel conversion for the SSEP catalyst was 10 folds of that for the noble metal catalyst and the yield of hydrogen and carbon monoxide for the SSEP catalysts was 100 folds of that for the noble metal catalyst at 450°C. 2) The mechanism of the SSEP catalysts was proved by the experimental results. 3) The study of the effect of each component and the effect of the concentration clearly reveals that the performance of the SSEP catalysts can be further improved to a higher level by many ways. In addition, all the catalysts were characterized by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), Transmission Electron Microscopy (TEM) and Accelerated Surface Area and Porosimetry Analyzer 2020 (ASAP 2020).

The main goal of this thesis was to develop new methods and knowledge that will explain and predict species differences in sensitivity to dioxin-like compounds (DLCs) in birds. The important achievements and results obtained from the four experimental chapters of this thesis are summarized as follow: (1) an efficient luciferase reporter gene (LRG) assay was developed for use with 96-well cell culture plates; (2) the results obtained from LRG assay were shown to be highly correlated to available in ovo toxicity data; (3) amino acids at positions 324 and 380 within the aryl hydrocarbon receptor 1 ligand binding domain (AHR1 LBD) were shown to be responsible for reduced Japanese quail (Coturnix japonica) AHR1 activity to induce a dioxin-responsive reporter gene in comparison to chicken (Gallus gallus domesticus), and ring-necked pheasant (Phasianus colchicus) AHR1 in response to different DLCs; (4) AHR1 LBD sequences of 86 avian species were studied and differences at amino acid sites 256, 257, 297, 324, 337 and 380 were identified. It was discovered that only positions 324 and 380 play a role in AHR1 activity to induce a dioxin-responsive gene; (5) in COS-7 cells expressing chicken AHR1, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and 2,3,4,7,8-pentachlorodibenzofuran (PeCDF) are equipotent inducers of the reporter gene and bind with similar affinity to chicken AHR1, however, in the cells expressing pheasant, Japanese quail and common tern (Sterna hirundo) AHR1, PeCDF is a stronger inducer than TCDD. PeCDF also binds with higher affinity to pheasant and quail AHR1 than TCDD. The results of this thesis show that embryo lethal effect of DLCs in avian species can be predicted by use of two new non-lethal methods: (1) the LRG assay and (2) determination of the identity of the amino acids at positions 324 and 380. The findings and methods described in this thesis will be of use for environmental risk assessments of DLCs.

The aryl hydrocarbon receptor (AHR) mediates the toxic effects of halogenated aromatic hydrocarbons (HAHs), including 2,3,7,8-tetrachlorodibenzo-p-dioxin, 2,3,4,7,8-pentachlorodibenzofuran and 2,3,7,8-tetrachlorodibenzofuran. Y322 is believed to play a role in binding-independent activation of AHR by atypical inducers, such as omeprazole. I examined AHR-mediated regulation of and coactivator recruitment to CYP1A1, CYP1B1, HES1 and TiPARP in T-47D and HuH7 cells. All compounds induced expression of each gene in both cell lines, with some temporal differences between the HAHs and omeprazole. Chromatin immunoprecipitation assays demonstrated activator-, cell line- and gene-selectivity in AHR coactivator recruitment. Omeprazole induced AHR degradation which was prevented by MG-132 pre-treatment. Y322 was found to be important for maximal AHR activation by 2,3,7,8-TCDD and 2,3,4,7,8-PeCDF, but required for 2,3,7,8-TCDF and Omp in an AHR-deficient MCF-7 cells. My findings provide further evidence for cell-, gene- and ligand-dependent differences in AHR-mediated gene expression and coactivator recruitment, and a role for Y322 in AHR activation.