Physical and chemical characteristics of potential seal strata in regions considered for demonstrating geological saline CO<Subscript>2</Subscript> sequestration

Capture and geological sequestration of CO₂ from energy production is proposed to help mitigate climate change caused by anthropogenic emissions of CO₂ and other greenhouse gases. Performance goals set by the US Department of Energy for CO₂ storage permanence include retention of at least 99% of injected CO₂ which requires detailed assessments of each potential storage site’s geologic system, including reservoir(s) and seal(s). The objective of this study was to review relevant basin-wide physical and chemical characteristics of geological seals considered for saline reservoir CO₂ sequestration in the United States. Results showed that the seal strata can exhibit substantial heterogeneity in the composition, structural, and fluid transport characteristics on a basin scale. Analysis of available field and wellbore core data reveal several common inter-basin features of the seals, including the occurrence of quartz, dolomite, illite, calcite, and glauconite minerals along with structural features containing fractures, faults, and salt structures. In certain localities within the examined basins, some seal strata also serve as source rock for oil and gas production and can be subject to salt intrusions. The regional features identified in this study can help guide modeling, laboratory, and field studies needed to assess local seal performances within the examined basins.     

Sealing efficiency analysis for shallow-layer caprocks in CO<Subscript>2</Subscript> geological storage

The CO₂ migrated from deeper to shallower layers may change its phase state from supercritical state to gaseous state (called phase transition). This phase transition makes both viscosity and density of CO₂ experience a sharp variation, which may induce the CO₂ further penetration into shallow layers. This is a critical and dangerous situation for the security of CO₂ geological storage. However, the assessment of caprock sealing efficiency with a fully coupled multi-physical model is still missing on this phase transition effect. This study extends our previous fully coupled multi-physical model to include this phase transition effect. The dramatic changes of CO₂ viscosity and density are incorporated into the model. The impacts of temperature and pressure on caprock sealing efficiency (expressed by CO₂ penetration depth) are then numerically investigated for a caprock layer at the depth of 800 m. The changes of CO₂ physical properties with gas partial pressure and formation temperature in the phase transition zone are explored. It is observed that phase transition revises the linear relationship of CO₂ penetration depth and time square root as well as penetration depth. The real physical properties of CO₂ in the phase transition zone are critical to the safety of CO₂ sequestration. Pressure and temperature have different impact mechanisms on the security of CO₂ geological storage.     

Using hyperspectral plant signatures for CO<Subscript>2</Subscript> leak detection during the 2008 ZERT CO<Subscript>2</Subscript> sequestration field experiment in Bozeman,Montana

Hyperspectral plant signatures can be used as a short-term, as well as long-term (100-year timescale) monitoring technique to verify that CO₂ sequestration fields have not been compromised. An influx of CO₂ gas into the soil can stress vegetation, which causes changes in the visible to near-infrared reflectance spectral signature of the vegetation. For 29 days, beginning on July 9, 2008, pure carbon dioxide gas was released through a 100-m long horizontal injection well, at a flow rate of 300 kg day⁻¹. Spectral signatures were recorded almost daily from an unmown patch of plants over the injection with a “FieldSpec Pro” spectrometer by Analytical Spectral Devices, Inc. Measurements were taken both inside and outside of the CO₂ leak zone to normalize observations for other environmental factors affecting the plants. Four to five days after the injection began, stress was observed in the spectral signatures of plants within 1 m of the well. After approximately 10 days, moderate to high amounts of stress were measured out to 2.5 m from the well. This spatial distribution corresponded to areas of high CO₂ flux from the injection. Airborne hyperspectral imagery, acquired by Resonon, Inc. of Bozeman, MT using their hyperspectral camera, also showed the same pattern of plant stress. Spectral signatures of the plants were also compared to the CO₂ concentrations in the soil, which indicated that the lower limit of soil CO₂ needed to stress vegetation is between 4 and 8% by volume.     

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.     

Uncertainties of geochemical modeling during CO<Subscript>2</Subscript> sequestration applying batch equilibrium calculations

One of the uncertainties in the field of carbon dioxide capture and storage (CCS) is caused by the parameterization of geochemical models. The application of geochemical models contributes significantly to calculate the fate of the CO₂ after its injection. The choice of the thermodynamic database used, the selection of the secondary mineral assemblage as well as the option to calculate pressure dependent equilibrium constants influence the CO₂ trapping potential and trapping mechanism. Scenario analyses were conducted applying a geochemical batch equilibrium model for a virtual CO₂ injection into a saline Keuper aquifer. The amount of CO₂ which could be trapped in the formation water and in the form of carbonates was calculated using the model code PHREEQC. Thereby, four thermodynamic datasets were used to calculate the thermodynamic equilibria. Furthermore, the equilibrium constants were re-calculated with the code SUPCRT92, which also applied a pressure correction to the equilibrium constants. Varying the thermodynamic database caused a range of 61% in the amount of trapped CO₂ calculated. Simultaneously, the assemblage of secondary minerals was varied, and the potential secondary minerals dawsonite and K-mica were included in several scenarios. The selection of the secondary mineral assemblage caused a range of 74% in the calculated amount of trapped CO₂. Correcting the equilibrium constants with respect to a pressure of 125 bars had an influence of 11% on the amount of trapped CO₂. This illustrates the need for incorporating sensitivity analyses into reaction pathway modeling.     

Interactions between basalts and oil source rocks in rift basins： CO2 generation

Basalts interbedded with oil source rocks are discovered frequently in rift basins of eastern China, where CO2 is found in reservoirs around or within basalts, for example in the Binnan reservoir of the Dongying Depression. In the reservoirs, CO2 with heavy carbon isotopic composition (δ13C>-10‰ PDB) is in most cases accounts for 40% of the total gas reserve, and is believed to have resulted from degassing of basaltic magma from the mantle. In their investigations of the Binnan reservoir, the authors suggested that the CO2 would result from interactions between the source rocks and basalts. As the source rocks around basalts are rich in carbonate minerals, volcanic minerals, transition metals and organic matter, during their burial history some of the transition metals were catalyzed on the thermal degradation of organic matter into hydrocarbons and on the decomposition of carbonate minerals into CO2, which was reproduced in thermal simulations of the source rocks with the transition metals (Ni and Co). This kind of CO2 accounts for 55%-85% of the total gas reserve generated in the process of thermal simulation, and its δ13C values range from -11‰- -7.2‰ PDB, which are very similar to those of CO2 found in the Binnan reservoir. The co-generation of CO2 and hydrocarbon gases makes it possible their accumulation together in one trap. In other words, if the CO2 resulted directly from degassing of basaltic magma or was derived from the mantle, it could not be accumulated with hydrocarbon gases because it came into the basin much earlier than hydrocarbon generation and much earlier than trap formation. Therefore, the source rocks around basalts generated hydrocarbons and CO2 simultaneously through catalysis of Co and Ni transition metals, which is useful for the explanation of co-accumulation of hydrocarbon gases and CO2 in rift basins in eastern China.     

Near-surface soil carbon detection for monitoring CO<Subscript>2</Subscript> seepage from a geological reservoir

The promise of the Brookhaven National Laboratory (BNL) Inelastic Neutron Scattering (INS) System was evaluated for use as a long-term, in-field monitor to detect cumulative changes in belowground carbon resulting from the leakage of CO₂ stored in deep geological reservoirs. This system underwent tests at a facility constructed specifically for testing, under controlled conditions, various detection systems for monitoring near-surface transport and accumulations of CO₂ fluxes emanating from a shallow buried, slotted horizontal well. The INS System was assessed by comparing the results from placing it above the horizontal well at a spot with a known high CO₂ leak identified and quantified the previous years, with those obtained from background readings adjacent to the well. At two different “Hot Spots”, a suppression of about 14% in 2008 and about 7% in 2009 in carbon content above the well in comparison to the background signal was observed. An overview of these results is presented.     

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.     

Bayesian hierarchical models for soil CO<Subscript>2</Subscript> flux and leak detection at geologic sequestration sites

Proper characterizations of background soil CO₂ respiration rates are critical for interpreting CO₂ leakage monitoring results at geologic sequestration sites. In this paper, a method is developed for determining temperature-dependent critical values of soil CO₂ flux for preliminary leak detection inference. The method is illustrated using surface CO₂ flux measurements obtained from the AmeriFlux network fit with alternative models for the soil CO₂ flux versus soil temperature relationship. The models are fit first to determine pooled parameter estimates across the sites, then using a Bayesian hierarchical method to obtain both global and site-specific parameter estimates. Model comparisons are made using the deviance information criterion (DIC), which considers both goodness of fit and model complexity. The hierarchical models consistently outperform the corresponding pooled models, demonstrating the need for site-specific data and estimates when determining relationships for background soil respiration. A hierarchical model that relates the square root of the CO₂ flux to a quadratic function of soil temperature is found to provide the best fit for the AmeriFlux sites among the models tested. This model also yields effective prediction intervals, consistent with the upper envelope of the flux data across the modeled sites and temperature ranges. Calculation of upper prediction intervals using the proposed method can provide a basis for setting critical values in CO₂ leak detection monitoring at sequestration sites.     

An integrative approach to robust design and probabilistic risk assessment for CO<Subscript>2</Subscript> storage in geological formations

CO₂ storage in geological formations is currently being discussed intensively as a technology with a high potential for mitigating CO₂ emissions. However, any large-scale application requires a thorough analysis of the potential risks. Current numerical simulation models are too expensive for probabilistic risk analysis or stochastic approaches based on a brute-force approach of repeated simulation. Even single deterministic simulations may require parallel high-performance computing. The multiphase flow processes involved are too non-linear for quasi-linear error propagation and other simplified stochastic tools. As an alternative approach, we propose a massive stochastic model reduction based on the probabilistic collocation method. The model response is projected onto a higher-order orthogonal basis of polynomials to approximate dependence on uncertain parameters (porosity, permeability, etc.) and design parameters (injection rate, depth, etc.). This allows for a non-linear propagation of model uncertainty affecting the predicted risk, ensures fast computation, and provides a powerful tool for combining design variables and uncertain variables into one approach based on an integrative response surface. Thus, the design task of finding optimal injection regimes explicitly includes uncertainty, which leads to robust designs with a minimum failure probability. We validate our proposed stochastic approach by Monte Carlo simulation using a common 3D benchmark problem (Class et al., Comput Geosci 13:451–467, 2009). A reasonable compromise between computational efforts and precision was reached already with second-order polynomials. In our case study, the proposed approach yields a significant computational speed-up by a factor of 100 compared with the Monte Carlo evaluation. We demonstrate that, due to the non-linearity of the flow and transport processes during CO₂ injection, including uncertainty in the analysis leads to a systematic and significant shift of the predicted leakage rates toward higher values compared with deterministic simulations, affecting both risk estimates and the design of injection scenarios.     

Strategies for addressing climate change on the industrial level: affecting factors to CO<Subscript>2</Subscript> emissions of energy-intensive industries in China

This paper explores China’s strategies for addressing climate change on the industrial level. Focusing on six energy-intensive industries, this paper applies gray relational analysis theory to the affecting factors to CO₂ emissions of each industry after calculating each industry’s CO₂ emissions during 2001–2010. Further research based on GM(1, 1) model is conducted to forecast the trend of the factors, the energy consumption and each industry’s CO₂ emissions during the 12th Five-Year Plan period. As a breakthrough in previous conclusions, energy consumption structure was divided into the respective proportion of coal, oil, natural gas and electricity in the primary energy consumption, with which industrial output and energy intensity are combined to analyze each of their impacts on the energy-intensive industries. It turns out that all the factors’ impacts on emissions of the six major energy-intensive industries are significant, despite their differentiated extents. It is worth noting that, contrary to previous findings, industrial output is not the leading affecting factor to CO₂ emissions of the energy-intensive industries compared with the proportion of coal and electricity in the primary energy consumption. The GM(1, 1) forecast results of energy consumption and CO₂ emissions by the end of 2015 show that coal and electricity will remain a large proportion in primary energy consumption. This research may shed some light on China’s adjustment of energy structure under the pressure of addressing climate change and hence provide decision support for the acceleration of renewable energy utilization in the industrial departments.     

Screening and ranking framework for geologic CO<Subscript>2</Subscript> storage site selection on the basis of health,safety, and environmental risk

A screening and ranking framework (SRF) has been developed to evaluate potential geologic carbon dioxide (CO₂) storage sites on the basis of health, safety, and environmental (HSE) risk arising from CO₂ leakage. The approach is based on the assumption that CO₂ leakage risk is dependent on three basic characteristics of a geologic CO₂ storage site: (1) the potential for primary containment by the target formation; (2) the potential for secondary containment if the primary formation leaks; and (3) the potential for attenuation and dispersion of leaking CO₂ if the primary formation leaks and secondary containment fails. The framework is implemented in a spreadsheet in which users enter numerical scores representing expert opinions or published information along with estimates of uncertainty. Applications to three sites in California demonstrate the approach. Refinements and extensions are possible through the use of more detailed data or model results in place of property proxies.     

Feasibility of CO<Subscript>2</Subscript> migration detection using pressure and CO<Subscript>2</Subscript> saturation monitoring above an imperfect primary seal of a geologic CO<Subscript>2</Subscript> storage formation: a numerical investigation

A numerical model was developed to investigate the potential to detect fluid migration in a (homogeneous, isotropic, with constant pressure lateral boundaries) porous and permeable interval overlying an imperfect primary seal of a geologic CO₂ storage formation. The seal imperfection was modeled as a single higher-permeability zone in an otherwise low-permeability seal, with the center of that zone offset from the CO₂ injection well by 1400 m. Pressure response resulting from fluid migration through the high-permeability zone was detectable up to 1650 m from the centroid of that zone at the base of the monitored interval after 30 years of CO₂ injection (detection limit = 0.1 MPa pressure increase); no pressure response was detectable at the top of the monitored interval at the same point in time. CO₂ saturation response could be up to 774 m from the center of the high-permeability zone at the bottom of the monitored interval, and 1103 m at the top (saturation detection limit = 0.01). More than 6% of the injected CO₂, by mass, migrated out of primary containment after 130 years of site performance (including 30 years of active injection) in the case where the zone of seal imperfection had a moderately high permeability (10^??17 m² or 0.01 mD). Free-phase CO₂ saturation monitoring at the top of the overlying interval provides favorable spatial coverage for detecting fluid migration across the primary seal. Improved sensitivity of detection for pressure perturbation will benefit time of detection above an imperfect seal.     

Analytical model for screening potential CO<Subscript>2</Subscript> repositories

Assessing potential repositories for geologic sequestration of carbon dioxide using numerical models can be complicated, costly, and time-consuming, especially when faced with the challenge of selecting a repository from a multitude of potential repositories. This paper presents a set of simple analytical equations (model), based on the work of previous researchers, that could be used to evaluate the suitability of candidate repositories for subsurface sequestration of carbon dioxide. We considered the injection of carbon dioxide at a constant rate into a confined saline aquifer via a fully perforated vertical injection well. The validity of the analytical model was assessed via comparison with the TOUGH2 numerical model. The metrics used in comparing the two models include (1) spatial variations in formation pressure and (2) vertically integrated brine saturation profile. The analytical model and TOUGH2 show excellent agreement in their results when similar input conditions and assumptions are applied in both. The analytical model neglects capillary pressure and the pressure dependence of fluid properties. However, simulations in TOUGH2 indicate that little error is introduced by these simplifications. Sensitivity studies indicate that the agreement between the analytical model and TOUGH2 depends strongly on (1) the residual brine saturation, (2) the difference in density between carbon dioxide and resident brine (buoyancy), and (3) the relationship between relative permeability and brine saturation. The results achieved suggest that the analytical model is valid when the relationship between relative permeability and brine saturation is linear or quasi-linear and when the irreducible saturation of brine is zero or very small.     

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.     

Preparation of carbon molecular sieves and its impregnation with Co and Ni for CO<Subscript>2</Subscript>/N<Subscript>2</Subscript> separation

The carbon molecular sieves (CMSs) prepared by carbonaceous materials as precursors are effective in CO₂/N₂ separation. However, selectivity of these materials is too low, since hydrocarbon cracking for developing the desired microporosity in carbonaceous materials has not been done effectively. Hence, in this study, cobalt and nickel impregnation on the precursor was conducted to introduce catalysts for hydrocarbon cracking. Cobalt and nickel impregnation, carbonization under N₂ atmosphere, and chemical vapor deposition (CVD) by benzene were conducted on the extruded mixtures of activated carbon and coal tar pitch under different conditions to prepare CMSs. The best CMS prepared by carbon deposition on the cobalt-impregnated samples exhibited CO₂ adsorption capacity of 54.79 mg/g and uptake ratio of 28.9 at 0 °C and 1 bar. In terms of CO₂ adsorption capacity and uptake ratio, CMSs prepared by carbon deposition on non-impregnated and cobalt-impregnated samples presented the best results, respectively. As benzene concentration and CVD time increased, equilibrium adsorption capacity of CO₂ decreased, and uptake ratio increased. Cobalt was found to be the best catalyst for benzene cracking in the CVD process.