In this dissertation, I discuss the role of organic residue analysis in identifying economic activities and subsistence practices associated with the first uses of pottery in the Middle East, and present the results of my analyses of 280 potsherds recovered from 22 Neolithic and early Chalcolithic settlements dating between 7300 and 4300 cal BC. The adoption of pottery vessels in the early agricultural villages and pastoral encampments of the Middle East was not a uniform phenomenon, with this new technology not immediately of benefit, apparently, to all human groups. Results of my analyses have demonstrated that ‘conventional’ solvent extraction and alkaline hydrolysis techniques have limited utility in the recovery of diagnostic organic compounds from pottery from early ceramic horizons in the Middle East (Gregg et al. 2007), and that increased yields can be achieved through the use of a microwave-assisted liquid chromatography protocol (Gregg et al. 2009; Gregg and Slater in press). My research has established that there is greater diversity in the fractionation of stable carbon isotopes associated with the synthesis of fatty acids in domesticated animals than has previously been reported. In many instances, the ranges of modern isotopic values that have been used to categorize animal fats in archaeological potsherds in northern Europe cannot distinguish between the ∂13C ratios of ancient dairy residues and carcass fats of ruminant and non-ruminant species in central Europe or the Middle East (Gregg et al. 2009; Gregg and Slater in press). In light of these results, I evaluate the diagnostic potential and limitations of different methodological approaches in the recovery and characterization of organic residues, and propose a series of measures that will allow more confident categorization of the substances in early pottery vessels from the Middle East. I also make a number of recommendations for archaeologists considering the use of organic residue analysis, and suggest some practical ideas on how to develop the degree of confidence necessary to assess the methods used in acquisition of molecular and isotopic data, and ultimately, to evaluate the adequacy of the analytical criteria used to address specific archaeological research questions.

Viruses are ubiquitous biological entities whose importance and role in aquatic habits is beginning to take form. However, several habitats have undergone limited to no examination with viral-geochemical parameters minimally examined and viral-mineral relationships in the natural environment and the role of mineralization on viral-host dynamic completely lacking. To further develop knowledge on the presence and abundances of viruses, how viruses impact aquatic systems, and how viral-host interactions can be impacted under mineralizing conditions, viruses were examined under a variety of habitats and experimental conditions. Water samples were collected from the deep subsurface (up to 450 m underground) and acid mine drainage (AMD) systems in order to determine the presence, abundance, and viral-geochemical relationships within the systems. Samples were also collected from a variety of freshwater habitats, which have undergone limited examination, to determine viral-geochemical and viral-mineral relationships. Lastly, bacteriophage-host dynamics were examined under authigenic mineral precipitation to determine how mineralization impacts this relationship. Results reveal that not only are viruses present in the deep subsurface and AMD systems, but they are abundant (up to 107 virus-like particles/mL) and morphogically diverse. Viruses are also the strongest predictor of prokaryotic abundance in southern Ontario freshwater systems where potential nutrients are rich. Geochemical variables, such as pH and Eh, were shown to have negative impacts of viral abundance indicting that AMD environments are detrimental for free viruses (i.e. not particle associated). Direct evidence of viral-mineral interactions was found using transmission electron microscopy as viral particles were shown attached to iron-bearing mineral phases (determined through elemental analysis). In addition, evidence of viral participation in mineralization events was found in both AMD and freshwater environments where inverse correlations were noted between viral abundance and jarosite saturation indices (r = -0.71 and r = -0.33, respectively), and goethite saturation indices were also noted to be the strongest predictor of VLP abundance in freshwater habitats explaining 78% of the variability in the data. Lastly, iron precipitation and/or metal ion binding to bacterial surfaces greatly reduced phage replication (~98%) revealing bacterial mineralization has a protective benefit strongly hindering viral replication.

North Range low-sulfide mineralization is dominantly hosted by Sudbury breccia, with amphibole-plagioclase equilibrium metamorphic temperatures of 440 to 533 ± 75oC, produced by the SICs thermal aureole. Mineralization led to increases in the bulk halogen content of the host Sudbury breccia and the formation of Ni-enriched ferromagnesian silicates. South Range low-sulfide mineralization is typically hosted by metabasalts of the Huronian Supergroup. Garnet-biotite-plagioclase-quartz geothermobarometry produced equilibrium metamorphic conditions of 513 to 645 ± 50oC and 2.0 to 7.7 ± 1.0 kbar, probably corresponding to a late-Penokean overprint of peak Blezardian/Penokean metamorphism. Silicates associated with South Range mineralization are compositionally similar to the host rock equivalents and no alteration selvage is commonly observed due to subsequent recrystallization. Platinum-group minerals (PGM) from the North Range comprise platinum and palladium tellurides and bismuth-tellurides, with Sb-bearing palladium bismuth-tellurides and sperrylite from the South Range. Kotulskite-sobolevskite from the North Range shows a previously unreported Ag-Pd substitution, with michenerite from irregular veinlet style mineralization showing the substitution of Se and Sb for Bi. Two unknown PGMs were identified from the South Range, along with kotulskite-sobolevskite-sudburyite crystals displaying extensive Te-Bi-Sb solid-solution not noted before at Sudbury. A new Se-bearing variant of pilsenite was identified at McKim. Polyphase aggregates from both Ranges indicate that Bi-Te melts may have been widespread at some stage postdating the emplacement of the main magmatic sulfides. Normalized plots for low-sulfide mineralization show enrichments in the precious and semimetals relative to contact and sharp-walled vein mineralization. This enrichment has resulted in elevated concentrations of Ag and Se in chalcopyrite and Pd+Ag and Se in pentlandite from the North Range. The mass balance for North Range samples found that a significant fraction of Ag and Se occurs in sulfides with all other elements preferring discrete phases. A substantial fraction of Pd is hosted by pentlandite on the South Range, with gersdorffite also a major host despite its low abundance. The enrichments observed reflect the formation of low-sulfide mineralization from a fractionated sulfide liquid and hydrothermal fluids that have interacted with a fractionated sulfide source, and suggest that the precious and semimetals behave incompatibly with crystallizing sulfide.

North Range low-sulfide mineralization is dominantly hosted by Sudbury breccia, with amphibole-plagioclase equilibrium metamorphic temperatures of 440 to 533 ± 75oC, produced by the SICs thermal aureole. Mineralization led to increases in the bulk halogen content of the host Sudbury breccia and the formation of Ni-enriched ferromagnesian silicates. South Range low-sulfide mineralization is typically hosted by metabasalts of the Huronian Supergroup. Garnet-biotite-plagioclase-quartz geothermobarometry produced equilibrium metamorphic conditions of 513 to 645 ± 50oC and 2.0 to 7.7 ± 1.0 kbar, probably corresponding to a late-Penokean overprint of peak Blezardian/Penokean metamorphism. Silicates associated with South Range mineralization are compositionally similar to the host rock equivalents and no alteration selvage is commonly observed due to subsequent recrystallization. Platinum-group minerals (PGM) from the North Range comprise platinum and palladium tellurides and bismuth-tellurides, with Sb-bearing palladium bismuth-tellurides and sperrylite from the South Range. Kotulskite-sobolevskite from the North Range shows a previously unreported Ag-Pd substitution, with michenerite from irregular veinlet style mineralization showing the substitution of Se and Sb for Bi. Two unknown PGMs were identified from the South Range, along with kotulskite-sobolevskite-sudburyite crystals displaying extensive Te-Bi-Sb solid-solution not noted before at Sudbury. A new Se-bearing variant of pilsenite was identified at McKim. Polyphase aggregates from both Ranges indicate that Bi-Te melts may have been widespread at some stage postdating the emplacement of the main magmatic sulfides. Normalized plots for low-sulfide mineralization show enrichments in the precious and semimetals relative to contact and sharp-walled vein mineralization. This enrichment has resulted in elevated concentrations of Ag and Se in chalcopyrite and Pd+Ag and Se in pentlandite from the North Range. The mass balance for North Range samples found that a significant fraction of Ag and Se occurs in sulfides with all other elements preferring discrete phases. A substantial fraction of Pd is hosted by pentlandite on the South Range, with gersdorffite also a major host despite its low abundance. The enrichments observed reflect the formation of low-sulfide mineralization from a fractionated sulfide liquid and hydrothermal fluids that have interacted with a fractionated sulfide source, and suggest that the precious and semimetals behave incompatibly with crystallizing sulfide.

Understanding Earth’s accretion and primary differentiation is a long-standing goal of geology. The segregation of FeNi metal from molten silicate to form Earth’s core is expected to deplete and fractionate the highly siderophile elements (HSEs). Estimates of the primitive upper mantle (PUM) composition however, reveal only modest HSE depletions and chondritic element ratios. Past experiments to determine if the mantle composition is set by high-temperature metal-silicate equilibrium have involved measuring the solubility of HSEs in silicate melt at conditions more reducing than the iron-wustite (IW) buffer. Accurate determination of solubilities at such conditions has been hindered by the formation of dispersed metal inclusions; this work describes methods to circumvent the problem. Results of three separate studies are presented which document the solubility of Re, Pt and Au in molten silicate which is demonstrably nugget-free. Data obtained from experiments done at 0.1 MPa–2 GPa, 1573–2573 K and ~ IW -1.5 to +3 reveal: 1) Re, Pt and Au solubility increases with increasing temperature, 2) Re solubility increases with increasing oxygen fugacity (fO2), consistent with dissolution as oxide species, 3) Below ~ IW +3, Pt and Au solubility increases with decreasing fO2, consistent with dissolution as neutral or silicide species, and 4) that Au is amongst the most soluble HSE in molten silicate, with values increasing with temperature, but insensitive to changes in P, fO2 and melt composition, making it well suited as a geothermometer for core formation. Partition coefficients calculated from these and previous solubility measurements indicate that metal-silicate equilibrium is unable to reproduce the Re/Os and Pt/Os ratios required by PUM Os isotope systematics if simultaneously accounting for the observed absolute element abundances. Instead, results support late accretion of material following core formation, elevating element abundances and endowing chondritic inter-element ratios. Experimental results are incorporated into a terrestrial accretion model, which differs from the standard approach by explicitly accounting for the distribution of oxygen. Model results show siderophile element abundances in PUM are best reproduced if the mantle undergoes oxidation during accretion and metal-silicate equilibrium occurs near the peridotite solidus.

Understanding Earth’s accretion and primary differentiation is a long-standing goal of geology. The segregation of FeNi metal from molten silicate to form Earth’s core is expected to deplete and fractionate the highly siderophile elements (HSEs). Estimates of the primitive upper mantle (PUM) composition however, reveal only modest HSE depletions and chondritic element ratios. Past experiments to determine if the mantle composition is set by high-temperature metal-silicate equilibrium have involved measuring the solubility of HSEs in silicate melt at conditions more reducing than the iron-wustite (IW) buffer. Accurate determination of solubilities at such conditions has been hindered by the formation of dispersed metal inclusions; this work describes methods to circumvent the problem. Results of three separate studies are presented which document the solubility of Re, Pt and Au in molten silicate which is demonstrably nugget-free. Data obtained from experiments done at 0.1 MPa–2 GPa, 1573–2573 K and ~ IW -1.5 to +3 reveal: 1) Re, Pt and Au solubility increases with increasing temperature, 2) Re solubility increases with increasing oxygen fugacity (fO2), consistent with dissolution as oxide species, 3) Below ~ IW +3, Pt and Au solubility increases with decreasing fO2, consistent with dissolution as neutral or silicide species, and 4) that Au is amongst the most soluble HSE in molten silicate, with values increasing with temperature, but insensitive to changes in P, fO2 and melt composition, making it well suited as a geothermometer for core formation. Partition coefficients calculated from these and previous solubility measurements indicate that metal-silicate equilibrium is unable to reproduce the Re/Os and Pt/Os ratios required by PUM Os isotope systematics if simultaneously accounting for the observed absolute element abundances. Instead, results support late accretion of material following core formation, elevating element abundances and endowing chondritic inter-element ratios. Experimental results are incorporated into a terrestrial accretion model, which differs from the standard approach by explicitly accounting for the distribution of oxygen. Model results show siderophile element abundances in PUM are best reproduced if the mantle undergoes oxidation during accretion and metal-silicate equilibrium occurs near the peridotite solidus.

This thesis addresses various issues in U-Pb zircon geochronology, proposing new experimental protocols in conventional chemical abrasion-isotope dilution thermal ionization mass spectrometry or CA-(ID)-TIMS and developing a new method for Pb evaporation-condensation from zircon that allows high precision Pb-Pb age determination on Precambrian samples. Various experiments are also done on zircon to extract U-Pb information by in situ flux aided fusion methods and to optimize a better silica gel Pb-ionization activator. Radiation damage caused by U decay in zircon disrupts its ‘closed system’ behavior leading to the loss of daughter radiogenic Pb and resulting in inaccurate ages. A high temperature thermal annealing procedure has been proposed to prevent such Pb loss. Studies presented here have been carried out using Laser Raman Spectroscopy and Scanning Electron Microscopy to characterize radiation damage and effects of laboratory induced thermal annealing on such damage. Backscattered electron images reveal a variety of textures for ZrO2 overgrowths on zircon annealed at 1450oC. Highly damaged zircon produces finer polycrystalline aggregates (<5µm) than zircon with less damage. Raman spectroscopy indicates that crystals with different levels of radiation damage are only partially restored by annealing at 1000oC for 2–3 or 20 days. Annealing at 1450oC for 1 h results in partial breakdown of zircon but restores Raman peak widths and wave numbers. Raman spectra are much less sensitive to polarization angle for annealed highly damaged grains than for weakly damaged zircon showing that when highly damaged zircon is recrystallized, it becomes a polycrystalline aggregate that pseudomorphs the original single crystal. The whole grain Pb evaporation-condensation method is based on 206Pb-207Pb age analyses where zircon grains are pre-treated at 1450oC to drive out all disturbed Pb and then they are kept at 1600oC for an hour or two during which Pb atoms are evaporated out of the grain and deposited directly into a clean Savillex teflon vial or a wide Re filament. This technique allows the use of a 202Pb-205Pb double spike for precise isotopic fractionation correction. Examples are shown in which application of this technique to zircon from Precambrian samples has successfully yielded sub-million year age precisions.

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.