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.     

Assessment of soil carbon pool,carbon sequestration and soil CO<Subscript>2</Subscript> flux in unreclaimed and reclaimed coal mine spoils

Surface coal mining inevitably deforests the land, reduces carbon (C) pool and generates different land covers. To re-establish the ecosystem C pool, post-mining lands are often afforested with fast-growing trees. A field study was conducted in the 5-year-old unreclaimed dump and reclaimed coal mine dump to assess the changes in soil CO₂ flux and compared with the reference forest site. Changes in soil organic carbon (SOC) and total nitrogen stocks were estimated in post-mining land. Soil CO₂ flux was measured using close dynamic chamber method, and the influence of environmental variables on soil CO₂ flux was determined. Woody biomass C and SOC stocks of the reference forest site were threefold higher than that of 5-year-old reclaimed site. The mean soil CO₂ flux was highest in 5-year-old reclaimed dump (2.37 μmol CO₂ m^?2 s^?1) and lowest in unreclaimed dump (0.21 μmol CO₂ m^?2 s^?1). Soil CO₂ flux was highly influenced by environmental variables, where soil temperature positively influenced the soil CO₂ flux, while soil moisture, relative humidity and surface CO₂ concentration negatively influenced the soil CO₂ flux. Change in soil CO₂ flux under different land cover depends on plant and soil characteristics and environmental variables. The study concluded that assessment of soil CO₂ flux in post-mining land is important to estimate the potential of afforestation to combat increased emission of soil CO₂ at regional and global scale.     

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.     

Relationship between soil CO<Subscript>2</Subscript> flux and volcanic tremor at Mt. Etna: Implications for magma dynamics

Large variations of the CO₂ flux through the soil were observed between November 2002 and January 2006 at Mt. Etna volcano. In many cases, the CO₂ flux was strongly influenced by changes in air temperature and atmospheric pressure. A new filtering method was then developed to remove the atmospheric influences on soil CO₂ flux and, at the same time, to highlight the variations strictly related to volcanic activity. Successively, the CO₂ corrected data were quantitatively compared with the spectral amplitude of the volcanic tremor by cross correlation function, cross-wavelet spectrum and wavelet coherence. These analyses suggested that the soil CO₂ flux variations preceded those of volcanic tremor by about 50 days. Given that volcanic tremor is linked to the shallow (a few kilometer) magma dynamics and soil CO₂ flux related to the deeper (~12 km b.s.l.) magma dynamics, the “delayed similarity” between the CO₂ flux and the volcanic tremor amplitude was used to assess the average speed in the magma uprising into the crust, as about 170–260 m per day. Finally, the large amount of CO₂ released before the onset of the 2004–2005 eruption indicated a deep ingression of new magma, which might have triggered such an eruption.     

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.     

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.     

Analysis of the spatial and temporal changes in soil CO<Subscript>2</Subscript> flux in alpine meadow of Qilian Mountain

Field experiments on the CO₂ flux of alpine meadow soil in the Qilian Mountain were conducted along the elevation gradient during the growing season of 2004 and 2005. The soil CO₂ flux was measured using the Li-6400-09 soil respiration chamber attached to the Li-6400 portable photosynthesis system. The effects of water and heat and roots on the soil CO₂ flux were statistically analyzed. The results show that soil CO₂ flux along the elevation gradient gradually decreases. The soil CO₂ flux was low at night, with lowest value occurring between 0200 and 0600 hours, started to rise rapidly during 0700–0830 hours, and then descend during 1600–1830 hours. The peak CO₂ efflux appears during 1100–1600 hours. The diurnal average of soil CO₂ efflux was between 0.56 ± 0.32 and 2.53 ± 0.76 μmol m⁻² s⁻¹. Seasonally, soil CO₂ fluxes are relatively high in summer and autumn and low in spring and winter. The soil CO₂ efflux, from the highest to the lowest in the ranking order, occurred in July and August (4.736 μmol m⁻² s⁻¹), June and September, and May and October, respectively. The soil CO₂ efflux during the growing season is positively correlated with soil temperature, root biomass and soil water content.     

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.     

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.     

The impact of CO<Subscript>2</Subscript> on shallow groundwater chemistry: observations at a natural analog site and implications for carbon sequestration

In a natural analog study of risks associated with carbon sequestration, impacts of CO₂ on shallow groundwater quality have been measured in a sandstone aquifer in New Mexico, USA. Despite relatively high levels of dissolved CO₂, originating from depth and producing geysering at one well, pH depression and consequent trace element mobility are relatively minor effects due to the buffering capacity of the aquifer. However, local contamination due to influx of brackish waters in a subset of wells is significant. Geochemical modeling of major ion concentrations suggests that high alkalinity and carbonate mineral dissolution buffers pH changes due to CO₂ influx. Analysis of trends in dissolved trace elements, chloride, and CO₂ reveal no evidence of in situ trace element mobilization. There is clear evidence, however, that As, U, and Pb are locally co-transported into the aquifer with CO₂-rich brackish water. This study illustrates the role that local geochemical conditions will play in determining the effectiveness of monitoring strategies for CO₂ leakage. For example, if buffering is significant, pH monitoring may not effectively detect CO₂ leakage. This study also highlights potential complications that CO₂ carrier fluids, such as brackish waters, pose in monitoring impacts of geologic sequestration.     

Human impact on the historical change of CO<Subscript>2</Subscript>degassing flux in River Changjiang

The impact of water quality changes in River Changjiang (formally known as the Yangtze River) on dissolved CO₂ and silicate concentrations and seasonal carbon flux in the past several decades (1960s–2000) was evaluated, based on monitoring data from hydrographic gauge. It was found that dissolved CO₂ and silicate in Changjiang decreased dramatically during this decades, as opposed to a marked increase in nutrient (e.g. NO₃ ^-) concentrations. Our analyses revealed that dissolved CO₂ in Changjiang was over-saturated with the atmosphere CO₂, and its concentration had showed a declining trend since the 1960s, despite that fluvial DIC flux had maintained stable. Analysis results also suggested that the decrease in dissolved CO₂ concentration was attributed to changes on the riverine trophic level and river damming activities in the Changjiang drainage basin. Due to the economic innovation (e.g. agriculture and industry development) across the Changjiang watershed, fertilizers application and river regulations have significantly altered the original state of the river. Its ecosystem and hydrological condition have been evolving toward the "lacustrine/reservoir" autotrophic type prevailing with plankton. Accordingly, average CO₂ diffusing flux to the atmosphere from the river had been reduced by three-fourth from the 1960s to 1990s, with the flux value being down to 14.2 mol.m^-2.yr^-1 in the 1990s. For a rough estimate, approximately 15.3 Mt of carbon was degassed annually into the atmosphere from the entire Changjiang drainage basin in the 1990s.     

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.     

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.