Contact angle measurements of CO2–water–quartz/calcite systems in the perspective of carbon sequestration

This work presents contact angle measurements for CO₂–water–quartz/calcite systems at general sequestration pressure and temperature conditions (200–3000 psig and 77–122 °F). The effect of drop volume, repeated exposure of the substrates to dense water saturated CO₂, pressure and temperature on the contact angles is examined. In the 1st measurement cycle, the contact angles for the quartz substrate varied from 46 to 48° and 47 to 46° for gaseous (water saturated) CO₂ and liquid (water saturated) CO₂ respectively, at 77 °F. For calcite substrate, these values varied from 45 to 48° and 42 to 40°, respectively. Remarkably, this work highlights a characteristic permanent shift in the contact angle data with repeated exposure to dense, water saturated, CO₂. The contact angle data trends after repeated exposure to the dense, water saturated CO₂ varied from 89 to 91° and 85 to 80° for the quartz substrate for gaseous (water saturated) CO₂ and liquid (water saturated) CO₂ respectively, at 77 °F. For calcite substrates, these values varied from 60 to 59° and 54 to 48°, respectively. This important observation has serious implications towards the design and safety issues, as a permanent positive contact angle shift indicates lower CO₂ retention capabilities of sequestration sites due to a reduction in the capillary pressure. It is further confirmed that the permanent shift in the contact angle is due to surface phenomena. With an increase in temperature (from 77 to 122 °F), the contact angle shift is reduced from about 45° to about 20° for quartz substrates. Other observations in the contact angle data with respect to pressure are in good agreement with the trends reported in the literature.     

Carbonate mineralization of volcanic province basalts

Flood basalts are receiving increasing attention as possible host formations for geologic sequestration of anthropogenic CO₂, with studies underway in the United States, India, Iceland, and Canada. Basalts from the United States, India, and South Africa were reacted with aqueous dissolved CO₂ and aqueous dissolved CO₂–H₂S mixtures under supercritical CO₂ (scCO₂) conditions to study the geochemical reactions resulting from injection of CO₂ in such formations. Despite the basalt samples having similar bulk chemical composition, mineralogy and dissolution kinetics, long-term static experiments show significant differences in rates of mineralization as well as compositions and morphologies of precipitates that form when the basalts are reacted with CO₂ and CO₂–H₂S mixtures in water. For example, basalt from the Newark Basin in the United States was by far the most reactive of any basalt tested to date. Reacted grains from the Newark Basin basalt appeared severely weathered and contained extensive carbonate precipitates with significant Fe content. In comparison, the post-reacted samples associated with the Columbia River basalts from the United States contained calcite grains with classic “dogtooth spar” morphology and trace cation substitution (Mg and Mn). Carbonation of the other basalts produced precipitates with compositions that varied chemically throughout the entire testing period. The Karoo basalt from South Africa appeared the least reactive, with very limited mineralization occurring during the testing with CO₂-saturated water. Compositional differences in the precipitates suggest changes in fluid chemistry unique to the dissolution behavior of each basalt sample reacted with CO₂-saturated water. No convincing correlations were identified between basalt reactivity and differences in bulk composition, mineralogy, glassy mesostasis quantity or composition. Moreover, the relative reactivity of different basalt samples was unexpectedly different in the experiments conducted with aqueous dissolved CO₂–H₂S mixtures versus those with CO₂ only. For example, the Karoo basalt was highly reactive in the presence of aqueous dissolved CO₂–H₂S, as evident by nodules of carbonate coating the basalt grains after 181 days of testing. However, the most reactive basalt in CO₂–H₂O, Newark Basin, formed only iron sulfide coatings in tests with a CO₂–H₂S mixture, which inhibited carbonate mineralization.     

Predicting δCDIC dynamics in CCS: A scheme based on a review of inorganic carbon chemistry under elevated pressures and temperatures

Stable carbon isotopes are important tools to assess potential storage sites for CO₂, as they allow the quantification of ionic trapping via isotope mass balances. In deep geological formations high p/T conditions need to be considered, because CO₂ dissolution, equilibrium constants and isotope fractionation of dissolved inorganic carbon (DIC) depend on temperature, pressure and solute composition. After reviewing different approaches to account for these dependencies, an expanded scheme is presented for speciation and carbon isotope fractionation of DIC and dissolution of CaCO₃ for pCO₂ up to 100 bar, pH down to 3 and temperatures of up to 200 °C. The scheme evaluates the influence of respective parameters on isotope ratios during CO₂ sequestration. The pCO₂ and pH are the dominant controlling factors in the DIC/δ¹³C/pH system. The fugacity of CO₂ has major impact on DIC concentrations at temperatures below 100 °C at high pCO₂. Temperature dependency of activities and equilibrium dominates at temperatures above 100 °C. Isotope ratios of DIC are expected to be about 1–2‰ more depleted in ¹³C compared to the free CO₂ at pCO₂ values above 10 bar. This depletion is controlled by carbon isotope fractionation between CO₂ and H₂CO₃* which is the dominant species of DIC at the resulting pH below 5.     

Wellbore integrity analysis of a natural CO2 producer

Long-term integrity of existing wells in a CO₂-rich environment is essential for ensuring that geological sequestration of CO₂ will be an effective technology for mitigating greenhouse gas-induced climate change. The potential for wellbore leakage depends in part on the quality of the original construction as well as geochemical and geomechanical stresses that occur over its life-cycle. Field data are essential for assessing the integrated effect of these factors and their impact on wellbore integrity, defined as the maintenance of isolation between subsurface intervals. In this report, we investigate a 30-year-old well from a natural CO₂ production reservoir using a suite of downhole and laboratory tests to characterize isolation performance.These tests included mineralogical and hydrological characterization of 10 core samples of casing/cement/formation, wireline surveys to evaluate well conditions, fluid samples and an in situ permeability test. We find evidence for CO₂ migration in the occurrence of carbonated cement and calculate that the effective permeability of an 11′-region of the wellbore barrier system was between 0.5 and 1 milliDarcy. Despite these observations, we find that the amount of fluid migration along the wellbore was probably small because of several factors: the amount of carbonation decreased with distance from the reservoir, cement permeability was low (0.3–30 microDarcy), the cement–casing and cement-formation interfaces were tight, the casing was not corroded, fluid samples lacked CO₂, and the pressure gradient between reservoir and caprock was maintained. We conclude that the barrier system has ultimately performed well over the last 3 decades. These results will be used as part of a broader effort to develop a long-term predictive simulation tool to assess wellbore integrity performance in CO₂ storage sites.     

Mineral sequestration of carbon dioxide in basalt: A pre-injection overview of the CarbFix project

In this paper we describe the thermodynamic and kinetic basis for mineral storage of carbon dioxide in basaltic rock, and how this storage can be optimized. Mineral storage is facilitated by the dissolution of CO₂ into the aqueous phase. The amount of water required for this dissolution decreases with decreased temperature, decreased salinity, and increased pressure. Experimental and field evidence suggest that the factor limiting the rate of mineral fixation of carbon in silicate rocks is the release rate of divalent cations from silicate minerals and glasses. Ultramafic rocks and basalts, in glassy state, are the most promising rock types for the mineral sequestration of CO₂ because of their relatively fast dissolution rate, high concentration of divalent cations, and abundance at the Earth's surface. Admixture of flue gases, such as SO₂ and HF, will enhance the dissolution rates of silicate minerals and glasses. Elevated temperature increases dissolution rates but porosity of reactive rock formations decreases rapidly with increasing temperature. Reduced conditions enhance mineral carbonation as reduced iron can precipitate in carbonate minerals. Elevated CO₂ partial pressure increases the relative amount of carbonate minerals over other secondary minerals formed. The feasibility to fix CO₂ by carbonation in basaltic rocks will be tested in the CarbFix project by: (1) injection of CO₂ charged waters into basaltic rocks in SW Iceland, (2) laboratory experiments, (3) studies of natural analogues, and (4) geochemical modelling.     

Study on the failure mechanism of potassium-based sorbent for CO2 capture and the improving measure

With thermogravimetric apparatus (TGA), X-ray diffraction (XRD) and barium sulfate gravimetric methods, the carbonation reactivities of K₂CO₃ and K₂CO₃/Al₂O₃ in the simulated flue gases with SO₂ are investigated and the reaction equations are inferred. Results show that there are KHCO₃ and K₂SO₃ generated. The generation K₂SO₃ reduces the utilization ratio of the sorbent. H₂O may accelerates the sulfation reaction of AR K₂CO₃ as K₄H₂(CO₃)₃·1.5H₂O is generated in the reaction among K₂CO₃, SO₂ and H₂O. K₂SO₃ is directly generated from sulfation reaction of K₂CO₃/Al₂O₃, because there are K₂CO₃·1.5H₂O and K₂SO₃ generated in the reaction among K₂CO₃/Al₂O₃, SO₂ and H₂O. K₂CO₃·1.5H₂O does not react with SO₂, and K₂CO₃·1.5H₂O/Al₂O₃ reacts with SO₂ slowly. Compare with the reaction process without H₂O pretreatment, the reaction rates of KAl30 increased after H₂O pretreatment and the failure ratio is about a half of that without H₂O pretreatment. So, K₂CO₃/Al₂O₃ shows good carbonation and anti-sulfation characteristic after H₂O pretreatment.     

Viscosities, thermal conductivities and diffusion coefficients of CO2 mixtures: Review of experimental data and theoretical models

Accurate experimental data on the thermo-physical properties of CO₂-mixtures are pre-requisites for development of more accurate models and hence, more precise design of CO₂ capture and storage (CCS) processes. A literature survey was conducted on both the available experimental data and the theoretical models associated with the transport properties of CO₂-mixtures within the operation windows of CCS. Gaps were identified between the available knowledge and requirements of the system design and operation. For the experimental gas-phase measurements, there are no available data about any transport properties of CO₂/H₂S, CO₂/COS and CO₂/NH₃; and except for CO₂/H₂O(/NaCl) and CO₂/amine/H₂O mixtures, there are no available measurements regarding the transport properties of any liquid-phase mixtures. In the prediction of gas-phase viscosities using Chapman–Enskog theory, deviations are typically <2% at atmospheric pressure and moderate temperatures. The deviations increase with increasing temperatures and pressures. Using both the Rigorous Kinetic Theory (RKT) and empirical models in the prediction of gas-phase thermal conductivities, typical deviations are 2.2–9%. Comparison of popular empirical models for estimation of gas-phase diffusion coefficients with newer experimental data for CO₂/H₂O shows deviations of up to 20%. For many mixtures relevant for CCS, the diffusion coefficient models based on the RKT show predictions within the experimental uncertainty. Typical reported deviations of the CO₂/H₂O system using empirical models are below 3% for the viscosity and the thermal conductivity and between 5 and 20% for the diffusion coefficients. The research community knows little about the effect of other impurities in liquid CO₂ than water, and this is an important area to focus in future work.     

Intermediate storage of carbon dioxide in geological formations: A technical perspective

Enhanced oil recovery (EOR) through CO₂ flooding has been practiced on a commercial basis for the last 35 years and continues today at several sites, currently injecting in total over 30 million tons of CO₂ annually. This practice is currently exclusively for economic gain, but can potentially contribute to the reduction of emissions of greenhouse gases provided it is implemented on a large scale. Optimal operations in distributing CO₂ to CO₂-EOR or enhanced gas recovery (EGR) projects (referred to here collectively as CO₂-EHR) on a large scale and long time span imply that intermediate storage of CO₂ in geological formations may be a key component. Intermediate storage is defined as the storage of CO₂ in geological media for a limited time span such that the CO₂ can be sufficiently reproduced for later use in CO₂-EHR. This paper investigates the technical aspects, key individual parameters and possibilities of intermediate storage of CO₂ in geological formations aiming at large scale implementation of carbon dioxide capture and storage (CCS) for deep emission reduction. The main parameters are thus the depth of injection and density, CO₂ flow and transport processes, storage mechanisms, reservoir heterogeneity, the presence of impurities, the type of the reservoirs and the duration of intermediate storage. Structural traps with no flow of formation water combined with proper injection planning such as gas-phase injection favour intermediate storage in deep saline aquifers. In depleted oil and gas fields, high permeability, homogeneous reservoirs with structural traps (e.g. anticlinal structures) are good candidates for intermediate CO₂ storage. Intuitively, depleted natural gas reservoirs can be potential candidates for intermediate storage of carbon dioxide due to similarity in storage characteristics.     

Numerical parametric study on CO2 capture by indirect thermal swing adsorption

Post-combustion CO₂ capture remains one of the most-challenging issue to lower CO₂ emissions of existing power plants or heavy industry installations because of strong economy and energy efficiency aspects. The major issue comes from CO₂ dilution (4% for NGCC and 14% for PC) and the high flow rates to be treated. Furthermore, CO₂ purity has to be higher than 95% with recovery at 90%, to match the transportation/injection requirements.The MEA absorption process remains the reference today but its energy consumption (about 3 MJ/kg_CO2) and the amine consumption are still challenging drawbacks.The interest of CO₂ capture by indirect TSA (Temperature Swing Adsorption) was demonstrated experimentally in a previous work. The aim of this paper is to present the results of a numerical parametric study. Two main parameters are explored: the desorption temperature (100–200 °C) and the purge flow rate (0.1–0.5 Ndm³ min⁻¹). Four performance indicators are evaluated: CO₂ purity, recovery, productivity and specific energy consumption.Results show that purity above 95% can be achieved. Keeping the 95% target, it is possible to achieve recovery at 81% with productivity at 57.7 g_CO2/kg_ads h and a specific energy consumption of 3.23 MJ/kg_CO2, which is less than for the reference MEA process.Comparison with other adsorption processes exhibits that this process has good potential especially since some improvements are still expected from further research.     

Time-lapse carbon dioxide monitoring with pulsed neutron logging

Elevated levels of CO₂ in the atmosphere have been linked to the rise in land and sea temperature [Climate Change, 2001. In: Houghton, J.T., Ding, Y., Griggs, D.J., Noguer, M., van der Linden, P.J., Xiaosu, D. (Eds.), The Scientific Basis Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change (IPCC). Cambridge University Press, UK, p. 944]. To demonstrate geological carbon sequestration as a mitigation technique, a carbon dioxide injection experiment was conducted in East Texas. The target – Frio formation – is a highly porous, permeable and unconsolidated sandstone. The specific interval is the Frio C sand, which originally was saturated with saline formation water. At the injection location, the Frio C sand dips 18° to the south. To monitor the injected CO₂ spreading in the formation, an old well from 1956 drilled into the deeper Yegua formation was selected as the observation well. The injection well was drilled at a distance of 100 ft downdip from the monitoring well. Several borehole measurement methods were available to monitor the CO₂ injection, but the most suitable technology was thought to be the pulsed neutron logging. This logging is used widely in cased hole, and the measured macroscopic thermal absorption cross-section (Σ) is sensitive to CO₂ saturation in high porosity saline water environments. Several log examples are given demonstrating successful the monitoring of the CO₂ plume moving through the two boreholes and the resulting saturation changes.     

Coastal spreading of olivine to control atmospheric CO2 concentrations: A critical analysis of viability

Qualitative proposals to control atmospheric CO₂ concentrations by spreading crushed olivine rock along the Earth's coastlines, thereby accelerating weathering reactions, are presently attracting considerable attention. This paper provides a critical evaluation of the concept, demonstrating quantitatively whether or not it can contribute significantly to CO₂ sequestration. The feasibility of the concept depends on the rate of olivine dissolution, the sequestration capacity of the dominant reaction, and its CO₂ footprint. Kinetics calculations show that offsetting 30% of worldwide 1990 CO₂ emissions by beach weathering means distributing of 5.0 Gt of olivine per year. For mean seawater temperatures of 15–25 °C, olivine sand (300 μm grain size) takes 700–2100 years to reach the necessary steady state sequestration rate and is therefore of little practical value. To obtain useful, steady state CO₂ uptake rates within 15–20 years requires grain sizes <10 μm. However, the preparation and movement of the required material poses major economic, infrastructural and public health questions. We conclude that coastal spreading of olivine is not a viable method of CO₂ sequestration on the scale needed. The method certainly cannot replace CCS technologies as a means of controlling atmospheric CO₂ concentrations.     

Water/acid gas interfacial tensions and their impact on acid gas geological storage

Acid gas geological disposal is a promising process to reduce CO₂ atmospheric emissions and an environment-friendly and economic alternative to the transformation of H₂S into sulphur by the Claus process. Acid gas confinement in geological formations is to a large extent controlled by the capillary properties of the water/acid–gas/caprock system, because a significant fraction of the injected gas rises buoyantly and accumulates beneath the caprock. These properties include the water/acid gas interfacial tension (IFT), to which the so-called capillary entry pressure of the gas in the water-saturated caprock is proportional. In this paper we present the first ever systematic water/acid gas IFT measurements carried out by the pendant drop technique under geological storage conditions. We performed IFT measurements for water/H₂S systems over a large range of pressure (up to P = 15 MPa) and temperature (up to T = 120 °C). Water/H₂S IFT decreases with increasing P and levels off at around 9–10 mN/m at high T (≥70 °C) and P (>12 MPa). The latter values are around 30–40% of water/CO₂ IFTs, and around 20% of water/CH₄ IFTs at similar T and P conditions. The IFT between water and a CO₂ + H₂S mixture at T = 77 °C and P > 7.5 MPa is observed to be approximately equal to the molar average IFT of the water/CO₂ and water/H₂S binary mixtures. Thus, when the H₂S content in the stored acid gas increases the capillary entry pressure decreases, together with the maximum height of acid gas column and potential storage capacity of a given geological formation. Hence, considerable attention should be exercised when refilling with a H₂S-rich acid gas a depleted gas reservoir, or a depleted oil reservoir with a gas cap: in the case of hydrocarbon reservoirs that were initially (i.e., at the time of their discovery) close to capillary leakage, acid gas leakage through the caprock will inevitably occur if the refilling pressure approaches the initial reservoir pressure.     

Land-use changes and carbon sequestration through the twentieth century in a Mediterranean mountain ecosystem: Implications for land management

Ecosystems in the western Mediterranean basin have undergone intense changes in land use throughout the centuries, resulting in areas with severe alterations. Today, most these areas have become sensitive to human activity, prone to profound changes in land-use configuration and ecosystem services. A consensus exists amongst stakeholders that ecosystem services must be preserved but managerial strategies that help to preserve them while ensuring sustainability are often inadequate. To provide a basis for measuring implications of land-use change on carbon sequestration services, changes in land use and associated carbon sequestration potential throughout the 20th century in a rural area at the foothills of the Sierra Nevada range (SE Spain) were explored. We found that forest systems replaced dryland farming and pastures from the middle of the century onwards as a result of agricultural abandonment and afforestation programs. The area has always acted as a carbon sink with sequestration rates ranging from 28,961 t CO₂ year^?1 in 1921 to 60,635 t CO₂ year^?1 in 1995, mirroring changes in land use. Conversion from pastures to woodland, for example, accounted for an increase in carbon sequestration above 30,000 t CO₂ year^?1 by the end of the century. However, intensive deforestation would imply a decrease of approximately 66% of the bulk CO₂ fixed. In our study area, woodland conservation is essential to maintain the ecosystem services that underlie carbon sequestration. Our essay could inspire policymakers to better achieve goals of increasing carbon sequestration rates and sustainability within protected areas.     

Petrophysical analysis to investigate the effects of carbon dioxide storage in a subsurface saline aquifer at Ketzin, Germany (CO2SINK)

To test the injection behaviour of CO₂ into brine-saturated rock and to evaluate the dependence of geophysical properties on CO₂ injection, flow and exposure experiments with brine and CO₂ were performed on sandstone samples of the Stuttgart Formation representing potential reservoir rocks for CO₂ storage. The sandstone samples studied are generally fine-grained with porosities between 17 and 32% and permeabilities between 1 and 100 mD.Additional batch experiments were performed to predict the long-term behaviour of geological CO₂ storage. Reservoir rock samples were exposed over a period of several months to CO₂-saturated reservoir fluid in high-pressure vessels under in situ temperature and pressure conditions. Petrophysical parameters, porosity and the pore radius distribution were investigated before and after the experiments by NMR (Nuclear Magnetic Resonance) relaxation and mercury injection. Most of the NMR measurements of the tested samples showed a slight increase of porosity and a higher proportion of large pores.     

Characterization of a limestone in a batch fluidized bed reactor for sulfur retention under oxy-fuel operating conditions

CO₂ and SO₂ are some of the main polluting gases emitted into atmosphere in combustion processes using fossil fuel for energy production. The former is one of the major contributors to build-up the greenhouse effect implicated in global climate change and the latter produces acid rain. Oxy-fuel combustion is a technology, which consists in burning the fuel with a mix of pure O₂ and recirculated CO₂. With this technology the CO₂ concentration in the flue gas may be enriched up to 95%, becoming possible an easy CO₂ recovery. In addition, oxy-fuel combustion in fluidized beds allows in situ desulfurization of combustion gases by supplying calcium based sorbent.In this work, the effect of the principal operation variables affecting the sulfation reaction rate in fluidized bed reactors (temperature, CO₂ partial pressure, SO₂ concentration and particle size) under typical oxy-fuel combustion conditions have been analyzed in a batch fluidized bed reactor using a limestone as sorbent. It has been observed that sulfur retention can be carried out by direct sulfation of the CaCO₃ or by sulfation of the CaO (indirect sulfation) formed by CaCO₃ calcination. Direct sulfation and indirect sulfation operating conditions depended on the temperature and CO₂ partial pressure. The rate of direct sulfation rose with temperature and the rate of indirect sulfation for long reaction times decreased with temperature. An increase in the CO₂ partial pressure had a negative influence on the sulfation conversion reached by the limestone due to a higher temperature was needed to work in conditions of indirect sulfation. Thus, it is expected that the optimum temperature for sulfur retention in oxy-fuel combustion in fluidized bed reactors be about 925–950 °C. Sulfation reaction rate rose with decreasing sorbent particle size and increasing SO₂ concentration.     

The influence of the precursor and synthesis method on the CO2 capture capacity of carpet waste-based sorbents

Adsorption is one of the most promising technologies for reducing CO₂ emissions and at present several different types of sorbents are being investigated. The use of sorbents obtained from low-cost and abundant precursors (i.e. solid wastes) appears an attractive strategy to adopt because it will contribute to a reduction not only in operational costs but also in the amount of waste that is dumped and burned in landfills every year. Following on from previous studies by the authors, in this work several carbon-based adsorbents were developed from different carpet wastes (pre-consumer and post-consumer wastes) by chemical activation with KOH at various activation temperatures (600–900 °C) and KOH:char impregnation ratios (0.5:1 to 4:1). The prepared materials were characterised by chemical analysis and gas adsorption (N₂, −196 °C; CO₂, 0 °C), and tested for CO₂ adsorption at temperatures of 25 and 100 °C. It was found that both the type of precursor and the conditions of activation (i.e. impregnation ratios, and activation temperatures), had a huge influence on the microporosity of the resultant samples and their CO₂ capture capacities. The carbon-based adsorbent that presented the maximum CO₂ capture capacities at 25 and 100 °C (13.8 wt.% and 3.1 wt.%, respectively), was prepared from a pre-consumer carpet waste and was activated at 700 °C using a KOH:char impregnation ratio of 1:1. This sample showed the highest narrow microporosity volume (0.47 cm³ g⁻¹), thus confirming that only pores of less than 1 nm are effective for CO₂ adsorption at atmospheric pressure.     

Basin-scale hydrogeologic impacts of CO2 storage: Capacity and regulatory implications

Industrial-scale injection of CO₂ into saline formations in sedimentary basins will cause large-scale fluid pressurization and migration of native brines, which may affect valuable groundwater resources overlying the deep sequestration aquifers. In this paper, we discuss how such basin-scale hydrogeologic impacts (1) may reduce current storage capacity estimates, and (2) can affect regulation of CO₂ storage projects. Our assessment arises from a hypothetical future carbon sequestration scenario in the Illinois Basin, which involves twenty individual CO₂ storage projects (sites) in a core injection area most suitable for long-term storage. Each project is assumed to inject five million tonnes of CO₂ per year for 50 years. A regional-scale three-dimensional simulation model was developed for the Illinois Basin that captures both the local-scale CO₂–brine flow processes and the large-scale groundwater flow patterns in response to CO₂ storage. The far-field pressure buildup predicted for this selected sequestration scenario support recent studies in that environmental concerns related to near- and far-field pressure buildup may be a limiting factor on CO₂ storage capacity. In other words, estimates of storage capacity, if solely based on the effective pore volume available for safe trapping of CO₂, may have to be revised based on assessments of pressure perturbations and their potential impacts on caprock integrity and groundwater resources. Our results suggest that (1) the area that needs to be characterized in a permitting process may comprise a very large region within the basin if reservoir pressurization is considered, and (2) permits cannot be granted on a single-site basis alone because the near- and far-field hydrogeologic response may be affected by interference between individual storage sites. We also discuss some of the challenges in making reliable predictions of large-scale hydrogeologic impacts related to CO₂ sequestration projects.     

Lessons learned from natural and industrial analogues for storage of carbon dioxide

The deployment of CCS (carbon capture and storage) at industrial scale implies the development of effective monitoring tools. Noble gases are tracers usually proposed to track CO₂. This methodology, combined with the geochemistry of carbon isotopes, has been tested on available analogues.At first, gases from natural analogues were sampled in the Colorado Plateau and in the French carbogaseous provinces, in both well-confined and leaking-sites. Second, we performed a 2-years tracing experience on an underground natural gas storage, sampling gas each month during injection and withdrawal periods.In natural analogues, the geochemical fingerprints are dependent on the containment criterion and on the geological context, giving tools to detect a leakage of deep-CO₂ toward surface. This study also provides information on the origin of CO₂, as well as residence time of fluids within the crust and clues on the physico-chemical processes occurring during the geological story.The study on the industrial analogue demonstrates the feasibility of using noble gases as tracers of CO₂. Withdrawn gases follow geochemical trends coherent with mixing processes between injected gas end-members. Physico-chemical processes revealed by the tracing occur at transient state.These two complementary studies proved the interest of geochemical monitoring to survey the CO₂ behaviour, and gave information on its use.     

Laboratory calibration of the seismo-acoustic response of CO2 saturated sandstones

Ultrasonic experiments were undertaken on CO₂ flooded sandstone core samples, both synthetic sandstones and core plugs from the CRC1 CO₂ injection well in the Otway Basin, Victoria, South Eastern. Australia. The aim of these laboratory tests was to investigate the effects of CO₂ as a pore fluid on the seismo-acoustic response of the sandstone and ultimately to provide an indication of the sensitivity of time-lapse seismic imaging of the eventual CO₂/CH₄ plume in the Otway, Waarre C formation.The synthetic sandstones were manufactured using both a proprietary calcium in situ precipitation (CIPS) process and a silica cementing technique. Samples were tested in a computer controlled triaxial pressure cell where pore pressures can be controlled independently of the confining pressures. The pressure cell is equipped with ultrasonic transducers housed in the loading platens. Consequently, effective pressures equivalent to those expected in the reservoir can be applied while ultrasonic testing is undertaken. Both compressional, P and shear waves, S were recorded via a digital oscilloscope at a range of effective pressure steps. Pore pressures were varied from 4 MPa to 17 MPa to represent both the gaseous and liquid phase regions of the CO₂ phase diagram. Similar experiments were conducted on core plugs from the Waarre C reservoir horizon obtained from the CRC1 injection well, but with an intervening brine-saturated step and in some cases with a CO₂/CH₄ mix of 80%/20% molar fraction which is representative of the field situation. However, the pore pressure in these experiments was held at 4 MPa. Finally, acoustic impedances and reflection coefficients were calculated for the reservoir using Gassmann theory and the implications for imaging the CO₂ plume is discussed.     

Global Warming and Global Dioxide Emission: An Empirical Study

In this paper, the dynamic relationship between global surface temperature (global warming) and global carbon dioxide emission (CO₂) is modelled and analyzed by causality and spectral analysis in the time domain and frequency domain, respectively. Historical data of global CO₂emission and global surface temperature anomalies over 129 years from 1860–1988 are used in this study. The causal relationship between the two phenomena is first examined using the Sim and Granger causality test in the time domain after the data series are filtered by ARIMA models. The Granger causal relationship is further scrutinized and confirmed by cross-spectral and multichannel spectral analysis in the frequency domain. The evidence found from both analyses proves that there is a positive causal relationship between the two variables. The time domain analysis suggests that Granger causality exists between global surface temperature and global CO₂emission. Further, CO₂emission causes the change in temperature. The conclusions are further confirmed by the frequency domain analysis, which indicates that the increase in CO₂emission causes climate warming because a high coherence exists between the two variables. Furthermore, it is proved that climate changes happen after an increase in CO₂emission, which confirms that the increase in CO₂emission does cause global warming.