Chemical affinity and pH effects on chlorite dissolution kinetics under geological CO2 sequestration related conditions

Zhang, Shuo; Yang, Li; DePaolo, Donald J.; Steefel, Carl I.

doi:10.1016/j.chemgeo.2015.01.001

Title: Chemical affinity and pH effects on chlorite dissolution kinetics under geological CO₂ sequestration related conditions

Abstract

The kinetic dissolution of Flagstaff Hill chlorite (CCa-2 from Clay Minerals Society), (Mg_4.55Al_1.23Fe_0.12)(Al_1.04Si_2.96)O₁₀(OH)₈, was investigated using a well-mixed flow-through reactor at 100 °C, pH values ranging from 3.0 to 7.5, and variable saturation states. The objective was to measure the dependence of chlorite dissolution rate on pH as well as on degree of undersaturation under conditions applicable to geologic carbon storage. A batch experiment was conducted to determine the equilibrium constant of the dissolution reaction at 100 °C for the chlorite mineral phase used in this study. A series of experiments was run at varying CO₂ partial pressures (0–60 bars) and different flow rates (0.01–0.25 ml/min). Here, we use our experimental results in conjunction with previously published data to separate the effects of pH and solution saturation state. At constant pH, the chlorite dissolution rate decreases slowly as a function of the Gibbs free energy of reaction (ΔG_r), which is a quantitative measure of the degree of undersaturation.

Authors:

Zhang, Shuo ^[1]; Yang, Li ^[2]; DePaolo, Donald J. ^[1]; Steefel, Carl I. ^[2]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Publication Date:: Wed Jan 14 00:00:00 EST 2015

Research Org.:: Energy Frontier Research Centers (EFRC) (United States). Center for Nanoscale Control of Geologic CO2 (NCGC)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1210470

Alternate Identifier(s):: OSTI ID: 1246656

Grant/Contract Number:: AC02–05CH11231; AC02-CH11231

Resource Type:: Accepted Manuscript

Journal Name:: Chemical Geology

Additional Journal Information:: Journal Volume: 396; Journal Issue: C; Related Information: NCGC partners with Lawrence Berkeley National Laboratory (lead); University of California, Davis; Lawrence Livermore National Laboratory; Massachusetts Institute of Technology; Ohio State University; Oak Ridge National Laboratory; Washington University, St. Louis; Journal ID: ISSN 0009-2541

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 58 GEOSCIENCES; bio-inspired; mechanical behavior; carbon sequestration; chlorite dissolution kinetics; chemical affinity effects; CO2 sequestration

Citation Formats


                    Zhang, Shuo, Yang, Li, DePaolo, Donald J., and Steefel, Carl I. Chemical affinity and pH effects on chlorite dissolution kinetics under geological CO2 sequestration related conditions.  United States: N. p., 2015. 
Web.  doi:10.1016/j.chemgeo.2015.01.001.

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                    Zhang, Shuo, Yang, Li, DePaolo, Donald J., & Steefel, Carl I. Chemical affinity and pH effects on chlorite dissolution kinetics under geological CO2 sequestration related conditions.  United States.  https://doi.org/10.1016/j.chemgeo.2015.01.001

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                    Zhang, Shuo, Yang, Li, DePaolo, Donald J., and Steefel, Carl I. Wed .  
"Chemical affinity and pH effects on chlorite dissolution kinetics under geological CO2 sequestration related conditions".  United States.  https://doi.org/10.1016/j.chemgeo.2015.01.001.  https://www.osti.gov/servlets/purl/1210470.

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@article{osti_1210470,

  title        = {Chemical affinity and pH effects on chlorite dissolution kinetics under geological CO2 sequestration related conditions},

  author       = {Zhang, Shuo and Yang, Li and DePaolo, Donald J. and Steefel, Carl I.},

  abstractNote = {The kinetic dissolution of Flagstaff Hill chlorite (CCa-2 from Clay Minerals Society), (Mg4.55Al1.23Fe0.12)(Al1.04Si2.96)O10(OH)8, was investigated using a well-mixed flow-through reactor at 100 °C, pH values ranging from 3.0 to 7.5, and variable saturation states. The objective was to measure the dependence of chlorite dissolution rate on pH as well as on degree of undersaturation under conditions applicable to geologic carbon storage. A batch experiment was conducted to determine the equilibrium constant of the dissolution reaction at 100 °C for the chlorite mineral phase used in this study. A series of experiments was run at varying CO2 partial pressures (0–60 bars) and different flow rates (0.01–0.25 ml/min). Here, we use our experimental results in conjunction with previously published data to separate the effects of pH and solution saturation state. At constant pH, the chlorite dissolution rate decreases slowly as a function of the Gibbs free energy of reaction (ΔGr), which is a quantitative measure of the degree of undersaturation.},

  doi          = {10.1016/j.chemgeo.2015.01.001},

  journal      = {Chemical Geology},

  number       = C,

  volume       = 396,

  place        = {United States},

  year         = {Wed Jan 14 00:00:00 EST 2015},

  month        = {Wed Jan 14 00:00:00 EST 2015}

}

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Works referenced in this record:

Thermodynamic and kinetic constraints on reaction rates among minerals and aqueous solutions; I, Theoretical considerations
journal, March 1982

Aagaard, P.; Helgeson, H. C.
American Journal of Science, Vol. 282, Issue 3
DOI: 10.2475/ajs.282.3.237

The stability of Fe-Mg chlorites in hydrothermal solutions: II. thermodynamic properties
journal, October 2002

Aja, Stephen U.
Clays and Clay Minerals, Vol. 50, Issue 5
DOI: 10.1346/000986002320679323

Atomic-resolution transmission electron microscope evidence for the mechanism by which chlorite weathers to 1:1 semi-regular chlorite-vermiculite
journal, April 1998

Banfield, Jillian F.; Murakami, Takashi
American Mineralogist, Vol. 83, Issue 3-4
DOI: 10.2138/am-1998-3-419

Chlorite dissolution in the acid ph-range: a combined microscopic and macroscopic approach
journal, April 2003

Brandt, Felix; Bosbach, Dirk; Krawczyk-Bärsch, Evelyn
Geochimica et Cosmochimica Acta, Vol. 67, Issue 8
DOI: 10.1016/S0016-7037(02)01293-0

Free energy dependence of albite dissolution kinetics at 80°C and pH 8.8
journal, March 1993

Burch, T. E.; Nagy, K. L.; Lasaga, A. C.
Chemical Geology, Vol. 105, Issue 1-3
DOI: 10.1016/0009-2541(93)90123-Z

Smectite dissolution kinetics at 80°C and pH 8.8
journal, August 2000

Cama, Jordi; Ganor, Jiwchar; Ayora, Carles
Geochimica et Cosmochimica Acta, Vol. 64, Issue 15
DOI: 10.1016/S0016-7037(00)00378-1

Amorphous silica precipitation (60 to 120°C): comparison of laboratory and field rates
journal, April 1998

Carroll, Susan; Mroczek, Edward; Alai, Maureen
Geochimica et Cosmochimica Acta, Vol. 62, Issue 8
DOI: 10.1016/S0016-7037(98)00052-0

Thermodynamic properties of chlorite CCa-2. Heat capacities, heat contents and entropies
journal, August 2009

Gailhanou, H.; Rogez, J.; Miltenburg, J. C. van
Geochimica et Cosmochimica Acta, Vol. 73, Issue 16
DOI: 10.1016/j.gca.2009.04.040

Kinetics of Dissolution of Noncrystalline Oxides and Crystalline Clay Minerals in a Basic Tiron Solution
journal, January 1990

Hayashi, Hisato
Clays and Clay Minerals, Vol. 38, Issue 3
DOI: 10.1346/CCMN.1990.0380310

Dissolution kinetics as a function of the Gibbs free energy of reaction: An experimental study based on albite feldspar
journal, January 2006

Hellmann, Roland; Tisserand, Delphine
Geochimica et Cosmochimica Acta, Vol. 70, Issue 2
DOI: 10.1016/j.gca.2005.10.007

Solubility of Two High-Mg and Two High-Fe Chlorites Using Multiple Equilibria1
journal, January 1982

Kittrick, J. A.
Clays and Clay Minerals, Vol. 30, Issue 3
DOI: 10.1346/CCMN.1982.0300302

Measurement of accessible reactive surface area in a sandstone, with application to CO2 mineralization
journal, July 2012

Landrot, Gautier; Ajo-Franklin, Jonathan B.; Yang, Li
Chemical Geology, Vol. 318-319
DOI: 10.1016/j.chemgeo.2012.05.010

Chemical kinetics of water-rock interactions
journal, June 1984

Lasaga, Antonio C.
Journal of Geophysical Research: Solid Earth, Vol. 89, Issue B6
DOI: 10.1029/JB089iB06p04009

The kinetics of the dissolution of chlorite as a function of pH and at 25°C
journal, April 2005

Lowson, Richard T.; Comarmond, M. -C. Josick; Rajaratnam, Geetha
Geochimica et Cosmochimica Acta, Vol. 69, Issue 7
DOI: 10.1016/j.gca.2004.09.028

The kinetics of chlorite dissolution
journal, March 2007

Lowson, Richard T.; Brown, Paul L.; Comarmond, M. -C. Josick
Geochimica et Cosmochimica Acta, Vol. 71, Issue 6
DOI: 10.1016/j.gca.2006.12.008

CO2–rock–brine interactions in Lower Tuscaloosa Formation at Cranfield CO2 sequestration site, Mississippi, U.S.A.
journal, January 2012

Lu, Jiemin; Kharaka, Yousif K.; Thordsen, James J.
Chemical Geology, Vol. 291
DOI: 10.1016/j.chemgeo.2011.10.020

The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California
journal, May 2009

Maher, Kate; Steefel, Carl I.; White, Art F.
Geochimica et Cosmochimica Acta, Vol. 73, Issue 10
DOI: 10.1016/j.gca.2009.01.030

The dissolution of biotite and chlorite at 25°C in the near-neutral pH region
journal, February 1996

Malmström, Maria; Banwart, Steven; Lewenhagen, Jeanette
Journal of Contaminant Hydrology, Vol. 21, Issue 1-4
DOI: 10.1016/0169-7722(95)00047-X

Dissolution and precipitation kinetics of gibbsite at 80°C and pH 3: The dependence on solution saturation state
journal, August 1992

Nagy, K. L.; Lasaga, A. C.
Geochimica et Cosmochimica Acta, Vol. 56, Issue 8
DOI: 10.1016/0016-7037(92)90291-P

Gibbsite growth kinetics on gibbsite, kaolinite, and muscovite substrates: atomic force microscopy evidence for epitaxy and an assessment of reactive surface area
journal, August 1999

Nagy, Kathryn L.; Cygan, Randall T.; Hanchar, John M.
Geochimica et Cosmochimica Acta, Vol. 63, Issue 16
DOI: 10.1016/S0016-7037(99)00118-0

The solubility of chlorite solid solutions in 3.2 wt% NaCl fluids from 300–400°C, 500 bars
journal, January 1994

Saccocia, Peter J.; Seyfried, William E.
Geochimica et Cosmochimica Acta, Vol. 58, Issue 2
DOI: 10.1016/0016-7037(94)90489-8

Kinetics of chlorite dissolution at elevated temperatures and CO2 conditions
journal, June 2013

Smith, Megan M.; Wolery, Thomas J.; Carroll, Susan A.
Chemical Geology, Vol. 347
DOI: 10.1016/j.chemgeo.2013.02.017

A coupled model for transport of multiple chemical species and kinetic precipitation/dissolution reactions with application to reactive flow in single phase hydrothermal systems
journal, May 1994

Steefel, C. I.; Lasaga, A. C.
American Journal of Science, Vol. 294, Issue 5
DOI: 10.2475/ajs.294.5.529

Reactive transport modeling: An essential tool and a new research approach for the Earth sciences
journal, December 2005

Steefel, C.; Depaolo, D.; Lichtner, P.
Earth and Planetary Science Letters, Vol. 240, Issue 3-4
DOI: 10.1016/j.epsl.2005.09.017

Pore Scale Processes Associated with Subsurface CO2 Injection and Sequestration
journal, January 2013

Steefel, C. I.; Molins, S.; Trebotich, D.
Reviews in Mineralogy and Geochemistry, Vol. 77, Issue 1
DOI: 10.2138/rmg.2013.77.8

Numerical simulation of CO2 disposal by mineral trapping in deep aquifers
journal, June 2004

Xu, Tianfu; Apps, John A.; Pruess, Karsten
Applied Geochemistry, Vol. 19, Issue 6
DOI: 10.1016/j.apgeochem.2003.11.003

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Title: Chemical affinity and pH effects on chlorite dissolution kinetics under geological CO2 sequestration related conditions

Abstract

Citation Formats

Thermodynamic and kinetic constraints on reaction rates among minerals and aqueous solutions; I, Theoretical considerations journal, March 1982

The stability of Fe-Mg chlorites in hydrothermal solutions: II. thermodynamic properties journal, October 2002

Atomic-resolution transmission electron microscope evidence for the mechanism by which chlorite weathers to 1:1 semi-regular chlorite-vermiculite journal, April 1998

Chlorite dissolution in the acid ph-range: a combined microscopic and macroscopic approach journal, April 2003

Free energy dependence of albite dissolution kinetics at 80°C and pH 8.8 journal, March 1993

Smectite dissolution kinetics at 80°C and pH 8.8 journal, August 2000

Amorphous silica precipitation (60 to 120°C): comparison of laboratory and field rates journal, April 1998

Thermodynamic properties of chlorite CCa-2. Heat capacities, heat contents and entropies journal, August 2009

Kinetics of Dissolution of Noncrystalline Oxides and Crystalline Clay Minerals in a Basic Tiron Solution journal, January 1990

Dissolution kinetics as a function of the Gibbs free energy of reaction: An experimental study based on albite feldspar journal, January 2006

Solubility of Two High-Mg and Two High-Fe Chlorites Using Multiple Equilibria1 journal, January 1982

Measurement of accessible reactive surface area in a sandstone, with application to CO2 mineralization journal, July 2012

Chemical kinetics of water-rock interactions journal, June 1984

The kinetics of the dissolution of chlorite as a function of pH and at 25°C journal, April 2005

The kinetics of chlorite dissolution journal, March 2007

CO2–rock–brine interactions in Lower Tuscaloosa Formation at Cranfield CO2 sequestration site, Mississippi, U.S.A. journal, January 2012

The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California journal, May 2009

The dissolution of biotite and chlorite at 25°C in the near-neutral pH region journal, February 1996

Dissolution and precipitation kinetics of gibbsite at 80°C and pH 3: The dependence on solution saturation state journal, August 1992

Gibbsite growth kinetics on gibbsite, kaolinite, and muscovite substrates: atomic force microscopy evidence for epitaxy and an assessment of reactive surface area journal, August 1999

The solubility of chlorite solid solutions in 3.2 wt% NaCl fluids from 300–400°C, 500 bars journal, January 1994

Kinetics of chlorite dissolution at elevated temperatures and CO2 conditions journal, June 2013

A coupled model for transport of multiple chemical species and kinetic precipitation/dissolution reactions with application to reactive flow in single phase hydrothermal systems journal, May 1994

Reactive transport modeling: An essential tool and a new research approach for the Earth sciences journal, December 2005

Pore Scale Processes Associated with Subsurface CO2 Injection and Sequestration journal, January 2013

Numerical simulation of CO2 disposal by mineral trapping in deep aquifers journal, June 2004

Title: Chemical affinity and pH effects on chlorite dissolution kinetics under geological CO₂ sequestration related conditions

Thermodynamic and kinetic constraints on reaction rates among minerals and aqueous solutions; I, Theoretical considerations
journal, March 1982

The stability of Fe-Mg chlorites in hydrothermal solutions: II. thermodynamic properties
journal, October 2002

Atomic-resolution transmission electron microscope evidence for the mechanism by which chlorite weathers to 1:1 semi-regular chlorite-vermiculite
journal, April 1998

Chlorite dissolution in the acid ph-range: a combined microscopic and macroscopic approach
journal, April 2003

Free energy dependence of albite dissolution kinetics at 80°C and pH 8.8
journal, March 1993

Smectite dissolution kinetics at 80°C and pH 8.8
journal, August 2000

Amorphous silica precipitation (60 to 120°C): comparison of laboratory and field rates
journal, April 1998

Thermodynamic properties of chlorite CCa-2. Heat capacities, heat contents and entropies
journal, August 2009

Kinetics of Dissolution of Noncrystalline Oxides and Crystalline Clay Minerals in a Basic Tiron Solution
journal, January 1990

Dissolution kinetics as a function of the Gibbs free energy of reaction: An experimental study based on albite feldspar
journal, January 2006

Solubility of Two High-Mg and Two High-Fe Chlorites Using Multiple Equilibria1
journal, January 1982

Measurement of accessible reactive surface area in a sandstone, with application to CO2 mineralization
journal, July 2012

Chemical kinetics of water-rock interactions
journal, June 1984

The kinetics of the dissolution of chlorite as a function of pH and at 25°C
journal, April 2005

The kinetics of chlorite dissolution
journal, March 2007

CO2–rock–brine interactions in Lower Tuscaloosa Formation at Cranfield CO2 sequestration site, Mississippi, U.S.A.
journal, January 2012

The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California
journal, May 2009

The dissolution of biotite and chlorite at 25°C in the near-neutral pH region
journal, February 1996

Dissolution and precipitation kinetics of gibbsite at 80°C and pH 3: The dependence on solution saturation state
journal, August 1992

Gibbsite growth kinetics on gibbsite, kaolinite, and muscovite substrates: atomic force microscopy evidence for epitaxy and an assessment of reactive surface area
journal, August 1999

The solubility of chlorite solid solutions in 3.2 wt% NaCl fluids from 300–400°C, 500 bars
journal, January 1994

Kinetics of chlorite dissolution at elevated temperatures and CO2 conditions
journal, June 2013

A coupled model for transport of multiple chemical species and kinetic precipitation/dissolution reactions with application to reactive flow in single phase hydrothermal systems
journal, May 1994

Reactive transport modeling: An essential tool and a new research approach for the Earth sciences
journal, December 2005

Pore Scale Processes Associated with Subsurface CO2 Injection and Sequestration
journal, January 2013

Numerical simulation of CO2 disposal by mineral trapping in deep aquifers
journal, June 2004