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.     

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.     

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.     

CO<Subscript>2</Subscript> fluid inclusions in Jack Hills zircons

The discovery of Hadean to Paleoarchean zircons in a metaconglomerate from Jack Hills, Western Australia, has catalyzed intensive study of these zircons and their mineral inclusions, as they represent unique geochemical archives that can be used to unravel the geological evolution of early Earth. Here, we report the occurrence and physical properties of previously undetected CO₂ inclusions that were identified in 3.36–3.47 Ga and 3.80–4.13 Ga zircon grains by confocal micro-Raman spectroscopy. Minimum P–T conditions of zircon formation were determined from the highest density of the inclusions, determined from the density-dependence of the Fermi diad splitting in the Raman spectrum and Ti-in-zircon thermometry. For both age periods, the CO₂ densities and Ti-in-zircon temperatures correspond to high-grade metamorphic conditions (≥5 to ≥7 kbar/~670 to 770 °C) that are typical of mid-crustal regional metamorphism throughout Earth’s history. In addition, fully enclosed, highly disordered graphitic carbon inclusions were identified in two zircon grains from the older population that also contained CO₂ inclusions. Transmission electron microscopy on one of these inclusions revealed that carbon forms a thin amorphous film on the inclusion wall, whereas the rest of the volume was probably occupied by CO₂ prior to analysis. This indicates a close relationship between CO₂ and the reduced carbon inclusions and, in particular that the carbon precipitated from a CO₂-rich fluid, which is inconsistent with the recently proposed biogenic origin of carbon inclusions found in Hadean zircons from Jack Hills.     

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.     

Pore pressure during metamorphism of carbonate rock: effect of volumetric properties of H<Subscript>2</Subscript>O–CO<Subscript>2</Subscript> mixtures

The molar volume of mixtures of CO₂ and H₂O is a strong function of the fluid composition. Both CO₂ and H₂O participate in the metamorphism of carbonate rocks, resulting in a change in the fluid composition during reaction. One of the effects of the change in composition is the increase in pore-fluid pressure with only small increases in extent of reaction, ;. Pressure calculated from the volumetric properties of CO₂-H₂O mixtures at 400 °C increases greatly with small increases of ; but drops at greater values because of the increase in pore volume as a result of (V_solid. The pore pressure increase at small values of ;, though, readily exceeds the reported tensile strength of carbonate rocks, and the rock cannot sustain significant reaction without fracturing. The result of a small amount of reaction is a fractured rock with increased permeability, which promotes fluid transport.     

The Role of CaCO<Subscript>3</Subscript> Reactions in the Contemporary Oceanic CO<Subscript>2</Subscript> Cycle

The present analysis adjusts previous estimates of global ocean CaCO₃ production rates substantially upward, to 133 × 10¹² mol yr^?1 plankton production and 42 × 10¹² mol yr^?1 shelf benthos production. The plankton adjustment is consistent with recent satellite-based estimates; the benthos adjustment includes primarily an upward adjustment of CaCO₃ production on so-called carbonate-poor sedimentary shelves and secondarily pays greater attention to high CaCO₃ mass (calcimass) and turnover of shelf communities on temperate and polar shelves. Estimated CaCO₃ sediment accumulation rates remain about the same as they have been for some years: ~20 × 10¹² mol yr^?1 on shelves and 11 × 10¹² mol yr^?1 in the deep ocean. The differences between production and accumulation of calcareous materials call for dissolution of ~22 × 10¹² mol yr^?1 (~50 %) of shelf benthonic carbonate production and 122 × 10¹² mol yr^?1 (>90 %) of planktonic production. Most CaCO₃ production, whether planktonic or benthonic, is assumed to take place in water depths of <100 m, while most dissolution is assumed to occur below this depth. The molar ratio of CO₂ release to CaCO₃ precipitation (CO₂↑/CaCO₃↓) is <1.0 and varies with depth. This ratio, Ψ, is presently about 0.66 in surface seawater and 0.85 in ocean waters deeper than about 1000 m. The net flux of CO₂ associated with CaCO₃ reactions in the global ocean in late preindustrial time is estimated to be an apparent influx from the atmosphere to the ocean, of +7 × 10¹² mol C yr^?1, at a time scale of 10²–10³ years. The CaCO₃-mediated influx of CO₂ is approximately offset by CO₂ release from organic C oxidation in the water column. Continuing ocean acidification will have effects on CaCO₃ and organic C metabolic responses to the oceanic inorganic C cycle, although those responses remain poorly quantified.     

Ab-initio calculations of the proton location in topaz-OH,Al<Subscript>2</Subscript>SiO<Subscript>4</Subscript>(OH)<Subscript>2</Subscript>

The position of hydrogen in the structure of topaz-OH was determined by means of ab-initio quantum-mechanic calculations. Static lattice energy calculations predict the existence of four non-equivalent positions of protons, which are characterized by O4–H1... O1, O4–H2... O2, O4–H3... O3 and O4–H4... O4 hydrogen bonds. The distribution of the protons between positions of local equilibrium is controlled by the proton–proton avoidance rule and the strength of the hydrogen bonds. The most favourable configuration of hydrogen atoms is achieved for adjacent protons, which form O4–H3... O3 and O4–H4... O4 hydrogen bonds, respectively. The thermal excitation of atoms at a temperature of 55 K is large enough for the hydrogen atoms occasionally to change their positions to form O4–H1... O1 and O4–H2... O2 bonds. At ambient pressures and higher temperatures the protons are in a dynamic exchange between the allowed positions of local minima. As a consequence, for nearly room-temperature conditions, the dynamic change between different structural configurations leads to the violation of all possible symmetry elements and with that to space group #E5/E5#1. The flipping of the protons between different sites is achieved by simple rotation of the OH-dipole and does not produce any significant distortion of the framework of topaz, whose symmetry remains that of the space group Pbnm. Therefore, no reduction of symmetry has been observed in former X-ray studies on topaz-OH. Calculated IR absorption spectra of topaz-OH were found to be in good agreement with measured spectra. According to the calculations, the two favourable configurations of protons might correspond to the measured peak splitting within the OH-stretching range. An experimentally observed low-frequency band at 3520 cm^–1 was assigned to the OH-stretching of the O4–H3... O3 bond, while the band at 3600 cm^–1 was attributed to OH-stretching of the O4–H4... O4 hydrogen bond. The broad peak in FAR-IR frequency range at 100–150 cm^–1 is attributed to the stretching of H3... O3 and H4... O4 contacts. The rate of proton exchange at 670 K among different sites was estimated by ab-inito molecular dynamic simulations. The calculations predict that flipping of adjacent protons between O4–H3... O3 and O4–H4... O4 bonds at 670 K occur at a rate of about 1.96 THz.     

Delineating hazardous CO<Subscript>2</Subscript> fluxes from acid mine drainage

Incidents of hazardous accumulations of CO₂ in homes built on or near reclaimed mine land, in the last decade, have been shown to be linked to neutralization reactions between acidic mine drainage and carbonate material. Recent research has shown that CO₂ fluxes on reclaimed mine land with this hazard are, sometimes, spatially autocorrelated (i.e., the spatial variability is not random). This result implies geostatistics can be used to delineate hazardous areas where fluxes are likely to exceed established thresholds. This study applies sequential Gaussian simulation to delineate this emerging hazard on a site in southwestern Indiana, USA. Due to lack of regulatory threshold limits for CO₂ flux at the current time, the authors conduct a sensitivity analysis of the threshold limit using the 75th, 90th and 95th percentiles of the measured fluxes for the first day of monitoring. These limits are used to produce hazard maps, which are validated with the known hazard at the site. This work further shows the potential of surface CO₂ flux monitoring as a cheap and effective strategy to monitor and delineate such hazards to avoid residential and commercial real estate development in high risk zones.     

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.     

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.     

Dissolution sequestration mechanism of CO<Subscript>2</Subscript> at the Shiqianfeng saline aquifer in the Ordos Basin,northwestern China

This study focused on the target injection layers of deep saline aquifers in the Shiqianfeng Fm. in the Carbon Capture and Sequestration (CCS) Demonstration Projects in the Ordos Basin, northwestern China. The study employed a combination method of experiments and numerical simulation to investigate the dissolution mechanism and impact factors of CO₂ in these saline aquifers. The results showed (1) CO₂ solubility in different types of water chemistry were shown in ascending order: MgCl₂-type water < CaCl₂-type water < Na₂SO₄-type water < NaCl-type water < Na₂CO₃-type water < distilled water. These results were consistent with the calculated results undertaken by TOUGHREACT with about 5% margin of error. CO₂ solubility of Shiqianfeng Fm. saline was 1.05 mol/L; (2) compared with distilled water, the more complex the water’s chemical composition, the greater the increase in HCO₃ ^?concentration. While the water’s composition was relatively simple, the tested water’s HCO₃ ^?concentrations were in close accord with the calculated value undertaken by the TOUGHREACT code, and the more complex the water’s composition, the poorer the agreement was, probably due to the complex and unstable HCO₃ ^? complicating matters when in an aqueous solution system including both tested HCO₃ ^?concentration and calculated HCO₃ ^?concentration; (3) the CO₂ solubility in the saline at the temperature conditions of 55 °C and 70 °C were 1.17 and 1.02 mol/L. When compared with the calculated value of 1.20 and 1.05 mol/L, they were almost the same with only 1 and 3% margin of error; concentrations of HCO₃ ^? were 402.73 mg/L (0.007 mol/L) and 385.65 mg/L (0.006 mol/L), while the simulation results were 132.16 mg/L (0.002 mol/L) and 128.52 mg/L (0.002 mol/L). From the contrast between the tested data and the calculated data undertaken by the TOUGHREACT code, it was shown that TOUGHRACT code could better simulate the interaction between saline and CO₂ in the dissolution sequestration capacity. Therefore, TOUGHREACT code could be used for the inter-process prediction of CO₂ long-term geological storage of CO₂; (4) The Ca²⁺ concentration and SO₄ ^2?concentration in saline water had less effect on the solubility of CO₂ and HCO₃ ^?concentration. In addition, TDS and pH values of saline affected not only the solubility of CO₂, but also the conversion of CO₂ to HCO₃ ^? due to that they can affect the activity and acid-base balance. So in fact, we just need to consider that the TDS and pH values are main impact factors in the dissolution sequestration capacity of CO₂ geological sequestration in deep saline aquifers.