Low-permeability Ordovician shale and limestone formations of the Michigan Basin are a target of interest for a deep geological repository for the long-term isolation of low and intermediate-level radioactive waste. Porewater studies contribute to an understanding of the age and evolution of paleofluids as part of ongoing research. Sulfur and oxygen isotope data presented here add to the characterization of these formations. For this work, a method was developed and used to extract porewater sulfate from low permeability rocks for the analysis of sulfate concentration and its δ34S and δ18O values, using an elemental analyzer interfaced with an isotope ratio mass spectrometer (EA-IRMS). Porewater sulfate concentrations were very low, varying from 0.02 to 228.88 mmol/ kgw. Values for δ34S were all near or below those for Ordovician seawater. The earlier work examined the δ34S and the morphology of framboidal pyrite in the Ordovician formations provides strong evidence for diagenetic sulfate reduction (Jautzy et al. in prep.). The lack of enrichment for δ34S and δ18O in porewater sulfate suggests that diagenetic sulfate reduction was quantitative and that the porewater sulfate measured in these samples is not residual sulfate remaining from that time. The distribution of sulfur isotope values between that of Silurian seawater and those of the framboidal pyrite suggests an origin from the infiltration of Silurian brines with contributions from pyrite oxidation. The δ18O values are consistent with this, showing mixtures between Silurian seawater sulfate and sulfide oxidation without the involvement of atmospheric oxygen. This evidence for anoxic sulfide oxidation indicates that inadvertent exposure to atmospheric O2 during porewater leaching in the laboratory is unlikely and that in-situ oxidation involving electron acceptors with lower electromotive potential took place, possibly over geological time. The combination of sulfate mass and the stable isotopes of porewater sulfate, along with the presence of Fe (III) and Mn (IV) bearing minerals indicate potential evidence of in-situ sulfide oxidation in one third of twenty-six core samples. The relative timing of events is not clear as to whether sulfide oxidation could have occurred during the Ordovician and/or after the infiltration of evaporated Silurian seawater into the Ordovician strata. This study adds a new understanding of the redox evolution within this sedimentary system with implications for contaminant transport.

Silurian strata of eastern North America have been thoroughly studied for nearly two centuries. Through these investigations a general understanding of unit distribution and correlative relationships were established throughout the region. Many of these interpretations remain valid still to this day, however, with advancements in stratigraphic methodologies in the last few decades (e.g., sequence-, chemo-, and biostratigraphy), numerous discrepancies have come to light with regards to the chronostratigraphic correlation of several stratigraphic intervals throughout the region. A number of these discrepancies within the lower Silurian (Llandovery—lower Wenlock) have been resolved in the last two decades permitting the establishment of refined depositional models and sequence stratigraphic hierarchies for strata deposited during this interval of time for the Appalachian, Illinois, and Michigan basins. Though these studies provided significant improvement to the chronostratigraphy of eastern North America, there remained a large under-evaluated stratigraphic interval spanning the remainder of the Silurian (Wenlock—Pridoli), which is host to expansive evaporite reserves and hydrocarbon resources throughout eastern North America. As such, it is critical that these strata are accurately and precisely correlated throughout the region and that temporal constraint be applied to these resources in order to evaluate their potential and develop predictive models for their future utilization. The investigation herein provides high-resolution chronostratigraphic analyses of several core and outcrop from the eastern, southwestern, and western margins of the Appalachian Basin. These analyses included the integration of δ13Ccarb chemostratigraphy, conodont biostratigraphy, sequence stratigraphy, and subsurface geophysical data. The work herein now permits the establishment of global series and stage boundaries for the upper Silurian throughout the Appalachian and Michigan basins and also addresses regional miscorrelations within strata on both the eastern and western margins of the Appalachian Basin to provide a united sequence stratigraphic hierarchy between the Appalachian, Illinois, and Michigan basins.

No description available.

Nuclear power generation is being regarded as a solution to ever increasing demand for electricity, and concerns over global warming and climate change due to the use of fossil fuels. Although nuclear power generation is considered to be reliable, economical, clean, and safe, the wastes produced from the nuclear fuel cycle are not, and can remain hazardous for hundreds of thousands of years. An international consensus has developed over the past several decades that deep geologic disposal of low, intermediate, and high level radioactive wastes is the best option to protect the biosphere. In this thesis, both regional scale and sub-regional scale models are created to simulate groundwater flow and transport for a representative Canadian Shield setting, honouring site-specific topography and surface water features. Sub-surface characteristics and properties are derived from numerous geoscience studies. In addition, a regional scale model is developed, centred on the Bruce Nuclear Power Development (BNPD) site near Tiverton, Ontario, and located within the Michigan Basin. Ontario Power Generation (OPG) has proposed a Deep Geologic Repository (DGR) for low & intermediate level waste (L&ILW) at the BNPD site. Paleoclimate simulations using various combinations of parameters are performed for both the Canadian Shield Sub-Regional model, and the Michigan Basin Regional model. Fracture zone permeability is a very important parameter when modelling crystalline rock settings. Migration of a unit tracer representing glacial recharge water can occur to depth in fractures of high permeability. Representative rock compressibility values are necessary as compressibilities are used to calculate storage coefficients, and the one-dimensional loading efficiency; these affect the subsurface propagation of elevated pore pressures due to glacial loading at surface. Coupled density-dependent flow and transport in paleoclimate simulations affects deep flow systems and provides a measure of flow stability, as well as increasing the mean life expectancy at depth. Finally, hydromechanical coupling is a very important mechanism for reducing vertical hydraulic gradients during a glaciation event when a hydraulic boundary condition equal to the pressure at the base of an ice-sheet is applied at ground surface. Pore water velocities are reduced, thereby retarding migration of surface waters into the subsurface environment.

Nuclear power generation is being regarded as a solution to ever increasing demand for electricity, and concerns over global warming and climate change due to the use of fossil fuels. Although nuclear power generation is considered to be reliable, economical, clean, and safe, the wastes produced from the nuclear fuel cycle are not, and can remain hazardous for hundreds of thousands of years. An international consensus has developed over the past several decades that deep geologic disposal of low, intermediate, and high level radioactive wastes is the best option to protect the biosphere. In this thesis, both regional scale and sub-regional scale models are created to simulate groundwater flow and transport for a representative Canadian Shield setting, honouring site-specific topography and surface water features. Sub-surface characteristics and properties are derived from numerous geoscience studies. In addition, a regional scale model is developed, centred on the Bruce Nuclear Power Development (BNPD) site near Tiverton, Ontario, and located within the Michigan Basin. Ontario Power Generation (OPG) has proposed a Deep Geologic Repository (DGR) for low & intermediate level waste (L&ILW) at the BNPD site. Paleoclimate simulations using various combinations of parameters are performed for both the Canadian Shield Sub-Regional model, and the Michigan Basin Regional model. Fracture zone permeability is a very important parameter when modelling crystalline rock settings. Migration of a unit tracer representing glacial recharge water can occur to depth in fractures of high permeability. Representative rock compressibility values are necessary as compressibilities are used to calculate storage coefficients, and the one-dimensional loading efficiency; these affect the subsurface propagation of elevated pore pressures due to glacial loading at surface. Coupled density-dependent flow and transport in paleoclimate simulations affects deep flow systems and provides a measure of flow stability, as well as increasing the mean life expectancy at depth. Finally, hydromechanical coupling is a very important mechanism for reducing vertical hydraulic gradients during a glaciation event when a hydraulic boundary condition equal to the pressure at the base of an ice-sheet is applied at ground surface. Pore water velocities are reduced, thereby retarding migration of surface waters into the subsurface environment.

Deep subsurface rock samples from Upper Ordovician strata in the Michigan Basin were analyzed for the presence of microbial communities. High concentrations of biogenic methane were observed in the Upper and Middle Ordovician formations. Total porosity values for the shale, shale hard bed and limestone samples were 7.4%, 2.5% and 1.9%, respectively. Hydrocarbon presence ranged from petroliferous shale, to bituminous layering in shale hard beds, to hydrocarbon odour in limestone. Organic carbon content ranged from 0.5 to 2.5%, highest amount being present in the shale. Environmental DNA was extracted from core samples and PCR amplified using 16S rDNA bacterial primers. PCR performed with archaeal 16S rDNA and methanogen-specific (mcrA) primers did not yield DNA amplification. Gene analysis indicated that bacterial sequences similar to Proteobacteria, Cyanobacteria, Firmicutes, and Actinobacteria were present. Most sequences were not related to known cultivated species. Proteobacteria was the most dominant phyla at all depths and included heterotrophic, lithotrophic, acidophilic, radiotolerant, and sulphate-reducing species of bacteria. This study concludes that the observed biogenic methane is a product of ancient methanogenesis.

Deep subsurface rock samples from Upper Ordovician strata in the Michigan Basin were analyzed for the presence of microbial communities. High concentrations of biogenic methane were observed in the Upper and Middle Ordovician formations. Total porosity values for the shale, shale hard bed and limestone samples were 7.4%, 2.5% and 1.9%, respectively. Hydrocarbon presence ranged from petroliferous shale, to bituminous layering in shale hard beds, to hydrocarbon odour in limestone. Organic carbon content ranged from 0.5 to 2.5%, highest amount being present in the shale. Environmental DNA was extracted from core samples and PCR amplified using 16S rDNA bacterial primers. PCR performed with archaeal 16S rDNA and methanogen-specific (mcrA) primers did not yield DNA amplification. Gene analysis indicated that bacterial sequences similar to Proteobacteria, Cyanobacteria, Firmicutes, and Actinobacteria were present. Most sequences were not related to known cultivated species. Proteobacteria was the most dominant phyla at all depths and included heterotrophic, lithotrophic, acidophilic, radiotolerant, and sulphate-reducing species of bacteria. This study concludes that the observed biogenic methane is a product of ancient methanogenesis.

Deep subsurface rock samples from Upper Ordovician strata in the Michigan Basin were analyzed for the presence of microbial communities. High concentrations of biogenic methane were observed in the Upper and Middle Ordovician formations. Total porosity values for the shale, shale hard bed and limestone samples were 7.4%, 2.5% and 1.9%, respectively. Hydrocarbon presence ranged from petroliferous shale, to bituminous layering in shale hard beds, to hydrocarbon odour in limestone. Organic carbon content ranged from 0.5 to 2.5%, highest amount being present in the shale. Environmental DNA was extracted from core samples and PCR amplified using 16S rDNA bacterial primers. PCR performed with archaeal 16S rDNA and methanogen-specific (mcrA) primers did not yield DNA amplification. Gene analysis indicated that bacterial sequences similar to Proteobacteria, Cyanobacteria, Firmicutes, and Actinobacteria were present. Most sequences were not related to known cultivated species. Proteobacteria was the most dominant phyla at all depths and included heterotrophic, lithotrophic, acidophilic, radiotolerant, and sulphate-reducing species of bacteria. This study concludes that the observed biogenic methane is a product of ancient methanogenesis.

The effect of partially saturated conditions on aqueous diffusion was investigated on the Upper Ordovician Queenston Formation shale from the Michigan Basin of southwest Ontario, Canada. Effective diffusion coefficients (De) were determined for iodide tracer on duplicate cm-scale samples from a core segment. Partially saturated conditions were created with a new gas-ingrowth method that takes advantage of the variability of N2 solubility with pressure. The method is designed to create partially saturated pores, quantify the level of partial gas/brine saturation within the tracer-accessible pore space, and measure De under fully porewater-saturated and partially gas-saturated conditions for the same sample. X-ray radiography is used with an iodide tracer for quantifying the degree of partial saturation and measuring De. The saturated De values range from 2.8 x 10-12 to 3.1 x 10-12 m2/s. Following generation of a gas phase in the pores (average gas saturations of 4 to 6.7 %), De values decrease by 20 to 22 % relative to the porewater-saturated condition, indicating that the tortuosity factor (ratio of constrictivity to tortuosity) is sensitive to saturation. Suggesting that a small volume of the pore fraction is responsible for majority of the transport. The gas-ingrowth method was successful for generating partial gas saturation, but the distribution of the gas phase is non-uniform, with relatively high gas saturations near boundaries and lower saturations in the interior of the samples.

Deep subsurface rock samples from Upper Ordovician strata in the Michigan Basin were analyzed for the presence of microbial communities. High concentrations of biogenic methane were observed in the Upper and Middle Ordovician formations. Total porosity values for the shale, shale hard bed and limestone samples were 7.4%, 2.5% and 1.9%, respectively. Hydrocarbon presence ranged from petroliferous shale, to bituminous layering in shale hard beds, to hydrocarbon odour in limestone. Organic carbon content ranged from 0.5 to 2.5%, highest amount being present in the shale. Environmental DNA was extracted from core samples and PCR amplified using 16S rDNA bacterial primers. PCR performed with archaeal 16S rDNA and methanogen-specific (mcrA) primers did not yield DNA amplification. Gene analysis indicated that bacterial sequences similar to Proteobacteria, Cyanobacteria, Firmicutes, and Actinobacteria were present. Most sequences were not related to known cultivated species. Proteobacteria was the most dominant phyla at all depths and included heterotrophic, lithotrophic, acidophilic, radiotolerant, and sulphate-reducing species of bacteria. This study concludes that the observed biogenic methane is a product of ancient methanogenesis.