Robert Dilmore

Volumetrics of CO2 Storage in Deep Saline Formations

Concern about the role of greenhouse gases in global climate change has generated interest in sequestering CO(2) from fossil-fuel combustion in deep saline formations. Pore space in these formations is initially filled with brine, and space to accommodate injected CO(2) must be generated by displacing brine, and to a lesser extent by compression of brine and rock. The formation volume required to store a given mass of CO(2) depends on the storage mechanism. We compare the equilibrium volumetric requirements of three end-member processes: CO(2) stored as a supercritical fluid (structural or stratigraphic trapping); CO(2) dissolved in pre-existing brine (solubility trapping); and CO(2) solubility enhanced by dissolution of calcite. For typical storage conditions, storing CO(2) by solubility trapping reduces the volume required to store the same amount of CO(2) by structural or stratigraphic trapping by about 50%. Accessibility of CO(2) to brine determines which storage mechanism (structural/stratigraphic versus solubility) dominates at a given time, which is a critical factor in evaluating CO(2) volumetric requirements and long-term storage security.

Measurement and Modeling of CO2 Solubility in Natural and Synthetic Formation Brines for CO2 Sequestration

CO2 solubility data in the natural formation brine, synthetic formation brine, and synthetic NaCl+CaCl2 brine were collected at the pressures from 100 to 200 bar, temperatures from 323 to 423 K. Experimental results demonstrate that the CO2 solubility in the synthetic formation brines can be reliably represented by that in the synthetic NaCl+CaCl2 brines. We extended our previously developed model (PSUCO2) to calculate CO2 solubility in aqueous mixed-salt solution by using the additivity rule of the Setschenow coefficients of the individual ions (Na(+), Ca(2+), Mg(2+), K(+), Cl(-), and SO4(2-)). Comparisons with previously published models against the experimental data reveal a clear improvement of the proposed PSUCO2 model. Additionally, the path of the maximum gradient of the CO2 solubility contours divides the P-T diagram into two distinct regions: in Region I, the CO2 solubility in the aqueous phase decreases monotonically in response to increased temperature; in region II, the behavior of the CO2 solubility is the opposite of that in Region I as the temperature increases.

Spatial and Temporal Characteristics of Historical Oil and Gas Wells in Pennsylvania: Implications for New Shale Gas Resources.

Recent large-scale development of oil and gas from low-permeability unconventional formations (e.g., shales, tight sands, and coal seams) has raised concern about potential environmental impacts. If left improperly sealed, legacy oil and gas wells colocated with that new development represent a potential pathway for unwanted migration of fluids (brine, drilling and stimulation fluids, oil, and gas). Uncertainty in the number, location, and abandonment state of legacy wells hinders environmental assessment of exploration and production activity. The objective of this study is to apply publicly available information on Pennsylvania oil and gas wells to better understand their potential to serve as pathways for unwanted fluid migration. This study presents a synthesis of historical reports and digital well records to provide insights into spatial and temporal trends in oil and gas development. Areas with a higher density of wells abandoned prior to the mid-20th century, when more modern well-sealing requirements took effect in Pennsylvania, and areas where conventional oil and gas production penetrated to or through intervals that may be affected by new Marcellus shale development are identified. This information may help to address questions of environmental risk related to new extraction activities.

Kinetics of chemoheterotrophic microbially mediated reduction of ferric EDTA and the nitrosyl adduct of ferrous EDTA for the treatment and regeneration of spent nitric oxide scrubber liquor.

Biomass from a prototype reactor was used to investigate the kinetics of chemoheterotrophic reduction of solutions of ferric ethylenediaminetetraacetic acid (EDTA) and solutions containing the nitrosyl adduct of ferrous EDTA using ethanol as the primary electron donor and carbon source. A series of batch experiments were conducted using biomass extracted from the scrubber solution treatment and regeneration stage of a prototype iron EDTA-based unit process for the absorption of nitric oxide with subsequent biological treatment. Using a linear-sweep voltammetric method for analysis of the ferric EDTA concentration, iron-reducing bacteria were found to behave according to the Monod kinetic model, at initial concentrations up to 2.16 g chemical oxygen demand (COD) as ethanol per liter, with a half-velocity constant of 0.532 g COD as ethanol/L and a maximum specific utilization rate of 0.127 mol/L of ferric ethylenediamine-tetraacetic acid [Fe(III)EDTA]*(g volatile suspended solids [VSS]/L)d(-1). Based on batch analyses, biomass yield and endogenous decay values of iron-reducing bacteria were estimated to be 0.055 g VSS/g COD and 0.017 L/d, respectively. An average of 1.64 times the theoretical (stoichiometric) demand of ethanol was used to complete reduction reactions. Kinetics of the reduction of the nitrosyl adduct of ferrous EDTA are summarized by the following kinetic constants: half-velocity constant (Ks) of 0.39 g COD/L, maximum specific utilization rate (k) of 0.2 mol/L [NO x Fe(II)EDTA(2-)](g VSS/L)d(-1), and inhibition constant (K(I)) of 0.33 g COD/L, as applied to the modified Monod kinetic expression described herein. Based on batch analyses, the biomass yield of nitrosyl-adduct-reducing bacteria was estimated to be 0.259 g VSS/g COD, endogenous decay was experimentally determined to be 0.0569 L/d, and an average of 1.26 times the stoichiometric demand of ethanol was used to complete reduction reactions.