Geologic and infrastructure factors for delineating areas for clean coal: examples in Texas, USA

Texas has a wide variety of areas that can be targeted for new clean-coal facilities. These areas are delineated by mapping spatial linkages between coal- and lignite-bearing formations, groundwater and surface-water resources, and CO₂ sinks in brine formations for long-term CO₂ storage or in mature oil fields with potential for enhanced oil recovery (EOR). However, a variety of infrastructure factors make it feasible to also target numerous areas outside coal and lignite basins in Texas. These infrastructure factors include pipelines for delivery of CO₂ to subsurface sinks and delivery of coal-produced hydrogen to refineries, ease of connection to existing transmission lines, distribution of nonattainment areas where new clean-coal facilities could be constructed and be compliant with strict air-quality standards, and railroads that can transport coal and other feedstock to new clean-coal facilities. Primary regions in Texas where favorably co-located CO₂ source-sink factors related to coal and lignite trends include the Gulf Coast, the Eastern Shelf of the Permian Basin, and the Fort Worth Basin. However, areas outside coal and lignite basins, particularly the Permian Basin where a new clean-coal facility is being planned, also have clean-coal potential because of existing CO₂ pipelines and proximity to EOR fields that can economically sustain new clean-coal facilities.     

Quick-look assessments to identify optimal CO2 EOR storage sites

A newly developed, multistage quick-look methodology allows for the efficient screening of an unmanageably large number of reservoirs to generate a workable set of sites that closely match the requirements for optimal CO₂ enhanced oil recovery (EOR) storage. The objective of the study is to quickly identify miscible CO₂ EOR candidates in areas that contain thousands of reservoirs and to estimate additional oil recovery and sequestration capacities of selected top options through dimensionless modeling and reservoir characterization. Quick-look assessments indicate that the CO₂ EOR resource potential along the US Gulf Coast is 4.7 billion barrels, and CO₂ sequestration capacity is 2.6 billion metric tons. In the first stage, oil reservoirs are screened and ranked in terms of technical and practical feasibility for miscible CO₂ EOR. The second stage provides quick estimates of CO₂ EOR potential and sequestration capacities. In the third stage, a dimensionless group model is applied to a selected set of sites to improve the estimates of oil recovery and storage potential using appropriate inputs for rock and fluid properties, disregarding reservoir architecture and sweep design. The fourth stage validates and refines the results by simulating flow in a model that describes the internal architecture and fluid distribution in the reservoir. The stated approach both saves time and allows more resources to be applied to the best candidate sites.     

A survey of oil and gas wells in the Texas Gulf Coast,USA, and implications for geological sequestration of CO<Subscript>2</Subscript>

Subsurface sequestration of CO₂ in oil and gas provinces where permanence of hydrocarbon accumulations has proven the reliability of potential traps is rightly seen as a solid option for containment of CO₂ atmospheric concentrations. However, one of the most promising provinces for carbon storage in North America, the Texas Gulf Coast, has also been heavily drilled for more than a century, puncturing many otherwise perfectly sound seals (>125,000 wells over ~50,000 km²). As a result, boreholes and, in particular, older abandoned wells could be major leakage pathways for sequestered CO₂. This article presents statistics on well spatial and depth distribution that have been drawn from public domain sources and relates these data to historical plugging and abandonment regulations in the Texas Gulf Coast. Surface-well density averages of 2.4 wells/km² can be locally much higher—but also much lower in larger areas. Average well penetration density drops to 0.27 and 0.05 well/km² below a depth of 2,440 and 3,660 m, respectively. Natural mitigating factors such as thief zones and heaving “shales” could also play a role in limiting the impact of these direct conduits to the shallow subsurface and surface.     

Optimal aquifers and reservoirs for CCS and EOR in the Kingdom of Saudi Arabia: an overview

An overview on the tectono-stratigraphic framework of the Arabian plate indicates obvious differences between two distinct areas: the hydrocarbon-prolific sector and non-hydrocarbon-prolific sector. These differences resulted from the interplay of a variety of factors; some of which are related to the paleo-geographic configuration (eustatic sea level fluctuations, climatic conditions, and salt Basins), others to differential subsidence (burial) and structural inversions. During the Paleozoic, the regional compression was caused by far field effects of the Hercynian orogeny. This led to major folded structures in central and eastern Saudi Arabia (e.g. Ghawar anticline). During the Mesozoic, the most important tectonic factor was the stretching of the crust (extension), accompanied with the increase in temperature, resulting in an increase of the accommodation space, and thicker sedimentary successions. Regional unconformities are mostly found where folded structures are dominant, and they acted as a carrier systems for the accumulation of hydrocarbon and groundwater. A good understanding of the stratigraphy and tectonic evolution is, thus, required to develop carbon capture and storage (CCS) and to design efficiently enhanced oil recovery (EOR) in both sectors. Oil and gas reservoirs offer geologic storage potential as well as the economic opportunity of better production through CO₂-EOR. The world greatest hydrocarbon reservoirs mainly consist of Jurassic carbonate rocks, and are located around the Arabian Basin (including the eastern KSA and the Arabian Gulf). The Cretaceous reservoirs, which mainly consist of calcarenite and dolomite, are located around the Gotnia salt Basin (northeast of KSA). Depleted oil and gas fields, which generally have proven as geologic traps, reservoirs and seals, are ideal sites for storage of injected CO₂. Each potential site for CO₂-EOR or CCS should be evaluated for its potential storage with respect to the containment properties, and to ensure that conditions for safe and effective long term storage are present. The secured deep underground storage of CO₂ implies appropriate geologic rock formations with suitable reservoir rocks, traps, and impermeable caprocks. Proposed targets for CCS, in the non-hydrocarbon-prolific sector, are Kharij super-aquifer (Triassic), Az-Zulfi aquifer (Middle Jurassic), Layla aquifer (Late Jurassic), and Wasia aquifer (Middle Cretaceous). Proposed targets for EOR are Safaniya oil field (Middle Cretaceous) (Safaniya, Wara and Khafji reservoirs), Manifa oil field (Las, Safaniya and Khafji reservoirs) (Late Jurassic), and Khuff reservoir (Late Permian-Early Triassic) in central to eastern KSA.     

Geologic factors controlling CO2 storage capacity and permanence: case studies based on experience with heterogeneity in oil and gas reservoirs applied to CO2 storage

A variety of structural and stratigraphic factors control geological heterogeneity, inferred to influence both sequestration capacity and effectiveness, as well as seal capacity. Structural heterogeneity factors include faults, folds, and fracture intensity. Stratigraphic heterogeneity is primarily controlled by the geometry of depositional facies and sandbody continuity, which controls permeability structure. The permeability structure, in turn, has implications for CO₂ injectivity and near-term migration pathways, whereas the long-term sequestration capacity can be inferred from the production history. Examples of Gulf Coast oil and gas reservoirs with differing styles of stratigraphic heterogeneity demonstrate the impact of facies variability on fluid flow and CO₂ sequestration potential. Beach and barrier-island deposits in West Ranch field in southeast Texas are homogeneous and continuous. In contrast, Seeligson and Stratton fields in south Texas, examples of major heterogeneity in fluvial systems, are composed of discontinuous, channel-fill sandstones confined to narrow, sinuous belts. These heterogeneous deposits contain limited compartments for potential CO₂ storage, although CO₂ sequestration effectiveness may be enhanced by the high number of intraformational shale beds. These field examples demonstrate that areas for CO₂ storage can be optimized by assessing sites for enhanced oil and gas recovery in mature hydrocarbon provinces.     

Assessing the feasibility of CO<Subscript>2</Subscript>-enhanced oil recovery and storage in mature oil field: A case study from Cambay basin

The utilization of anthropogenic CO₂ for enhanced oil recovery (EOR) can significantly extend the production life of an oil field, and help in the reduction of atmospheric emission of anthropogenic CO₂ if sequestration is considered. This work summarizes the prospect of EOR and sequestration using CO₂ flooding from an Indian mature oil field at Cambay basin through numerical modelling, simulation and pressure study based on limited data provided by the operator. To get an insight into CO₂-EOR and safe storage process in this oil field, a conceptual sector model is developed and screening standard is proposed keeping in mind the major pay zone of the producing reservoir. To construct the geomodel, depth maps, well positions and coordinates, well data and well logs, perforation depths and distribution of petrophysical properties as well as fluid properties provided by the operator, has been considered. Based on the results from the present study, we identified that the reservoir has the potential for safe and economic geological sequestration of 15.04×10⁶ metric ton CO₂ in conjunction with a substantial increase in oil recovery of 10.4% of original oil in place. CO₂-EOR and storage in this mature field has a bright application prospect since the findings of the present work could be a better input to manage the reservoir productivity, and the pressure field for significant enhancement of oil recovery followed by safe storage.     

Pressure transient technique to constrain CO<Subscript>2</Subscript> plume boundaries

Carbon dioxide (CO₂) has been injected in the subsurface permeable formations as a means to cut atmospheric CO₂ emissions and/or enhance oil recovery (EOR). It is important to constrain the boundaries of the CO₂ plume in the target formation and/or other formations hosting the CO₂ migrated from the target formation. Monitoring methods and technologies to assess the CO₂ plume boundaries over time within a reservoir of interest are required. Previously introduced methods and technologies on pressure monitoring to detect the extent of the CO₂ plume require at least two wells, i.e. pulser and observation wells. We introduce pressure transient technique requiring single well only. Single well pressure transient testing (drawdown/buildup/injection/falloff) is widely used to determine reservoir properties and wellbore conditions. Pressure diagnostic plots are used to identify different flow regimes and determine the reservoir/well characteristics. We propose a method to determine the plume extent for a constant rate pressure transient test at a single well outside the CO₂ plume. Due to the significant contrast between mobility and storativity of the CO₂ and native fluids (oil or brine), the CO₂ boundary causes deviation in the pressure diagnostic response from that corresponding to previously identified heterogeneities. Using the superposition principle, we develop a relationship between the deviation time and the plume boundary. We demonstrate the applicability of the proposed method using numerically generated synthetic data corresponding to homogeneous, heterogeneous, and anisotropic cases to evaluate its potential and limitations. We discuss ways to identify and overcome the potential limitations for application of the method in the field.     

Seal integrity and feasibility of CO<Subscript>2</Subscript> sequestration in the Teapot Dome EOR pilot: geomechanical site characterization

This paper reports a preliminary investigation of CO₂ sequestration and seal integrity at Teapot Dome oil field, Wyoming, USA, with the objective of predicting the potential risk of CO₂ leakage along reservoir-bounding faults. CO₂ injection into reservoirs creates anomalously high pore pressure at the top of the reservoir that could potentially hydraulically fracture the caprock or trigger slip on reservoir-bounding faults. The Tensleep Formation, a Pennsylvanian age eolian sandstone is evaluated as the target horizon for a pilot CO₂ EOR-carbon storage experiment, in a three-way closure trap against a bounding fault, termed the S1 fault. A preliminary geomechanical model of the Tensleep Formation has been developed to evaluate the potential for CO₂ injection inducing slip on the S1 fault and thus threatening seal integrity. Uncertainties in the stress tensor and fault geometry have been incorporated into the analysis using Monte Carlo simulation. The authors find that even the most pessimistic risk scenario would require ∼10 MPa of excess pressure to cause the S1 fault to reactivate and provide a potential leakage pathway. This would correspond to a CO₂ column height of ∼1,500 m, whereas the structural closure of the Tensleep Formation in the pilot injection area does not exceed 100 m. It is therefore apparent that CO₂ injection is not likely to compromise the S1 fault stability. Better constraint of the least principal stress is needed to establish a more reliable estimate of the maximum reservoir pressure required to hydrofracture the caprock.     

Investigating CO<Subscript>2</Subscript>-enhanced oil recovery potential for a mature oil field: a case study based on Ankleshwar oil field,Cambay Basin,India

CO₂-enhanced oil recovery (EOR) is an upcoming technology in India. At present, no Indian field is under CO₂-EOR and implementation of this technique to a mature oil field needs a rigorous study. In the present work, we made an attempt to investigate the CO₂-EOR potential of a mature oil field, situated in Cambay Basin, India. The field was put on production in 1961, and it has produced approximately 65.36 MMt oil during massive water flooding, leading to residual oil reserves of 6.49 MMt. The operator of the field is interested in incremental oil recovery from this field by injecting CO₂. This requires estimation of incremental oil recovery potential of the field by carrying out systematic study. We, therefore, developed a conceptual model inspired by Ankleshwar oil field of Cambay Basin using available information provided by the field operator and carried out systematic studies to establish an optimized strategy for CO₂ injection. To achieve this goal, we investigated the effect of various operational parameters on oil recovery efficiency of our conceptual model and selected optimum parameters for reservoir simulations. Simulation results clearly indicate that the field can be a good candidate for CO₂-EOR, and an additional oil recovery of 10.4% of hydrocarbon pore volume is feasible. Major outcome of the study is an optimized black-oil simulation model, which is in good agreement with the fine grid compositional model of high accuracy. The proposed black-oil model can easily be implemented and updated compared with compute intensive finer compositional simulation model.     

Site characterisation of a basin-scale CO<Subscript>2</Subscript> geological storage system: Gippsland Basin,southeast Australia

Geological storage of CO₂ in the offshore Gippsland Basin, Australia, is being investigated by the Cooperative Research Centre for Greenhouse Gas Technologies (CO2CRC) as a possible method for storing the very large volumes of CO₂ emissions from the nearby Latrobe Valley area. A storage capacity of about 50 million tonnes of CO₂ per annum for a 40-year injection period is required, which will necessitate several individual storage sites to be used both sequentially and simultaneously, but timed such that existing hydrocarbon assets will not be compromised. Detailed characterisation focussed on the Kingfish Field area as the first site to be potentially used, in the anticipation that this oil field will be depleted within the period 2015–2025. The potential injection targets are the interbedded sandstones of the Paleocene-Eocene upper Latrobe Group, regionally sealed by the Lakes Entrance Formation. The research identified several features to the offshore Gippsland Basin that make it particularly favourable for CO₂ storage. These include: a complex stratigraphic architecture that provides baffles which slow vertical migration and increase residual gas trapping and dissolution; non-reactive reservoir units that have high injectivity; a thin, suitably reactive, lower permeability marginal reservoir just below the regional seal providing mineral trapping; several depleted oil fields that provide storage capacity coupled with a transient production-induced flow regime that enhances containment; and long migration pathways beneath a competent regional seal. This study has shown that the Gippsland Basin has sufficient capacity to store very large volumes of CO₂. It may provide a solution to the problem of substantially reducing greenhouse gas emissions from future coal developments in the Latrobe Valley.     

CO<Subscript>2</Subscript> leakage through an abandoned well: problem-oriented benchmarks

The efficiency and sustainability of carbon dioxide (CO₂) storage in deep geological formations crucially depends on the integrity of the overlying cap-rocks. Existing oil and gas wells, which penetrate the formations, are potential leakage pathways. This problem has been discussed in the literature, and a number of investigations using semi-analytical mathematical approaches have been carried out by other authors to quantify leakage rates. The semi-analytical results are based on a number of simplifying assumptions. Thus, it is of great interest to assess the influence of these assumptions. We use a numerical model to compare the results with those of the semi-analytical model. Then we ease the simplifying restrictions and include more complex thermodynamic processes including sub- and supercritical fluid properties of CO₂ and non-isothermal as well as compositional effects. The aim is to set up problem-oriented benchmark examples that allow a comparison of different modeling approaches to the problem of CO₂ leakage.     

Dynamics of CO<Subscript>2</Subscript> fluxes and concentrations during a shallow subsurface CO<Subscript>2</Subscript> release

A field facility located in Bozeman, Montana provides the opportunity to test methods to detect, locate, and quantify potential CO₂ leakage from geologic storage sites. From 9 July to 7 August 2008, 0.3 t CO₂ day⁻¹ were injected from a 100-m long, ~2.5-m deep horizontal well. Repeated measurements of soil CO₂ fluxes on a grid characterized the spatio-temporal evolution of the surface leakage signal and quantified the surface leakage rate. Infrared CO₂ concentration sensors installed in the soil at 30 cm depth at 0–10 m from the well and at 4 cm above the ground at 0 and 5 m from the well recorded surface breakthrough of CO₂ leakage and migration of CO₂ leakage through the soil. Temporal variations in CO₂ concentrations were correlated with atmospheric and soil temperature, wind speed, atmospheric pressure, rainfall, and CO₂ injection rate.     

Geologic assessment and injection design for a pilot CO<Subscript>2</Subscript>-enhanced oil recovery and sequestration demonstration in a heterogeneous oil reservoir: Citronelle Field,Alabama, USA

CO₂ pilot injection studies, with site-specific geologic assessment and engineering reservoir design, can be instrumental for demonstrating both incremental enhanced oil recovery and permanent geologic storage of greenhouse gases. The purpose of this paper is to present the geologic and reservoir analyses in support of a field pilot test that will evaluate the technical and economic feasibility of commercial-scale CO₂-enhanced oil recovery to increase oil recovery and extend the productive life of the Citronelle Oil Field, the largest conventional oil field in Alabama (SE USA). Screening of reservoir depth, oil gravity, reservoir pressure, reservoir temperature, and oil composition indicates that the Cretaceous-age Donovan sand, which has produced more than 169 × 10⁶ bbl in Citronelle Oil Field, is amenable to miscible CO₂ flooding. The project team has selected an 81 ha (200 ac) 5-spot test site with one central gas injector, two producers, and two initially temporarily abandoned production wells that are now in production. Injection is planned in two separate phases, each consisting of 6,804 t (7,500 short tons) of food-grade CO₂. The Citronelle Unit B-19-10 #2 well (Permit No. 3232) is the CO₂ injector for the first injection test. The 14-1 and 16-2 sands of the upper Donovan are the target zones. These sandstone units consist of fine to medium-grained sandstone that is enveloped by variegated mudstone. Both of these sandstone units were selected based on the distribution of perforated zones in the test pattern, production history, and the ability to correlate individual sandstone units in geophysical well logs. The pilot injections will evaluate the applicability of tertiary oil recovery to Citronelle Field and will provide a large volume of information on the pressure response of the reservoirs, the mobility of fluids, time to breakthrough, and CO₂ sweep efficiency. The results of the pilot injections will aid in the formulation of commercial-scale reservoir management strategies that can be applied to Citronelle Field and other geologically heterogeneous oil fields and the design of similar pilot injection projects.     

Water–rock–CO2 interactions in saline aquifers aimed for carbon dioxide storage: Experimental and numerical modeling studies of the Rio Bonito Formation (Permian), southern Brazil

Mineral trapping is one of the safest ways to store CO₂ underground as C will be immobilized in a solid phase. Carbon dioxide will be, therefore, sequestered for geological periods of time, helping to diminish greenhouse gas emissions and mitigate global warming. Although mineral trapping is considered a fairly long process, owing to the existence of kinetic barriers for mineral precipitation, it has been demonstrated both experimentally and by numerical modeling. Here the results of experimental and numerical modeling studies performed in sandstones of the saline aquifer of the Rio Bonito Formation, Paraná Basin, are presented. The Rio Bonito Formation consists of paralic sandstones deposited in the intracratonic Paraná Basin, southern Brazil, during the Permian (Artinskian–Kungurian). These rocks have the largest potential for CO₂ storage because of their appropriated reservoir quality, depth and proximity to the most important stationary CO₂ sources in Brazil. Here it is suggested that CO₂ can be permanently stored as carbonates as CO₂ reacts with rocks of the Rio Bonito Formation and forms CaCO₃ at temperatures and pressures similar to those encountered for CO₂ storage in geological formations. Results of this work will be useful for studies of partitioning mechanisms for C trapping in CO₂ storage programs.     

3D seismic analysis of complex faulting patterns above the Snapper Field,Gippsland Basin: implications for CO2 storage

Mechanical damage (e.g. faults and fractures) related to tectonic forces and/or variations in formation pore pressures may enable the leakage of fluids through otherwise effective seal rocks. Characterisation of faults and fractures within seals is therefore essential for the assessment of long-term trap integrity in potential CO₂ storage sites. 3D seismic reflection data are used to describe a previously unrecognised network of extensive, small Miocene-age faults with displacement of generally <30 m and lengths that vary between ～300 and 2500 m above the Snapper Field, in the Gippsland Basin. The Snapper Field is a nearly depleted oil and gas field that presents an attractive site for potential CO₂ storage due its structural closure and because it has effectively retained significant natural hydrocarbon (including CO₂) columns over geological time-scales. Volume-based seismic attributes reveal that this fault system is located within the Oligocene Lakes Entrance Formation of the Seaspray Group, which acts as the regional seal to the Latrobe Group reservoirs in the Gippsland Basin. Detailed analysis of fault lengths and linkages suggests that the Miocene faults are non-tectonic, polygonal faults, although the displacement analysis of fault segments reveals strong correlations with the both the structure of the underlying Top Latrobe surface and normal faults that segment the Latrobe Group reservoirs, suggesting that the development of this fault system has been influenced by underlying structures. The geological evidence for long-term retention of hydrocarbons within the Snapper Field suggests that this fault system has not compromised the integrity of the Lakes Entrance Formation seal, although elevated pore pressures during CO₂ injection could potentially lead to reactivation of these structures.     

Carbonate cements in Miller field of the UK North Sea: a natural analog for mineral trapping in CO<Subscript>2</Subscript> geological storage

Miller field of the North Sea has had high concentrations of natural CO₂ for ~70 Ma. It is an ideal analog for the long-term fate of CO₂ during engineered storage, particularly for formation of carbonate minerals that permanently lock up CO₂ in solid form. The Brae Formation reservoir sandstone contains an unusually high quantity of calcite concretions; however, C and O stable isotopic signatures suggest that these are not related to the present-day CO₂ charge. Margins of the concretions are corroded, probably because of reduced pH due to CO₂ influx. Dispersed calcite cements are also present, some of which postdate the CO₂ charge and, therefore, are the products of mineral trapping. It is calculated that only a minority of the reservoired CO₂ in Miller (6–24%) has been sequestrated in carbonates, even after 70 Ma of CO₂ emplacement. Most of the CO₂ accumulation is dissolved in pore fluids. Therefore, in a reservoir similar to the Brae Formation, engineered CO₂ storage must rely on physical retention mechanisms because mineral trapping is both incomplete and slow.     

Can the long-term potential for carbonatization and safe long-term CO2 storage in sedimentary formations be predicted?

A sedimentary formation perturbated by supercritical CO₂ reacts by dissolving primary minerals and forming new secondary phases. In this process CO₂ may be trapped in stable carbonate minerals and may thereby be immobilized for long time spans. The potential for mineral trapping can be estimated by solving kinetic expressions for the reservoir minerals and possible secondary phases. This is, however, not trivial as kinetic data are uncertain or even lacking for the minerals of interest. Here, the rate equations most commonly used for CO₂ storage simulations have been solved, and the rate parameters varied, to obtain sensitivity on the total amount of CO₂ stored as mineral carbonate. As various expressions are in use to estimate growth rates of secondary carbonates, three formulations were compared, including one taking into account mineral nucleation preceding growth. The sensitivity studies were done on two systems, the Utsira Sand being representative for a cold quartz-rich sand (37 °C, 100 bar CO₂), and the Gulf Coast Sediment, being representative for a medium temperature quartz–plagioclase-rich system (75 °C, 300 bar CO₂).The simulations showed that the total predicted CO₂ mineral storage is especially sensitive to the choice of growth rate model and the reactive surface area. The largest sensitivity was found on α, fraction of total surface area available for reactions, with a reduction of one order of magnitude for all reacting phases leading to 3–4 times lower predicted CO₂ mineral storage. Because the reactive surface area is highly uncertain for natural systems, the range in predicted results may be even larger. The short-term predictions (<100–1000 a), such as the onset of carbonate growth, were highly sensitive to nucleation and growth rates. Moreover, the type of carbonate minerals formed was shown to be model dependent, with the simplest model predicting an unlikely carbonate assemblage at low temperature (i.e., formation of dolomite at 37 °C). Therefore, to use kinetic models to upscale short-term (<months) laboratory experiments in time, to identify the past reactions and physical conditions of natural CO₂ storage analogues, and finally to predict the potential for CO₂ trapping in existing and future storage projects, more knowledge has to be collected, especially on the reactive surface area of CO₂ storage reservoirs, and on the rate of secondary carbonate nucleation and growth.     

Potential risks to freshwater resources as a result of leakage from CO<Subscript>2</Subscript> geological storage: a batch-reaction experiment

In assessing the feasibility of widespread deployment of CO₂ geological storage, it is prudent to first assess potential consequences of an error or accident that could lead to CO₂ leakage into groundwater resources above a sequestration interval. Information about the sensitivity of the groundwater system to introduction of CO₂ is needed in order to design groundwater monitoring program. A laboratory-batch experiment was conducted to explore the range of CO₂ impact on groundwater quality of a spectrum of representative aquifers, in the Gulf Coast region, USA. Results show that CO₂ elevated concentrations of many cations within hours or days. Two types of cations were recognized according to their concentration trends. Type I cations—Ca, Mg, Si, K, Sr, Mn, Ba, Co, B, Zn—rapidly increased following initial CO₂ flux and reached stable concentrations before the end of the experiment. Type II cations—Fe, Al, Mo, U, V, As, Cr, Cs, Rb, Ni and Cu—increased at the start of CO₂ flux, but declined, in most cases, to levels lower than pre-CO₂ concentrations. Dissolution of dolomite and calcite caused the largest increase in concentrations for Ca, Mg, Mn, Ba and Sr. Cation release rates decreased linearly as pH increased during mineral buffering. Experiment results suggest that carbonate minerals are the dominant contributor of changes in groundwater quality. Risk assessments of potential degradation of groundwater and monitoring strategies should focus on these fast-reacting minerals. Mobilization risk of Type II cations, however, may be self-mitigated because adsorption occurs when pH rebounds.     

Modeling CO2–brine–rock interactions in the Knox Group: Implications of a deep carbon storage field test in western Kentucky

The Cambrian–Ordovician Knox Group, a thick sequence of dolostone and minor dolomitic sandstone, is a prospective CO₂ sequestration target in the southern Illinois Basin, USA. Thorough evaluation of the Knox Group is critical because the main sequestration target elsewhere in the Illinois Basin, the Cambrian Mount Simon Sandstone, is thin or absent throughout most of Kentucky. A 2477-m-deep carbon storage test well in Hancock County, Kentucky, was drilled, and 626 metric tons of CO₂ was injected into the Knox saline reservoirs. To understand the long-term fate of CO₂ injected into the Knox reservoirs, geochemical reactions between CO₂, brine and rock-forming minerals were modeled using TOUGHREACT. The modeling benefited from a robust data set collected from the test well, including core porosity and permeability, petrographic and X-ray powder diffraction mineralogy, brine chemistry, temperature and pressure measurements. Kinetic batch models and 2-D radial reactive transport models were used to evaluate the migration of the injected CO₂, changes in brine chemistry, and mineral dissolution and precipitation. Results from the kinetic models suggest that sections of the Knox dominated by dolomite have very limited mineral-trapping capacity for CO₂, whereas thin sections of dolomitic sandstone with aluminosilicate minerals such as K-feldspar facilitate mineral trapping. The 2-D model for the CO₂ injection test suggests that, because of the presence of thick permeable intervals in the Knox and the small volume of injected CO₂ in the test, the radius of influence is less than 11 m from the well. The hypothetical long-term injection model indicates, on the other hand, that commercial-scale injection would influence a much larger area and part of the injected CO₂ remains in the supercritical/gas phase for a long time. Because of the buoyancy effect, most supercritical/gas-phase CO₂ migrates upward and stays in the top of the reservoirs dominated by dolomite with small mineral-trapping capacity.