Master of Science / Geology / Matthew Kirk / The Cherokee basin in southeastern Kansas is a declining coalbed methane (CBM) field where little is known about how the CBM formed, the extent to which it continues to form, and what factors influence its formation. An understanding of methanogenic processes and geochemistry could lead to potential enhancement of methane formation in the basin. The objectives of this project are to (1) determine the pathway of methane formation and (2) determine whether geochemistry has influenced gas formation. In order to reach the objectives, we analyzed formation water geochemistry, production history, and gas composition and isotopes. Post Rock Energy Corporation gave us access to 16 wells for sampling purposes. We collected gas samples in Isotubes® for compositional and isotopic analyses at a commercial laboratory. We analyzed major ion chemistry from formation water using standard methods. Co-produced water samples we collected are Na-Cl type with total dissolved solids content ranging from 35,367 to 91,565 mg/L. TDS tended to be highest in samples collected from wells with greater total depth. The pH and temperature of sampled water averaged 7.0 and 19°C with an alkalinity ranging from 3.33 to 8.59. Gas dryness and δ¹³C CH[subscript 4] range from 196 to 4531 and -69.95 to -56.5, respectively, which indicate that methane is being produced biologically. Comparing the δ¹³C CH[subscript 4] to the δD CH[subscript 4], which ranges from -228.2 to -217.2, suggest that the primary pathway of methanogenesis is H[subscript 2]/CO[subscript 2] reduction. We calculated Δ (the difference between δ values) in order to correlate isotope data to produced water chemistry. Samples ΔD and Δ¹³C values range from -189.1 to -168.7 and 61.52 to 69.99. Calculated ΔD[subscript CH4-H2O] and Δ¹³C[subscript CO2-CH4] values approach the range for the acetate/methyl pathways as Clˉ concentration increases, potentially indicating a slight shift in methanogenic pathway in deeper, more saline portions of the basin. The culturing results revealed that living methanogens are still able to utilize H[subscript 2], acetate, and methanol present in co-produced formation water from all tested wells.

Master of Science / Department of Geology / Sambhudas Chaudhuri / The exploration and development of unconventional shale plays provide an opportunity to study the hydrocarbon generation process. These unconventional plays allow one to investigate the interactions between the fluid, mineral, and organic material that occur in a hydrocarbon-generating source bed, before any changes in composition that may occur during secondary migration or post migration processes. Previous studies have determined the chemical constituents of formation waters collected from conventional reservoirs after secondary migration has occurred. This investigation targets formation waters collected from the Woodford shale that acts as both source and reservoir, therefore samples have yet to experience any changes in composition that occur during secondary migration. This investigation focuses on the major element and trace element chemistry of the formation water (Cl, Br, Na, K, Rb, Mg, Ca, Sr, and Rare Earth Elements), which has been compared to chemical constituents of the associated crude oil and kerogens. Analytical data for this investigation were determined by the following methods; Ion Chromatography, Inductively Coupled Plasma Mass Spectrometry (ICP-MS), and Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES). The information is used to assess the presence of different sources of water that constitute the formation water, and also to investigate interaction between different minerals and formation waters within the source beds. The formation water data also yields new insights into compartmentalization of oil-gas rich zones within the source beds.

Master of Science / Department of Geology / Sambhudas Chaudhuri / Rare earth element (REE) concentrations were measured in a source (reference) clay Ca-smectite standard and in the roots, stems, and leaves of a species of poplar plant (Populus eugenei). The poplar plant was grown in the clay standard under controlled laboratory conditions during a period of about three months. REEs were shown to fractionate in the clay mineral and plant materials with greater fractionation observed in plant materials. The REE data provide insight into the process of weathering of clay minerals such as a Ca-bearing smectite and provide insight into the degradation of and the composition of clay minerals in the plant environment. The degradation process is not followed by significant interlayer ion exchange effect on remaining clay minerals in the root environment. REEs were found to be transported into complex forms, potentially as REE-carboxylic anion pair complexes. The plant materials in this study were in general heavy REE (HREE) enriched relative to the source clay minerals due to the complexation effect. The REE anomalies observed in this study, in addition to the Ce and Eu anomalies, may be explained by the selective uptake by the plant by an enzyme effect rather than due to the influence of oxidation-reduction. The enzyme influence was more evident in the REE distribution when compared among the plant organs. These REE characteristics described for the plants may eventually be incorporated with data from numerous other studies and also used as a guide in the assessment of the contribution of plant materials to dissolved REE content in surface water and groundwater.

Master of Science / Department of Geology / Kirsten Nicolaysen / The Kerguelen Archipelago and the submarine Northern Kerguelen Plateau consist primarily of basalt erupted by the intraplate Kerguelen hotspot. The exposed volcanic rocks are tholeiitic basalts (29 Ma) followed by lesser alkalic basalts, highly alkaline phonolites, and syenites (24 Ma). This study presents the mineralogy, isotopic and geochemical compositions of lavas (n=59) from a 650 m section exposed in the wall of a glacial valley at Trois Menestrels in the Kerguelen Archipelago. This basalt section, exposed south of the Cook Ice Cap and closest to the Raillier du Baty alkalic plutonic complex, is further south and west of previously studied basalts exposed on the Plateau Central. Results of 40Ar/39Ar dating show the Trois Menestrels lavas erupted approximately 25 Ma, approximately contemporaneously with other Plateau Central lavas and thus provide an opportunity to examine spatial compositional variations within the Kerguelen hotspot. Though the Trois Menestrels lavas are tholeiitic, The samples plot on the tholeiitic field at the stratigraphic section of Trois Menestrels, 80% of lavas from Mt. Tourmente are transitional to alkalic in the younger rocks (25.6 Ma). This sequence of tholeiitic to transitional to alkalic compositions is mirrored at Mt. Capitole and Mt. Marion Dufresne. Sr, Ba, Pb, Nb, Zr versus Nb plots show similar patterns across the Plateau Central and abundances overlap within error. Variations in isotopic composition reveal that Trois Menestrels is rather homogeneous compared to the other sections. A fundamental issue that derives from these results is the close relationship between these different rocks of the various region of the Plateau Central.

Master of Science / Department of Geology / Matthew E. Brueseke / Previous studies of the northern Great Basin have indicated that mid-Miocene epithermal gold and silver ore deposits distributed regionally are temporally related to the magmatic activity associated with the onset of widespread extension and the Yellowstone hotspot (Saunders and Crowe, 1996; Kamenov et al., 2007). This study is focused on the volcanic rocks and ore deposits from the Silver City district (SCD), ID to address the petrogenesis and magmatic evolution that was influential in forming local precious metal deposits. The goal is to understand the tectonomagmatic conditions that contributed to the petrogenesis of the volcanic suite in the Silver City district, which can be used to provide details on the relationship between coeval mid- Miocene magmatism and mineralization across the northern Great Basin and Oregon Plateau. In order to better constrain the magmatic evolution of the SCD and potential sources of the precious metals, we have undertaken detailed sampling of local crust and mid-Miocene volcanic units to constrain their physical, geochemical, isotopic, and geochronological characteristics, as well as provide constraints on the petrogenesis of the mid-Miocene volcanic package. Prior studies of the local volcanism have yielded K-Ar and [superscript]40Ar/[superscript]39Ar ages of ~16.6 to 14 Ma (Bonnichsen, 1983), while others have dated adularia from one SCD mineral vein and obtained [superscript]40Ar/[superscript]39Ar ages of between 15.6 and 16.3 Ma (Hames et al., 2009; and Aseto et al., 2011). Field observations are consistent with earlier work (Lindgren, 1900; Asher, 1968; Pansze, 1975; Halsor et al., 1988; Bonnichsen and Godchaux, 2006; Camp and Ross, 2009) and reveal a sequence of basalt consisting of regionally prevalent Steens Basalt that pre-dated precious metal mineralization. Some of the basalt appears to have been erupted locally, based on the presence of mafic dikes and thick pyroclastic deposits similar to other regional mid-Miocene magmatic systems. Stratigraphically overlying this lower basalt suite is a complex package of rhyolite flows and domes, thin silicic pyroclastic units, additional basaltic lava flows, intermediate lava flows, and mafic/silicic shallow intrusives. Geochemical analysis indicates that the basaltic and basaltic andesite lava flows are locally erupted flows of Steens Basalt while the intermediate and silicic volcanism in SCD can be classified into nine distinct units including two andesites, one dacite, four rhyolites and two rhyolite tuffaceous units. Geochemical modeling suggest that the intermediate and silicic magmas were formed by a combination of open system processes, including low pressure partial melting and assimilation of mid to upper crustal granitoid basement rock, and magma mixing between silicic and basaltic endmembers. The formation of silicic volcanism in the SCD is similar to other regional mid-Miocene silicic volcanic systems (e.g. Santa Rosa-Calico volcanic field and Jarbidge Rhyolite). Based on new [superscript]40Ar/[superscript]39Ar geochronology of both volcanic units and epithermally emplaced mineralization, SCD volcanism appears to have erupted over a relatively short amount of time that overlaps with local epithermal Au-Ag mineralization.

Master of Science / Department of Geology / Saugata Datta / In response to increasing concerns over release of anthropogenic greenhouse gases the Arbuckle saline aquifer in south-central Kansas has been proposed as a potential site for geologic storage for CO2. Two wells (KGS 1-32 and 1-28) have been drilled to provide data for site specific determination of the storage potential of the Arbuckle. Cores from specific depths within Arbuckle (4164`-5130`) were utilized for study and flow-through experiments. Examination of formation rocks by thin section studies, SEM, XRD and CT scans was carried out to characterize the mineralogy of the core. Dominant mineralogy throughout the formation is dolomite with large chert nodules and occasional zones with pyrite and argillaceous minerals. Carbonate-silica contacts contain extensive heterogeneity with sulfide minerals and argillaceous material in between. Extensive vugs and microfractures are common. This study focuses on three zones of interest: the Mississippian pay zone (3670`-3700`), a potential baffle in Arbuckle (4400`-4550`) and the proposed CO2 injection zone (4900`-5050`). Drill stem tests and swabbed brine samples collected from 13 depths throughout the aquifer reveal a saline brine (~50,000-190,000 TDS) dominated by Na+, Ca2+ and Cl-. Elemental ratios of major cations with Cl- demonstrate a typical saline aquifer system. Cl/Br ratios reveal mixing between primary and secondary brines within the aquifer. Ca/Cl and Mg/Cl ratios suggest effect of dolomitization within the brines. δ18O and δ2H isotopes and Li/Cl ratios in the brine suggest the separation of upper and lower Arbuckle by a baffle zone. Swabbed waters provide Fe speciation data and reveal the importance of it in the system. Laboratory experiments carried out at 40°C and 2100 psi using formation core plug and collected brine identify reaction pathways to be anticipated when supercritical CO2 is injected. Results showed fluctuating chemistries of elements with Ca2+, Mg2+, Na+ and Cl- increasing during the first 15 hours, while Fe, S, and SO42- decrease. For the next 15 hours a reverse trend of the same elements were observed. Alkalinity and pH show inverse relationship throughout the experiment. We conclude that dominant reactions will occur between brine, CO2 and dolomite, calcite, chert, pyrite and argillaceous minerals. There is no perceived threat to freshwater resources in Kansas due to CO2 injection.

Master of Science / Department of Geology / Matthew Totten / The REE distribution patterns and total concentrations of the organic matter of the Woodford shale reveal a potential avenue to investigate hydrocarbon maturation processes in a source rock. Ten samples of the organic matter fraction and 10 samples of the silicate-carbonate fraction of the Woodford shale from north central Oklahoma were analyzed by methods developed at KSU. Thirteen oil samples from Woodford Devonian oil and Mississippian oil samples were analyzed for REE also. REE concentration levels in an average shale range from 170 ppm to 185 ppm, and concentration levels in modern day plants occur in the ppb levels. The REE concentrations in the organic matter of the Woodford Shale samples analyzed ranged from 300 to 800 ppm. The high concentrations of the REEs in the Woodford Shale, as compared to the modern-day plants, are reflections of the transformations of buried Woodford Shale organic materials in post-depositional environmental conditions with potential contributions of exchanges of REE coming from associated sediments. The distribution patterns of REEs in the organic materials normalized to PAAS (post-Archean Australian Shale) had the following significant features: (1) all but two out of the ten samples had a La-Lu trend with HREE enrichment in general, (2) all but two samples showed Ho and Tm positive enrichments, (3) only one sample had positive Eu anomalies, (4) three samples had Ce negative anomalies, although one was with a positive Ce anomaly, (5) all but three out of ten had MREE enrichment by varied degrees. It is hypothesized that Ho and Tm positive anomalies in the organic materials of the Woodford Shale are reflections of enzymic influence related to the plant physiology. Similar arguments may be made for the Eu and the Ce anomalies in the Woodford Shale organic materials. The varied MREE enrichments are likely to have been related to some phosphate mineralization events, as the Woodford Shale is well known for having abundant presence of phosphate nodules. The trend of HREE enrichment in general for the Woodford Shale organic materials can be related to inheritance from sources with REE-complexes stabilized by interaction between the metals and carbonate ligands or carboxylate ligands or both. Therefore, a reasonable suggestion about the history of the REEs in the organic materials would be that both source and burial transformation effects of the deposited organic materials in association with the inorganic constituents had an influence on the general trend and the specific trends in the distribution patterns of the REEs. This study provides a valuable insight into the understandings of the REE landscapes in the organic fraction of the Woodford Shale in northern Oklahoma, linking these understandings to the REE analysis of an oil generated from the same source bed and comparing it to oil produced from younger Mississippian oil. The information gathered from this study may ultimately prove useful to trace the chemical history of oils generated from the Woodford Shale source beds.

Master of Science / Department of Geology / Matthew Brueseke / The Southern Oklahoma Aulacogen (SOA) produced more than 250,000 km[superscript]3 of Cambrian mafic to silicic magmatism, associated with the opening of the Iapetus Ocean. In the Arbuckle Mountains, oil and gas exploration showed mafic to intermediate volcanic rock interbedded with rhyolite lavas. The first description of these lavas was a result of the 1982 drilling of the Hamilton Brothers Turner Falls well. Cuttings have been collected from this well and five others, and whole rock major and trace element analysis, Sr and Nd isotope analysis, and rare earth element analysis has been completed on these samples. These samples plot primarily as tholeiitic to transitional basalts to andesites. Trace element ratios show Zr/Nb values ranging from 8-10, K/Nb values ranging from 300-600, and Ba/Nb values ranging from 10-20, which overlap with known EM1 OIB values. Applying a conservative age of 535 Ma for these rocks yields [superscript]87Sr/[superscript]86Sr[subscript]i values of 0.703970 to 0.706403 and epsilon Nd values of 1.67 to 3.22, which also fall within the accepted range of EMI values. [superscript]87Sr/[superscript]86Sr[subscript]i increases with wt. % SiO[subscript]2 and K/P, consistent with the generation of evolved compositions via open-system processes. The sample with the least radiogenic Sr isotope ratio, combined with its trace element ratios is most consistent with an EM1-type source. These results, coupled with existing isotope and trace element constraints from regionally exposed dikes and plutonic rocks that crop out in the Wichita Mts., give better insight into understanding what tectonic model (lower-mantle derived hotspot or extension of the lithosphere) drove the magmatic production of the SOA. The results are more consistent with a lower-mantle origin for SOA mafic-intermediate magmatism, and indicate the potential for flood basalt volcanism.

Master of Science / Department of Geology / Matthew Totten / Oil production in Kansas has a long history with plays being found on all sides of the state. The source of Kansas’s hydrocarbons has been traditionally thought to be outside the state due to low thermal maturity and the shallow burial of potential source rocks within Kansas. This research addresses the question regarding the source of the oil in Kansas, at least within a small geographic area of roughly 146mi[superscript]2. The Spivey-Grabs-Basil Field has been one of the more successful fields within the state of Kansas since the 1960’s. This field is compartmentalized and offers a natural laboratory in which to conduct the field’s first formal oil-source rock correlation since oils are locked into place. While the main focus of this research relies heavily on pyrolysis and GCMS for biomarker analysis, it also investigates the possibility of using rare earth element (REE) concentrations as a possible fingerprint of organic matter within a source bed. TOC values of the Chattanooga shale samples from the Spivey-Grabs-Basil filed range from 0.75 and 3.95 wt. %, well within productive capacity. Pyrograms show both the potential for additional production, and the likely previous expulsion of hydrocarbons. Biomarker concentration percentages between C[subscript]27, C[subscript]28, and C[subscript]29 steranes, as well as pentacyclic terpane ratios compared between crude oil from the Spivey-Grabs-Basil and the Chattanooga shale show a definite genetic relationship. REE values of the organic fraction of the Chattanooga inversely correlate with those of the crude oils, suggesting fractionation during oil generation. After comparison of results with the Woodford shale in Oklahoma, the conclusion of this study is that the Chattanooga shale which underlies the Spivey-Grabs-Basil oil field of southern Kansas is the probable source rock which generated the oil now being produced.

Master of Science / Geology / Matthew W. Totten / The most common practice of typing crude oils utilizes biomarkers to gain insight on the history of the oil. This practice only considers the organic chemistry of the oil, and does not consider the trace element concentrations within the oil. Rare earth element and other trace element concentrations in crude oil might provide further insight into the oil’s source and origin. This study analyzed REE and other trace metal concentrations of crude oil in the Spivey-Grabs field of south-central Kansas through analysis by ICP-MS and ICP-AES that, coupled with visual physical characteristics of oil and FT-IR analysis, could explain the reported “compartmentalization” of the field and provide insight on the origin of the oils. Analysis of physical characteristics of the crude oils suggested the presence of two types of oil, of differing viscosities, in the field. FT-IR confirmed the presence of these two oil types based on functional groups present in the oils. The existence of a high viscosity oil could potentially explain the compartmentalization behavior in the field. PAAS-normalized REE distribution patterns showed a general LREE enrichment, a positive cerium and negative europium anomaly, and a MREE and HREE depletion, but higher viscosity oils showed additional MREE and HREE enrichment. K/Rb values ranged from 2,864 to 44,118, with oils from mixed-viscosity wells having lower ratios overall. K/Rb values of Spivey-Grabs crude oils more closely resembled those of the Lansing-Kansas City formation than the K/Rb values of the Woodford shale and Mississippian formation of the Anadarko basin. Comparing the rare earth element distribution patterns and K/Rb values from this study to those of the Woodford shale suggests the Spivey-Grabs oil originated from a local source and not from the Woodford shale.