Changes in reactive surface area during limestone dissolution: An experimental and modelling study

Noiriel, Catherine; Luquot, Linda; Madé, Benoı̂t; Raimbault, Louis; Gouze, Philippe; Lee, Jan van der

doi:10.1016/j.chemgeo.2009.01.032

Cited by 237 publications

(205 citation statements)

References 40 publications

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“…However, issues were raised after comparing the macroscopic and microscopic results since, in some cases, both dissolution rates agree whereas, in other cases, orders of magnitude differences were observed [38,40,41]. This leads to a further debate on the applicability of the experimental macroscopic and microscopic dissolution rate in reactive transport models since the geometrical surface area strongly depends on the scale at which the process are observed [42].…”

Section: Introductionmentioning

confidence: 99%

Kinetics of calcite dissolution in CO2-saturated water at temperatures between (323 and 373) K and pressures up to 13.8 MPa

et al. 2015

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We report measurements of the calcite dissolution rate in CO2-saturated water at pressures ranging from (6.0 to 13.8) MPa and temperatures from (323 to 373) K. The rate of calcite dissolution in HCl(aq) at temperatures from (298 to 353) K was also measured at ambient pressure with pH between 2.0 and 3.3. A specially-designed batch reactor system, implementing a rotating disc technique, was used to obtain the dissolution rate at the solid/liquid interface of a single crystal, free of mass transfer effects. We used Vertical Scanning Interferometry to examine the texture of the calcite surface produced by the experiment and the results suggested that at far-from-equilibrium conditions, the measured calcite dissolution rate was independent of the initial defect density due to the development of a dynamic dissolution pattern which became steady-state shortly after the onset of dissolution. The results of this study indicate that the calcite dissolution rate under surface-reactioncontrolled conditions increases with increase of temperature from (323 to 373) K and CO2 partial pressure from (6.0 to 13.8) MPa. Fitting the conventional first order transition state kinetic model to the observed rate suggested that, although sufficient to describe calcite dissolution in CO2-free HCl(aq), this model clearly underestimate the calcite dissolution rate in the (CO2 + H2O) system over the range of conditions studied. A kinetic model incorporating both pH and the activity of CO2(aq) has been developed to represent the dissolution rates found in this study. We report correlations for the corresponding reaction rate coefficients based on the Arrhenius equation and compare the apparent activation energies with values from the literature. The results of this study should facilitate more rigorous modelling of mineral dissolution in deep saline aquifers used for CO2 storage.2

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Section: Introductionmentioning

confidence: 99%

Kinetics of calcite dissolution in CO2-saturated water at temperatures between (323 and 373) K and pressures up to 13.8 MPa

et al. 2015

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“…In these systems, therefore, mineral abundance alone may not accurately reflect the accessibility of mineral surfaces to reactive fluids and the effect of transport limitations needs to be considered , Scislewski and Zuddas, 2010, Salehikhoo and Li, 2015. In addition, existing estimates of reactive surface area do not account for the possibility that reactive surface area may evolve during reaction due to dissolution or armoring (Luquot and Gouze, 2009, Noiriel et al, 2009, Scislewski and Zuddas, 2010, Gouze and Luquot, 2011.…”

Section: Introductionmentioning

confidence: 99%

Evaluation of accessible mineral surface areas for improved prediction of mineral reaction rates in porous media

Beckingham

Steefel

Swift

et al. 2017

Geochimica et Cosmochimica Acta

121

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The rates of mineral dissolution reactions in porous media are difficult to predict, in part because of a lack of understanding of mineral reactive surface area in natural porous media. Common estimates of mineral reactive surface area used in reactive transport models for porous media are typically ad hoc and often based on average grain size, increased to account for surface roughness or decreased by several orders of magnitude to account for reduced surface reactivity of field as opposed to laboratory samples. In this study, accessible mineral surface areas are determined for a sample from the reservoir formation at the Nagaoka pilot CO2 injection site (Japan) using a multi-scale image analysis based on synchrotron Xray microCT, SEMQEMSCAN, XRD, SANS, and FIB-SEM. This analysis not only accounts for accessibility of mineral surfaces to macro-pores, but also accessibility through connected micro-pores in smectite, the most abundant clay mineral in this sample. While the imaging analysis reveals that most of the micro-and macro-pores are well connected, some pore regions are unconnected and thus inaccessible to fluid flow and diffusion. To evaluate whether mineral accessible surface area accurately reflects reactive surface area a flow-through core experiment is performed and modeled at the continuum scale. The core experiment is performed under conditions replicating the pilot site and the evolution of effluent solutes in the aqueous phase is tracked.Various reactive surface area models are evaluated for their ability to capture the observed effluent chemistry, beginning with parameter values determined as a best fit to a disaggregated sediment experiment (Beckingham et al., 2016) described previously.Simulations that assume that all mineral surfaces are accessible (as in the disaggregated sediment experiment) over-predict the observed mineral reaction rates, suggesting that a reduction of RSA by a factor of 10-20 is required to match the core flood experimental data. While the fit of the effluent chemistry (and inferred mineral dissolution rates) greatly improve when the pore-accessible mineral surface areas are used, it was also necessary to include highly reactive glass phases to match the experimental observations, in agreement with conclusions from the disaggregated sediment experiment. It is hypothesized here that the 10-20 reduction in reactive surface areas based on the limited pore accessibility of reactive phases in core flood experiment may be reasonable for poorly sorted and cemented sediments like those at the Nagaoka site, although this reflects pore rather than larger scale heterogeneity.

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“…The Lattice-Boltzmann and pore-network simulations were performed on images of dry samples of similar rock. A number of studies used micro CT imaging for investigating the geochemical transformation of the pores by stored carbon dioxide (Noiriel et al 2004;Bernard 2005;Luquot and Gouze 2009;Noiriel et al 2009;Flukiger and Bernard 2009).…”

Section: Introductionmentioning

confidence: 99%

Microtomography and Pore-Scale Modeling of Two-Phase Fluid Distribution

et al. 2010

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Synchrotron-based X-ray microtomography (micro CT) at the Advanced Light Source (ALS) line 8.3.2 at the Lawrence Berkeley National Laboratory produces threedimensional micron-scale-resolution digital images of the pore space of the reservoir rock along with the spacial distribution of the fluids. Pore-scale visualization of carbon dioxide flooding experiments performed at a reservoir pressure demonstrates that the injected gas fills some pores and pore clusters, and entirely bypasses the others. Using 3D digital images of the pore space as input data, the method of maximal inscribed spheres (MIS) predicts two-phase fluid distribution in capillary equilibrium. Verification against the tomography images shows a good agreement between the computed fluid distribution in the pores and the experimental data. The model-predicted capillary pressure curves and tomography-based porosimetry distributions compared favorably with the mercury injection data. Thus, micro CT in combination with modeling based on the MIS is a viable approach to study the porescale mechanisms of CO 2 injection into an aquifer, as well as more general multi-phase flows.

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Changes in reactive surface area during limestone dissolution: An experimental and modelling study

Cited by 237 publications

References 40 publications

Kinetics of calcite dissolution in CO2-saturated water at temperatures between (323 and 373) K and pressures up to 13.8 MPa

Kinetics of calcite dissolution in CO2-saturated water at temperatures between (323 and 373) K and pressures up to 13.8 MPa

Evaluation of accessible mineral surface areas for improved prediction of mineral reaction rates in porous media

Microtomography and Pore-Scale Modeling of Two-Phase Fluid Distribution

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