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DOE OSTI2013

Modeling and Evaluation of Geophysical Methods for Monitoring and Tracking CO2 Migration

Geological sequestration has been proposed as a viable option for mitigating the vast amount of CO 2 being released into the atmosphere daily. Test sites for CO 2 injection have been appearing across the world to ascertain the feasibility of capturing and sequestering carbon dioxide. A major concern with full scale implementation is monitoring and verifying the permanence of injected CO 2 . Geophysical methods, an exploration industry standard, are non-invasive imaging techniques that can be implemented to address that concern. Geophysical methods, seismic and electromagnetic, play a crucial role in monitoring the subsurface pre- and post-injection. Seismic techniques have been the most popular but electromagnetic methods are gaining interest. The primary goal of this project was to develop a new geophysical tool, a software program called GphyzCO2, to investigate the implementation of geophysical monitoring for detecting injected CO 2 at test sites. The GphyzCO2 software consists of interconnected programs that encompass well logging, seismic, and electromagnetic methods. The software enables users to design and execute 3D surface-to-surface (conventional surface seismic) and borehole-to-borehole (cross-hole seismic and electromagnetic methods) numerical modeling surveys. The generalized flow of the program begins with building a complex 3D subsurface geological model, assigning properties to the models that mimic a potential CO 2 injection site, numerically forward model a geophysical survey, and analyze the results. A test site located in Warren County, Ohio was selected as the test site for the full implementation of GphyzCO2. Specific interest was placed on a potential reservoir target, the Mount Simon Sandstone, and cap rock, the Eau Claire Formation. Analysis of the test site included well log data, physical property measurements (porosity), core sample resistivity measurements, calculating electrical permittivity values, seismic data collection, and seismic interpretation. The data was input into GphyzCO2 to demonstrate a full implementation of the software capabilities. Part of the implementation investigated the limits of using geophysical methods to monitor CO 2 injection sites. The results show that cross-hole EM numerical surveys are limited to under 100 meter borehole separation. Those results were utilized in executing numerical EM surveys that contain hypothetical CO 2 injections. The outcome of the forward modeling shows that EM methods can detect the presence of CO 2 .

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2012

Simulation Framework for Regional Geologic CO 2 Storage Along Arches Province of Midwestern United States

This report presents final technical results for the project Simulation Framework for Regional Geologic CO 2 Storage Infrastructure along Arches Province of the Midwest United States . The Arches Simulation project was a three year effort designed to develop a simulation framework for regional geologic carbon dioxide (CO 2 ) storage infrastructure along the Arches Province through development of a geologic model and advanced reservoir simulations of large-scale CO 2 storage. The project included five major technical tasks: (1) compilation of geologic, hydraulic and injection data on Mount Simon, (2) development of model framework and parameters, (3) preliminary variable density flow simulations, (4) multi-phase model runs of regional storage scenarios, and (5) implications for regional storage feasibility. The Arches Province is an informal region in northeastern Indiana, northern Kentucky, western Ohio, and southern Michigan where sedimentary rock formations form broad arch and platform structures. In the province, the Mount Simon sandstone is an appealing deep saline formation for CO 2 storage because of the intersection of reservoir thickness and permeability. Many CO 2 sources are located in proximity to the Arches Province, and the area is adjacent to coal fired power plants along the Ohio River Valley corridor. Geophysical well logs, rock samples, drilling logs, and geotechnical tests were evaluated for a 500,000 km2 study area centered on the Arches Province. Hydraulic parameters and historical operational information was also compiled from Mount Simon wastewater injection wells in the region. This information was integrated into a geocellular model that depicts the parameters and conditions in a numerical array. The geologic and hydraulic data were integrated into a three-dimensional grid of porosity and permeability, which are key parameters regarding fluid flow and pressure buildup due to CO 2 injection. Permeability data were corrected in locations where reservoir tests have been performed in Mount Simon injection wells. The geocellular model was used to develop a series of numerical simulations designed to support CO 2 storage applications in the Arches Province. Variable density fluid flow simulations were initially run to evaluate model sensitivity to input parameters. Two dimensional, multiple-phase simulations were completed to evaluate issues related to arranging injection fields in the study area. A basin-scale, multiple-phase model was developed to evaluate large scale injection effects across the region. Finally, local scale simulations were also completed with more detailed depiction of the Eau Claire formation to investigate to the potential for upward migration of CO 2 . Overall, the technical work on the project concluded that injection large-scale injection may be achieved with proper field design, operation, siting, and monitoring. Records from Mount Simon injection wells were compiled, documenting more than 20 billion gallons of injection into the Mount Simon formation in the Arches Province over the past 40 years, equivalent to approximately 60 million metric tons CO 2 . The multi-state team effort was useful in delineating the geographic variability in the Mount Simon reservoir properties. Simulations better defined potential well fields, well field arrangement, CO 2 pipeline distribution system, and operational parameters for large-scale injection in the Arches Province. Multiphase scoping level simulations suggest that injection fields with arrays of 9 to 50+ wells may be used to accommodate large injection volumes. Individual wells may need to be separated by 3 to 10 km. Injection fields may require spacing of 25 to 40 km to limit pressure and saturation front interference. Basin-scale multiple-phase simulations in STOMP reflect variability in the Mount Simon. While simulations suggest a total injection rate of 100 million metric tons per year (approximately to a 40% reduction of CO 2 emissions from large point sources across the Arches Province) may be feasible, some areas are more suitable due to favorable geology. Sustainable injection rates were higher in areas where there was higher thickness and reservoir permeability. Distribution of injection across well fields is an effective method to reduce pressure and CO 2 saturation front interference.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2012

Simulation Framework For Regional Geologic Co 2 Storage Along Arches Province Of Midwestern United States

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2014

Basin-Scale Leakage Risks from Geologic Carbon Sequestration: Impact on Carbon Capture and Storage Energy Market Competitiveness

This three-year project, performed by Princeton University in partnership with the University of Minnesota and Brookhaven National Laboratory, examined geologic carbon sequestration in regard to CO 2 leakage and potential subsurface liabilities. The research resulted in basin-scale analyses of CO 2 and brine leakage in light of uncertainties in the characteristics of leakage processes, and generated frameworks to monetize the risks of leakage interference with competing subsurface resources. The geographic focus was the Michigan sedimentary basin, for which a 3D topographical model was constructed to represent the hydrostratigraphy. Specifically for Ottawa County, a statistical analysis of the hydraulic properties of underlying sedimentary formations was conducted. For plausible scenarios of injection into the Mt. Simon sandstone, leakage rates were estimated and fluxes into shallow drinking-water aquifers were found to be less than natural analogs of CO 2 fluxes. We developed the Leakage Impact Valuation (LIV) model in which we identified stakeholders and estimated costs associated with leakage events. It was found that costs could be incurred even in the absence of legal action or other subsurface interference because there are substantial costs of finding and fixing the leak and from injection interruption. We developed a model framework called RISCS, which can be used to predict monetized risk of interference with subsurface resources by combining basin-scale leakage predictions with the LIV method. The project has also developed a cost calculator called the Economic and Policy Drivers Module (EPDM), which comprehensively calculates the costs of carbon sequestration and leakage, and can be used to examine major drivers for subsurface leakage liabilities in relation to specific injection scenarios and leakage events. Finally, we examined the competiveness of CCS in the energy market. This analysis, though qualitative, shows that financial incentives, such as a carbon tax, are needed for coal combustion with CCS to gain market share. In another part of the project we studied the role of geochemical reactions in affecting the probability of CO 2 leakage. A basin-scale simulation tool was modified to account for changes in leakage rates due to permeability alterations, based on simplified mathematical rules for the important geochemical reactions between acidified brines and caprock minerals. In studies of reactive flows in fractured caprocks, we examined the potential for permeability increases, and the extent to which existing reactive transport models would or would not be able to predict it. Using caprock specimens from the Eau Claire and Amherstburg, we found that substantial increases in permeability are possible for caprocks that have significant carbonate content, but minimal alteration is expected otherwise. We also found that while the permeability increase may be substantial, it is much less than what would be predicted from hydrodynamic models based on mechanical aperture alone because the roughness that is generated tends to inhibit flow.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2014

Risk Evaluation for CO 2 Geosequestration in the Knox Supergroup, Illinois Basin (Final Report)

This report describes a process and provides seed information for identifying and evaluating risks pertinent to a hypothetical carbon dioxide (CO 2 ) capture and sequestration (CCS) project. In the envisioned project, the target sequestration reservoir rock is the Potosi Formation of the Knox Supergroup. The Potosi is identified as a potential target formation because (1) at least locally, it contains vuggy to cavernous layers that have very high porosity, and (2) it is present in areas where the deeper Mt. Simon Sandstone (a known potential reservoir unit) is absent or nonporous. The key report content is discussed in Section 3.3, which describes two lists of Features, Events, and Processes (FEPs) that should be considered during the design stage of such a project. These lists primarily highlight risk elements particular to the establishment of the Potosi as the target formation in general. The lists are consciously incomplete with respect to risk elements that would be relevant for essentially all CCS projects regardless of location or geology. In addition, other risk elements specific to a particular future project site would have to be identified. Sources for the FEPs and scenarios listed here include the iconic Quintessa FEPs list developed for the International Energy Agency Greenhouse Gas (IEAGHG) Programme; previous risk evaluation projects executed by Schlumberger Carbon Services; and new input solicited from experts currently working on aspects of CCS in the Knox geology. The projects used as sources of risk information are primarily those that have targeted carbonate reservoir rocks similar in age, stratigraphy, and mineralogy to the Knox-Potosi. Risks of using the Potosi Formation as the target sequestration reservoir for a CCS project include uncertainties about the levels of porosity and permeability of that rock unit; the lateral consistency and continuity of those properties; and the ability of the project team to identify suitable (i.e., persistently porous and permeable) injection depths within the overall formation. Less direct implications include the vertical position of the Potosi within the rock column and the absence of a laterally extensive shale caprock immediately overlying the Potosi. Based on modeling work done partly in association with this risk report, risks that should also be evaluated include the ability of available methods to predict and track the development of a CO 2 plume as it migrates away from the injection point(s). The geologic and hydrodynamic uncertainties present risks that are compounded at the stage of acquiring necessary drilling and injection permits. It is anticipated that, in the future, a regional geologic study or CO 2 -emitter request may identify a small specific area as a prospective CCS project site. At that point, the FEPs lists provided in this report should be evaluated by experts for their relative levels of risk. A procedure for this evaluation is provided. The higher-risk FEPs should then be used to write project-specific scenarios that may themselves be evaluated for risk. Then, actions to reduce and to manage risk can be described and undertaken. The FEPs lists provided as Appendix 2 should not be considered complete, as potentially the most important risks are ones that have not yet been thought of. But these lists are intended to include the most important risk elements pertinent to a Potosi-target CCS project, and they provide a good starting point for diligent risk identification, evaluation, and management.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2014

Modeling CO 2 -Brine-Rock Interaction Including Mercury and H 2 S Impurities in the Context of CO 2 Geologic Storage

This study uses modeling and simulation approaches to investigate the impacts on injectivity of trace amounts of mercury (Hg) in a carbon dioxide (CO 2 ) stream injected for geologic carbon sequestration in a sandstone reservoir at ~2.5 km depth. At the range of Hg concentrations expected (7-190 ppbV, or ~ 0.06-1.6 mg/std.m 3 CO 2 ), the total volumetric plugging that could occur due to complete condensation of Hg, or due to complete precipitation of Hg as cinnabar, results in a very small porosity change. In addition, Hg concentration much higher than the concentrations considered here would be required for Hg condensation to even occur. Concentration of aqueous Hg by water evaporation into CO 2 is also unlikely because the higher volatility of Hg relative to H 2 O at reservoir conditions prevents the Hg concentration from increasing in groundwater as dry CO 2 sweeps through, volatilizing both H 2 O and Hg. Using a model-derived aqueous solution to represent the formation water, batch reactive geochemical modeling show that the reaction of the formation water with the CO 2 -Hg mixture causes the pH to drop to about 4.7 and then become buffered near 5.2 upon reaction with the sediments, with a negligible net volume change from mineral dissolution and precipitation. Cinnabar (HgS(s)) is found to be thermodynamically stable as soon as the Hg-bearing CO 2 reacts with the formation water which contains small amounts of dissolved sulfide. Liquid mercury (Hg(l)) is not found to be thermodynamically stable at any point during the simulation. Two-dimensional radial reactive transport simulations of CO 2 injection at a rate of 14.8 kg/s into a 400 m-thick formation at isothermal conditions of 106°C and average pressure near 215 bar, with varying amounts of Hg and H 2 S trace gases, show generally that porosity changes only by about ±0.05% (absolute, i.e., new porosity = initial porosity ±0.0005) with Hg predicted to readily precipitate from the CO 2 as cinnabar in a zone mostly matching the single-phase CO 2 plume. The precipitation of minerals other than cinnabar, however, dominates the evolution of porosity. Main reactions include the replacement of primarily Fe-chlorite by siderite, of calcite by dolomite, and of K-feldspar by muscovite. Chalcedony is also predicted to precipitate from the dissolution of feldspars and quartz. Although the range of predicted porosity change is quite small, the amount of dissolution and precipitation predicted for these individual minerals is not negligible. These reactive transport simulations assume that Hg gas behaves ideally. To examine effects of non-ideality on these simulations, approximate calculations of the fugacity coefficient of Hg in CO 2 were made. Results suggest that Hg condensation could be significantly overestimated when assuming ideal gas behavior, making our simulation results conservative with respect to impacts on injectivity. The effect of pressure on Henry’s constant for Hg is estimated to yield Hg solubilities about 10% lower than when this effect is not considered, a change that is considered too small to affect the conclusions of this report. Although all results in this study are based on relatively mature data and modeling approaches, in the absence of experimental data and more detailed site-specific information, it is not possible to fully validate the results and conclusions.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2013

High Fidelity Computational Analysis of CO2 Trapping at Pore Scales (Final Technical Report)

With an alarming rise in carbon dioxide (CO2) emission from anthropogenic sources, CO2 sequestration has become an attractive choice to mitigate the emission. Some popular storage media for CO 2 are oil reservoirs, deep coal-bed, and deep oceanic-beds. These have been used for the long term CO 2 storage. Due to special lowering viscosity and surface tension property of CO 2 , it has been widely used for enhanced oil recovery. The sites for CO 2 sequestration or enhanced oil recovery mostly consist of porous rocks. Lack of knowledge of molecular mobility under confinement and molecule-surface interactions between CO2 and natural porous media results in generally governed by unpredictable absorption kinetics and total absorption capacity for injected fluids, and therefore, constitutes barriers to the deployment of this technology. Therefore, it is important to understand the flow dynamics of CO 2 through the porous microstructures at the finest scale (pore-scale) to accurately predict the storage potential and long-term dynamics of the sequestered CO 2 . This report discusses about pore-network flow modeling approach using variational method and analyzes simulated results this method simulations at pore-scales for idealized network and using Berea Sandstone CT scanned images. Variational method provides a promising way to study the kinetic behavior and storage potential at the pore scale in the presence of other phases. The current study validates variational solutions for single and two-phase Newtonian and single phase non-Newtonian flow through angular pores for special geometries whose analytical and/or empirical solutions are known. The hydraulic conductance for single phase flow through a triangular duct was also validated against empirical results derived from lubricant theory.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2013

Shallow Carbon Sequestration Demonstration Project

The potential for carbon sequestration at relatively shallow depths was investigated at four power plant sites in Missouri. Exploratory boreholes were cored through the Davis Shale confining layer into the St. Francois aquifer (Lamotte Sandstone and Bonneterre Formation). Precambrian basement contact ranged from 654.4 meters at the John Twitty Energy Center in Southwest Missouri to over 1100 meters near the Sioux Power Plant in St. Charles County. Investigations at the John Twitty Energy Center included 3D seismic reflection surveys, downhole geophysical logging and pressure testing, and laboratory analysis of rock core and water samples. Plans to perform injectivity tests at the John Twitty Energy Center, using food grade CO 2 , had to be abandoned when the isolated aquifer was found to have very low dissolved solids content. Investigations at the Sioux Plant and Thomas Hill Energy Center in Randolph County found suitably saline conditions in the St. Francois. A fourth borehole in Platte County was discontinued before reaching the aquifer. Laboratory analyses of rock core and water samples indicate that the St. Charles and Randolph County sites could have storage potentials worthy of further study. The report suggests additional Missouri areas for further investigation as well.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2014

Carbon Dioxide Sealing Capacity: Textural or Compositional Controls? (Final Scientific/Technical Report)

This research project is aiming to assess the carbon dioxide sealing capacity of most common seal-rocks, such as shales and non-fractured limestones, by analyzing the role of textural and compositional parameters of those rocks. We hypothesize that sealing capacity is controlled by textural and/or compositional parameters of caprocks. In this research, we seek to evaluate the importance of textural and compositional parameters affecting the sealing capacity of caprocks. The conceptual framework involves two testable end-member hypotheses concerning the sealing capacity of carbon dioxide reservoir caprocks. Better understanding of the elements controlling sealing quality will advance our knowledge regarding the sealing capacity of shales and carbonates. Due to relatively low permeability, shale and non-fractured carbonate units are considered relatively impermeable formations which can retard reservoir fluid flow by forming high capillary pressure. Similarly, these unites can constitute reliable seals for carbon dioxide capture and sequestration purposes. This project is a part of the comprehensive project with the final aim of studying the caprock sealing properties and the relationship between microscopic and macroscopic characteristics of seal rocks in depleted gas fields of Oklahoma Panhandle. Through this study we examined various seal rock characteristics to infer about their respective effects on sealing capacity in special case of replacing reservoir fluid with super critical carbon dioxide (scCO 2 ). To assess the effect of textural and compositional properties on scCO 2 maximum retention column height we collected 30 representative core samples in caprock formations in three counties (Cimarron, Texas, Beaver) in Oklahoma Panhandle. Core samples were collected from various seal formations (e.g., Cherokee, Keys, Morrowan) at different depths. We studied the compositional and textural properties of the core samples using several techniques. Mercury Injection Porosimetry (MIP), Scanning Electron Microscopy SEM, and Sedigraph measurements are used to assess the pore-throat-size distribution, sorting, texture, and grain size of the samples. Also, displacement pressure at 10% mercury saturation (Pd) and graphically derived threshold pressure (P c ) were determined by MIP technique. SEM images were used for qualitative study of the minerals and pores texture of the core samples. Moreover, EDS (Energy Dispersive X-Ray Spectrometer), BET specific surface area, and Total Organic Carbon (TOC) measurements were performed to study various parameters and their possible effects on sealing capacity of the samples. We found that shales have the relatively higher average sealing threshold pressure (P c ) than carbonate and sandstone samples. Based on these observations, shale formations could be considered as a promising caprock in terms of retarding scCO 2 flow and leakage into above formations. We hypothesized that certain characteristics of shales (e.g., 3 fine pore size, pore size distribution, high specific surface area, and strong physical chemical interaction between wetting phase and mineral surface) make them an efficient caprock for sealing super critical CO 2 . We found that the displacement pressure at 10% mercury saturation could not be the ultimate representative of the sealing capacity of the rock sample. On the other hand, we believe that graphical method, introduced by Cranganu (2004) is a better indicator of the true sealing capacity. Based on statistical analysis of our samples from Oklahoma Panhandle we assessed the effects of each group of properties (textural and compositional) on maximum supercritical CO 2 height that can be hold by the caprock. We conclude that there is a relatively strong positive relationship (+.40 to +.69) between supercritical CO 2 column height based on P c and hard/ soft mineral content index (ratio of minerals with Mohs hardness more than 5 over minerals with Mohs hardness less than 5) in both shales and limestone samples. Average median pore radius and porosity display a strong negative correlation with supercritical CO 2 retention column height. Also, increasing bulk density is positively correlated with the supercritical CO 2 retention column height. One of the most important factors affecting sealing capacity and consequently the height of supercritical CO 2 column is sorting of the pore throats. We observed a strong positive correlation between pore throat sorting and height of CO 2 retention column, especially in shales. This correlation could not be observed in limestone samples. It suggests that the pore throat sorting is more controlling the sealing capacity in shales and shales with well sorted pore throats are the most reliable lithology as seal. We observed that Brunauer–Emmett–Teller (BET) surface area shows a very strong correlation with CO 2 retention column height in limestone samples while BET surface area did not display significant correlation in shales. Pore structure based on SEM micrographs exhibits strong correlation with CO 2 retention column height in limestones. Both intercrystalline and vuggy structures have negative correlations while intergranular texture has positive correlation in limestone with respect to CO 2 retention column height. Textural effects observed on SEM micrographs did not show statistically significant correlation with supercritical CO 2 retention column height in shale samples. Finally, we showed that increasing hard/soft mineral index is strongly correlated with the displacement pressure in limestone samples. Vuggy texture displays a relatively strong and negative correlation with displacement pressure values at 10% mercury saturation in shale samples.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2013

Training Students to Analyze Spatial and Temporal Heterogeneities in Reservoir and Seal Petrology, Mineralogy, and Geochemistry: Implications for CO{sub 2} Sequestration Prediction, Simulation, and Monitoring

The objective of this project was to expose and train multiple students in geological tools that are essential to reservoir characterization and geologic sequestration including but not limited to advanced petrological methods, mineralogical methods, and geochemical methods; core analysis, and geophysical well-log interpretation. These efforts have included training of multiple students through geologically based curriculum and research using advanced petrological, mineralogical, and geochemical methods. In whole, over the last 3+ years, this award has supported 5,828 hours of student research, supporting the work of several graduate and undergraduate students. They have all received training directly related to ongoing CO{sub 2} sequestration demonstrations. The students have all conducted original scientific research on topics related to understanding the importance of lithological, textural, and compositional variability in formations that are being targeted as CO{sub 2} sequestration reservoirs and seals. This research was linked to the Mount Simon Sandstone reservoir and overlying Eau Claire Formation seal in the Illinois Basin- a system where over one million tons of CO{sub 2} are actively being injected with the first large-scale demonstration of anthropogenic CO{sub 2} storage in the U.S. Student projects focused specifically on 1) reservoir porosity characterization and evaluation, 2) petrographic, mineralogical, and geochemical evidence of fluid-related diagenesis in the caprock, 3) textural changes in reservoir samples exposed to experimental CO{sub 2} + brine conditions, 4) controls on spatial heterogeneity in composition and texture in both the reservoir and seal, 5) the implications of small-scale fractures within the reservoir, and 6) petrographic and stable isotope analyses of carbonates in the seal to understand the burial history of the system. The student-led research associated with this project provided real-time and hands-on experience with a relevant CO{sub 2} system, provided relevant information to the regional partnerships who are working within these formations, and provides more broadly applicable understanding and method development for other carbon capture and storage systems.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2014

DE-SC0004118 (Wong & Lindquist). Final Report: Changes of Porosity, Permeability and Mechanical Strength Induced by Carbon Dioxide Sequestration.

In the context of CO{sub 2} sequestration, the overall objective of this project is to conduct a systematic investigation of how the flow of the acidic, CO{sub 2} saturated, single phase component of the injected/sequestered fluid changes the microstructure, permeability and strength of sedimentary rocks, specifically limestone and sandstone samples. Hydromechanical experiments, microstructural observations and theoretical modeling on multiple scales were conducted.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2013

No-Impact Threshold Values for NRAP's Reduced Order Models

The purpose of this study was to develop methodologies for establishing baseline datasets and statistical protocols for determining statistically significant changes between background concentrations and predicted concentrations that would be used to represent a contamination plume in the Gen II models being developed by NRAP’s Groundwater Protection team. The initial effort examined selected portions of two aquifer systems; the urban shallow-unconfined aquifer system of the Edwards-Trinity Aquifer System (being used to develop the ROM for carbon-rock aquifers, and the a portion of the High Plains Aquifer (an unconsolidated and semi-consolidated sand and gravel aquifer, being used to development the ROM for sandstone aquifers). Threshold values were determined for Cd, Pb, As, pH, and TDS that could be used to identify contamination due to predicted impacts from carbon sequestration storage reservoirs, based on recommendations found in the EPA’s ''Unified Guidance for Statistical Analysis of Groundwater Monitoring Data at RCRA Facilities'' (US Environmental Protection Agency 2009). Results from this effort can be used to inform a ''no change'' scenario with respect to groundwater impacts, rather than the use of an MCL that could be significantly higher than existing concentrations in the aquifer.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2013

Leakage Risk Assessment of CO{sub 2} Transportation by Pipeline at the Illinois Basin Decatur Project, Decatur, Illinois

The Illinois Basin Decatur Project (IBDP) is designed to confirm the ability of the Mt. Simon Sandstone, a major regional saline-water-bearing formation in the Illinois Basin, to store 1 million tons of carbon dioxide (CO{sub 2}) injected over a period of three years. The CO{sub 2} will be provided by Archer Daniels Midland (ADM) from its Decatur, Illinois, ethanol plant. In order to transport CO{sub 2} from the capture facility to the injection well (also located within the ADM plant boundaries), a high-pressure pipeline of length 3,200 ft (975 m) has been constructed, running above the ground surface within the ADM plant footprint. We have qualitatively evaluated risks associated with possible pipeline failure scenarios that lead to discharge of CO{sub 2} within the real-world environment of the ADM plant in which there are often workers and visitors in the vicinity of the pipeline. There are several aspects of CO{sub 2} that make its transportation and potential leakage somewhat different from other substances, most notable is its non-flammability and propensity to change to solid (dry ice) upon strong decompression. In this study, we present numerical simulations using Computational Fluid Dynamics (CFD) methods of the release and dispersion of CO{sub 2} from individual hypothetical pipeline failures (i.e., leaks). Failure frequency of the various components of a pipeline transportation system over time are taken from prior work on general pipeline safety and leakage modeling and suggest a 4.65% chance of some kind of pipeline failure over the three-years of operation. Following the Precautionary Principle (see below), we accounted for full-bore leakage scenarios, where the temporal evolution of the mass release rate from the high-pressure pipeline leak locations was simulated using a state-of-the-art Pipe model which considers the thermodynamic effects of decompression in the entire pipeline. Failures have been simulated at four representative locations along the pipeline route within the ADM plant. Leakage scenarios at sites along the route of the pipeline, where plant operations (e.g., vehicular and train transportation) seem to present a higher likelihood of accidental failure, for example due to vehicles or equipment crashing into the pipeline and completely severing it, were modeled by allowing them to have a double source consistent with the pipeline releasing high-pressure CO{sub 2} from both ends of the broken pipe after a full-bore offset rupture. Simulation results show that the built environment of the plant plays a significant role in the dispersion of the gas as leaking CO{sub 2} can impinge upon buildings and other infrastructure. In all scenarios simulated, the region of very high-concentration of CO{sub 2} is limited to a small area around the pipeline failure, suggesting the likelihood of widespread harmful CO{sub 2} exposure to plant personnel from pipeline leakage is low. An additional risk is posed by the blast wave that emanates from a high-pressure pipeline when it is breached quickly. We estimate the blast wave risk as low because it occurs only for a short time in the immediate vicinity of the rupture, and requires an instantaneous large-scale rupture to occur. We recommend consideration of signage and guard rails and posts to mitigate the likelihood of vehicles crashing into the pipeline. A standardized emergency response plan applicable to capture plants within industrial sites could be developed based on the IBDP that would be useful for other capture plants. Finally, we recommend carrying out coupled wellbore-reservoir blowout scenario modeling to understand the potential for hazardous conditions arising from an unexpected blowout at the wellhead.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2013

Leakage Risk Assessment of CO 2 Transportation by Pipeline at the Illinois Basin Decatur Project

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2013

Assessment of Brine Management for Geologic Carbon Sequestration

Geologic carbon sequestration (GCS) is the injection of carbon dioxide (CO 2 ), typically captured from stationary emission sources, into deep geologic formations to prevent its entry into the atmosphere. Active pilot facilities run by regional United States (US) carbon sequestration partnerships inject on the order of one million metric tonnes (mt) CO 2 annually while the US electric power sector emits over 2000 million mt-CO 2 annually. GCS is likely to play an increasing role in US carbon mitigation initiatives, but scaling up GCS poses several challenges. Injecting CO 2 into sedimentary basins raises fluid pressure in the pore space, which is typically already occupied by naturally occurring, or native, brine. The resulting elevated pore pressures increase the likelihood of induced seismicity, of brine or CO 2 escaping into potable groundwater resources, and of CO 2 escaping into the atmosphere. Brine extraction is one method for pressure management, in which brine in the injection formation is brought to the surface through extraction wells. Removal of the brine makes room for the CO 2 and decreases pressurization. Although the technology required for brine extraction is mature, this form of pressure management will only be applicable if there are cost-effective and sustainable methods of disposing of the extracted brine. Brine extraction, treatment, and disposal may increase the already substantial capital, energy, and water demands of Carbon dioxide Capture and Sequestration (CCS). But, regionally specific brine management strategies may be able to treat the extracted water as a source of revenue, energy, and water to subsidize CCS costs, while minimizing environmental impacts. By this approach, value from the extracted water would be recovered before disposing of any resulting byproducts. Until a price is placed on carbon, we expect that utilities and other CO 2 sources will be reluctant to invest in capital intensive, high risk GCS projects; early technical, economic, and environmental assessments of brine management are extremely valuable for determining the potential role of GCS in the US. We performed a first order feasibility and economic assessment, at three different locations in the US, of twelve GCS extracted-water management options, including: geothermal energy extraction, desalination, salt and mineral harvesting, rare-earth element harvesting, aquaculture, algae biodiesel production, road de-icing, enhanced geothermal system (EGS) recharge, underground reinjection, landfill disposal, ocean disposal, and evaporation pond disposal. Three saline aquifers from different regions of the US were selected as hypothetical GCS project sites to encompass variation in parameters that are relevant to the feasibility and economics of brine disposal. The three aquifers are the southern Mt. Simon Sandstone Formation in the Illinois Basin, IL; the Vedder Formation in the southern San Joaquin Basin, CA; and the Jasper Interval in the eastern Texas Gulf Basin, TX. These aquifers are candidates for GCS due to their physical characteristics and their close proximity to large CO 2 emission sources. Feasibility and impacts were calculated using one mt-CO 2 injected as the functional unit of brine management. Scenarios were performed for typical 1000MW coal-fired power plants (CFPP) that incurred an assumed 24 percent carbon capture energy penalty (EP), injected 90 percent of CO 2 emissions (~9 million mt- CO 2 injected annually), and treated extracted water onsite. Net present value (NPV), land requirements, laws and regulations, and technological limits were determined for each stage of disposal, and used to estimate feasibility. The boundary of the assessment began once extracted water was brought to the surface, and ended once the water evaporated, was injected underground, or was discharged into surface water bodies. Results of the assessment were generated, stored, and analyzed using Microsoft Excel spreadsheets and ESRI Geographical Information System (GIS) maps. Conclusions about the relative benefits and impacts of alternative brine-management strategies were highly sensitive to local climate and weather, and aquifer water chemistry. The NPV of certain scenarios ranged from -$50/mt-CO 2 (a cost) to +$10/mt-CO 2 (revenue). The land footprint of the scenarios in this study ranged from <1 km 2 to 100 km 2 . Brine extraction as a pressure management tool for GCS has potential for improving the economics and for minimizing the environmental impacts of CCS. In order to maximize this potential, careful analysis of each saline aquifer and region must be conducted to determine a regionally appropriate brine use sequence (BUS) at the time of site selection. Models that use GIS will be essential tools in determining such sequences for individual CFPP. Future studies that perform risk and life cycle assessments (LCA) of BUS scenarios, incorporate additional impact metrics into the BUS model, and enhance the temporal sensitivity of the model would improve the robustness of this regional assessment method.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2014

Deep Geothermal Drilling Using Millimeter Wave Technology (Final Technical Research Report)

Conventional drilling methods are very mature, but still have difficulty drilling through very deep,very hard and hot rocks for geothermal, nuclear waste entombment and oil and gas applications.This project demonstrated the capabilities of utilizing only high energy beams to drill such rocks,commonly called ‘Direct Energy Drilling’, which has been the dream of industry since the invention of the laser in the 1960s. A new region of the electromagnetic spectrum, millimeter wave (MMW) wavelengths at 30-300 giga-hertz (GHz) frequency was used to accomplish this feat. To demonstrate MMW beam drilling capabilities a lab bench waveguide delivery, monitoring and instrument system was designed, built and tested around an existing (but non-optimal) 28 GHz frequency, 10 kilowatt (kW) gyrotron. Low waveguide efficiency, plasma generation and reflected power challenges were overcome. Real-time monitoring of the drilling process was also demonstrated. Then the technical capability of using only high power intense millimeter waves to melt (with some vaporization) four different rock types (granite, basalt, sandstone, limestone) was demonstrated through 36 bench tests. Full bore drilling up to 2” diameter (size limited by the available MMW power) was demonstrated through granite and basalt samples. The project also demonstrated that MMW beam transmission losses through high temperature (260°C, 500oF), high pressure (34.5 MPa, 5000 psi) nitrogen gas was below the error range of the meter long path length test equipment and instruments utilized. To refine those transmission losses closer, to allow extrapolation to very great distances, will require a new test cell design and higher sensitivity instruments. All rock samples subjected to high peak temperature by MMW beams developed fractures due to thermal stresses, although the peak temperature was thermodynamically limited by radiative losses. Therefore, this limited drill rate and rock strength data were not able to be determined experimentally. New methods to encapsulate larger rock specimens must be developed and higher power intensities are needed to overcome these limitations. It was demonstrated that rock properties are affected (weakening then strengthened) by exposure to high temperatures. Since only MMW beams can economically reach rock temperatures of over 1650°C, even exceeding 3000°C, that can cause low viscosity melts or vaporization of rocks. Future encapsulated rock specimens must provide sufficiently large sizes of thermally impacted material to provide for the necessary rock strength, permeability and other analyzes required. Multiple MMW field systems, tools and methods for drilling and lining were identified. It was concluded that forcing a managed over-pressure drilling operation would overcome water influx and hot rock particulates handling problems, while simultaneously forming the conditions necessary to create a strong, sealing rock melt liner. Materials that contact hot rock surfaces were identified for further study. High power windows and gases for beam transmission under high pressures are critical paths for some of the MMW drilling systems. Straightness/ alignment can be a great benefit or a problem, especially if a MMW beam is transmitted through an existing, conventionally drilled bore.

04 OIL SHALES AND TAR SANDS↗

DOE OSTI2014

Gulf of Mexico miocene CO₂ site characterization mega transect

This project characterized the Miocene-age sub-seafloor stratigraphy in the near-offshore portion of the Gulf of Mexico adjacent to the Texas coast. The large number of industrial sources of carbon dioxide (CO₂) in coastal counties and the high density of onshore urbanization and environmentally sensitive areas make this offshore region extremely attractive for long-term storage of carbon dioxide emissions from industrial sources (CCS). The study leverages dense existing geologic data from decades of hydrocarbon exploration in and around the study area to characterize the regional geology for suitability and storage capacity. Primary products of the study include: regional static storage capacity estimates, sequestration “leads” and prospects with associated dynamic capacity estimates, experimental studies of CO₂-brine-rock interaction, best practices for site characterization, a large-format ‘Atlas’ of sequestration for the study area, and characterization of potential fluid migration pathways for reducing storage risks utilizing novel high-resolution 3D (HR3D) seismic surveys. In addition, three subcontracted studies address source-to-sink matching optimization, offshore well bore management and environmental aspects. The various geologic data and interpretations are integrated and summarized in a series of cross-sections and maps, which represent a primary resource for any near-term commercial deployment of CCS in the area. The regional study characterized and mapped important geologic features (e.g., Clemente-Tomas fault zone, the regionally extensive Marginulina A and Amphistegina B confining systems, etc.) that provided an important context for regional static capacity estimates and specific sequestration prospects of the study. A static capacity estimate of the majority of the Study area (14,467 mi 2 ) was estimated at 86 metric Gigatonnes. While local capacity estimates are likely to be lower due to reservoir-scale characteristics, the offshore Miocene interval is a storage resource of National interest for providing CO₂ storage as an atmospheric emissions abatement strategy. The natural petroleum system was used as an analog to infer seal quality and predict possible migration pathways of fluids in an engineered system of anthropogenic CO₂ injection and storage. The regional structural features (e.g., Clemente-Tomas fault zone) that exert primary control on the trapping and distribution of Miocene hydrocarbons are expected to perform similarly for CCS. Industrial-scale CCS will require storage capacity utilizing well-documented Miocene hydrocarbon (dominantly depleted gas) fields and their larger structural closures, as well as barren (unproductive, brine-filled) closures. No assessment was made of potential for CO₂ utilization for enhanced oil and gas recovery. The use of 3D numerical fluid flow simulations have been used in the study to greatly assist in characterizing the potential storage capacity of a specific reservoir. Due to the complexity of geologic systems (stratigraphic heterogeneity) and inherent limitations on producing a 3D geologic model, these simulations are typically simplified scenarios that explore the influence of model property variability (sensitivity study). A specific site offshore San Luis Pass (southern Galveston Island) was undertaken successfully, indicating stacked storage potential. Downscaling regional capacity estimates to the local scale (and the inverse) has proven challenging, and remains an outstanding gap in capacity assessments. In order to characterize regional seal performance and identify potential brine and CO₂ leakage pathways, results from three high-resolution 3D (HR3D) seismic datasets acquired by the study using novel HR3D (P-Cable) acquisition system showed steady and significant improvements in data quality because of improved acquisition and processing technique. Finely detailed faults and stratigraphy in the shallowest 1000 milliseconds (~800 m) of data allowed for the identification and mapping of unconformable surfaces including what is probably a surface associated with the last Pleistocene glacial lowstand. The identification of a previously unrecognized (in commercial seismic data) gas chimney that was clearly defined in the 2013 HR3D survey, indicates that HR3D surveys may be useful as both a characterization tool for the overburden of a potential carbon sequestration site and as an additional monitoring tool for future engineered injection sites. Geochemical modeling indicated that injection of CO₂ would result in minor dissolution of calcite, K-feldspar and albite. In addition, modeling of typical brines in Miocene age rocks indicate that approximately 5% of injection capacity would result from CO₂ dissolution into the brine. After extensive searches, no rock samples of the Marginulina A and Amphistegina B seals (“caprocks”) were obtained, but analyses of available core samples of other Miocene age mudrocks (seals or caprocks) indicate that they have sealing ability sufficient for potential CO 2 storage in underlying sandstone units.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2015

Area 2. Use Of Engineered Nanoparticle-Stabilized CO 2 Foams To Improve Volumetric Sweep Of CO 2 EOR Processes

The goal of this project was to develop a new CO 2 injection enhanced oil recovery (CO 2 -EOR) process using engineered nanoparticles with optimized surface coatings that has better volumetric sweep efficiency and a wider application range than conventional CO 2 -EOR processes. The main objectives of this project were to (1) identify the characteristics of the optimal nanoparticles that generate extremely stable CO 2 foams in situ in reservoir regions without oil; (2) develop a novel method of mobility control using “self-guiding” foams with smart nanoparticles; and (3) extend the applicability of the new method to reservoirs having a wide range of salinity, temperatures, and heterogeneity. Concurrent with our experimental effort to understand the foam generation and transport processes and foam-induced mobility reduction, we also developed mathematical models to explain the underlying processes and mechanisms that govern the fate of nanoparticle-stabilized CO 2 foams in porous media and applied these models to (1) simulate the results of foam generation and transport experiments conducted in beadpack and sandstone core systems, (2) analyze CO 2 injection data received from a field operator, and (3) aid with the design of a foam injection pilot test. Our simulator is applicable to near-injection well field-scale foam injection problems and accounts for the effects due to layered heterogeneity in permeability field, foam stabilizing agents effects, oil presence, and shear-thinning on the generation and transport of nanoparticle-stabilized C/W foams. This report presents the details of our experimental and numerical modeling work and outlines the highlights of our findings.

54 ENVIRONMENTAL SCIENCES↗