Experimental Study of Porosity Changes in Shale Caprocks Exposed to CO2-Saturated Brines I: Evolution of Mineralogy, Pore Connectivity, Pore Size Distribution, and Surface Area
Abstract
Carbon capture, utilization, and storage, one proposed method of reducing anthropogenic emissions of CO2, relies on low permeability formations, such as shales, above injection formations to prevent upward migration of the injected CO2. Porosity in caprocks evaluated for sealing capacity before injection can be altered by geochemical reactions induced by dissolution of injected CO2 into pore fluids, impacting long-term sealing capacity. Therefore, long-term performance of CO2 sequestration sites may be dependent on both initial distribution and connectivity of pores in caprocks, and on changes induced by geochemical reaction after injection of CO2, which are currently poorly understood. This paper presents results from an experimental study of changes to caprock porosity and pore network geometry in two caprock formations under conditions relevant to CO2 sequestration. Pore connectivity and total porosity increased in the Gothic Shale; while total porosity increased but pore connectivity decreased in the Marine Tuscaloosa. Gothic Shale is a carbonate mudstone that contains volumetrically more carbonate minerals than Marine Tuscaloosa. Carbonate minerals dissolved to a greater extent than silicate minerals in Gothic Shale under high CO2 conditions, leading to increased porosity at length scales <~200 nm that contributed to increased pore connectivity. In contrast, silicate minerals dissolved to amore »
- Authors:
-
- Colorado School of Mines, Golden, CO (United States). Hydrologic Sciences and Engineering Program
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
- Univ. of Wyoming, Laramie, WY (United States). Dept. of Geology and Geophysics
- Univ. of Wyoming, Laramie, WY (United States). Dept. of Geology and Geophysics. School of Energy Resources
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Univ. of Wyoming, Laramie, WY (United States). Chemical Engineering Dept.
- Colorado School of Mines, Golden, CO (United States). Civil and Environmental Engineering
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). High Flux Isotope Reactor (HFIR); Colorado School of Mines, Golden, CO (United States); 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); USEPA
- Contributing Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Univ. of Wyoming, Laramie, WY (United States)
- OSTI Identifier:
- 1327669
- Grant/Contract Number:
- AC05-00OR22725; FE0000730; R834387; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Environmental Engineering Science
- Additional Journal Information:
- Journal Name: Environmental Engineering Science; Journal ID: ISSN 1092-8758
- Publisher:
- Mary Ann Liebert, Inc.
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 54 ENVIRONMENTAL SCIENCES; caprock; carbon sequestration; Gothic Shale; high temperature and pressure experiments; Marine Tuscaloosa; nitrogen gas adsorption; porosity; scanning electron microscope; small angle neutron scattering (SANS)
Citation Formats
Mouzakis, Katherine M., Navarre-Sitchler, Alexis K., Rother, Gernot, Bañuelos, José Leobardo, Wang, Xiuyu, Kaszuba, John P., Heath, Jason E., Miller, Quin R. S., Alvarado, Vladimir, and McCray, John E. Experimental Study of Porosity Changes in Shale Caprocks Exposed to CO2-Saturated Brines I: Evolution of Mineralogy, Pore Connectivity, Pore Size Distribution, and Surface Area. United States: N. p., 2016.
Web. doi:10.1089/ees.2015.0588.
Mouzakis, Katherine M., Navarre-Sitchler, Alexis K., Rother, Gernot, Bañuelos, José Leobardo, Wang, Xiuyu, Kaszuba, John P., Heath, Jason E., Miller, Quin R. S., Alvarado, Vladimir, & McCray, John E. Experimental Study of Porosity Changes in Shale Caprocks Exposed to CO2-Saturated Brines I: Evolution of Mineralogy, Pore Connectivity, Pore Size Distribution, and Surface Area. United States. https://doi.org/10.1089/ees.2015.0588
Mouzakis, Katherine M., Navarre-Sitchler, Alexis K., Rother, Gernot, Bañuelos, José Leobardo, Wang, Xiuyu, Kaszuba, John P., Heath, Jason E., Miller, Quin R. S., Alvarado, Vladimir, and McCray, John E. Mon .
"Experimental Study of Porosity Changes in Shale Caprocks Exposed to CO2-Saturated Brines I: Evolution of Mineralogy, Pore Connectivity, Pore Size Distribution, and Surface Area". United States. https://doi.org/10.1089/ees.2015.0588. https://www.osti.gov/servlets/purl/1327669.
@article{osti_1327669,
title = {Experimental Study of Porosity Changes in Shale Caprocks Exposed to CO2-Saturated Brines I: Evolution of Mineralogy, Pore Connectivity, Pore Size Distribution, and Surface Area},
author = {Mouzakis, Katherine M. and Navarre-Sitchler, Alexis K. and Rother, Gernot and Bañuelos, José Leobardo and Wang, Xiuyu and Kaszuba, John P. and Heath, Jason E. and Miller, Quin R. S. and Alvarado, Vladimir and McCray, John E.},
abstractNote = {Carbon capture, utilization, and storage, one proposed method of reducing anthropogenic emissions of CO2, relies on low permeability formations, such as shales, above injection formations to prevent upward migration of the injected CO2. Porosity in caprocks evaluated for sealing capacity before injection can be altered by geochemical reactions induced by dissolution of injected CO2 into pore fluids, impacting long-term sealing capacity. Therefore, long-term performance of CO2 sequestration sites may be dependent on both initial distribution and connectivity of pores in caprocks, and on changes induced by geochemical reaction after injection of CO2, which are currently poorly understood. This paper presents results from an experimental study of changes to caprock porosity and pore network geometry in two caprock formations under conditions relevant to CO2 sequestration. Pore connectivity and total porosity increased in the Gothic Shale; while total porosity increased but pore connectivity decreased in the Marine Tuscaloosa. Gothic Shale is a carbonate mudstone that contains volumetrically more carbonate minerals than Marine Tuscaloosa. Carbonate minerals dissolved to a greater extent than silicate minerals in Gothic Shale under high CO2 conditions, leading to increased porosity at length scales <~200 nm that contributed to increased pore connectivity. In contrast, silicate minerals dissolved to a greater extent than carbonate minerals in Marine Tuscaloosa leading to increased porosity at all length scales, and specifically an increase in the number of pores >~1 μm. Mineral reactions also contributed to a decrease in pore connectivity, possibly as a result of precipitation in pore throats or hydration of the high percentage of clays. Finally, this study highlights the role that mineralogy of the caprock can play in geochemical response to CO2 injection and resulting changes in sealing capacity in long-term CO2 storage projects.},
doi = {10.1089/ees.2015.0588},
journal = {Environmental Engineering Science},
number = ,
volume = ,
place = {United States},
year = {Mon Jul 18 00:00:00 EDT 2016},
month = {Mon Jul 18 00:00:00 EDT 2016}
}
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Works referenced in this record:
Measurement of the Sealing Capacity of Shale Caprocks
conference, April 2013
- Al-Bazali, Talal M.; Zhang, Jianguo; Chenevert, Martin E.
- SPE Annual Technical Conference and Exhibition
Caprock interaction with CO2: A laboratory study of reactivity of shale with supercritical CO2 and brine
journal, December 2011
- Alemu, Binyam L.; Aagaard, Per; Munz, Ingrid Anne
- Applied Geochemistry, Vol. 26, Issue 12
A new approach to quantification of metamorphism using ultra-small and small angle neutron scattering
journal, December 2009
- Anovitz, Lawrence M.; Lynn, Gary W.; Cole, David R.
- Geochimica et Cosmochimica Acta, Vol. 73, Issue 24, p. 7303-7324
Geological storage of carbon dioxide
journal, January 2004
- Baines, Shelagh J.; Worden, Richard H.
- Geological Society, London, Special Publications, Vol. 233, Issue 1
How Oxidation and Dissolution in Diabase and Granite Control Porosity during Weathering
journal, January 2015
- Bazilevskaya, Ekaterina; Rother, Gernot; Mildner, David F. R.
- Soil Science Society of America Journal, Vol. 79, Issue 1
Effects of physical sorption and chemical reactions of CO2 in shaly caprocks
journal, February 2009
- Busch, Andreas; Alles, Sascha; Krooss, Bernhard M.
- Energy Procedia, Vol. 1, Issue 1
A national look at carbon capture and storage—National carbon sequestration database and geographical information system (NatCarb)
journal, February 2009
- Carr, Timothy R.; Iqbal, Asif; Callaghan, Nick
- Energy Procedia, Vol. 1, Issue 1
Wellbore integrity in carbon sequestration environments: 1. Experimental study of Cement–Sandstone/Shale–Brine–CO2
journal, January 2011
- Carroll, Susan; McNab, Walt; Torres, Sharon
- Energy Procedia, Vol. 4
Supercritical carbon dioxide–brine–rock reactions in the Madison Limestone of Southwest Wyoming: An experimental investigation of a sulfur-rich natural carbon dioxide reservoir
journal, September 2012
- Chopping, Curtis; Kaszuba, John P.
- Chemical Geology, Vol. 322-323
Experimental and modeling study of geochemical reactivity between clayey caprocks and CO2 in geological storage conditions
journal, February 2009
- Credoz, Anthony; Bildstein, Olivier; Jullien, Michel
- Energy Procedia, Vol. 1, Issue 1
An improved model for the calculation of CO2 solubility in aqueous solutions containing Na+, K+, Ca2+, Mg2+, Cl−, and SO42−
journal, February 2006
- Duan, Zhenhao; Sun, Rui; Zhu, Chen
- Marine Chemistry, Vol. 98, Issue 2-4
Deterioration of a fractured carbonate caprock exposed to CO 2 -acidified brine flow : Deterioration of a fractured carbonate caprock exposed to CO
journal, August 2011
- Ellis, Brian; Peters, Catherine; Fitts, Jeffrey
- Greenhouse Gases: Science and Technology, Vol. 1, Issue 3
Pores in Marcellus Shale: A Neutron Scattering and FIB-SEM Study
journal, February 2015
- Gu, Xin; Cole, David R.; Rother, Gernot
- Energy & Fuels, Vol. 29, Issue 3
Pore size distribution of shaley rock by small angle neutron scattering
journal, August 1983
- Hall, P. L.; Mildner, D. F. R.; Borst, R. L.
- Applied Physics Letters, Vol. 43, Issue 3
Pore networks in continental and marine mudstones: Characteristics and controls on sealing behavior
journal, April 2011
- Heath, Jason E.; Dewers, Thomas A.; McPherson, Brian J. O. L.
- Geosphere, Vol. 7, Issue 2
PRINSAS – a Windows-based computer program for the processing and interpretation of small-angle scattering data tailored to the analysis of sedimentary rocks
journal, November 2004
- Hinde, Alan L.
- Journal of Applied Crystallography, Vol. 37, Issue 6
Evolution of porosity and geochemistry in Marcellus Formation black shale during weathering
journal, October 2013
- Jin, Lixin; Mathur, Ryan; Rother, Gernot
- Chemical Geology, Vol. 356
Small-angle neutron scattering study of volcanic rocks [Small-angle neutron scattering study of volcanic rocks]
journal, June 2004
- Kahle, Andreas; Winkler, Björn; Radulescu, Aurel
- European Journal of Mineralogy, Vol. 16, Issue 3
Carbon dioxide reaction processes in a model brine aquifer at 200 °C and 200 bars: implications for geologic sequestration of carbon
journal, July 2003
- Kaszuba, John P.; Janecky, David R.; Snow, Marjorie G.
- Applied Geochemistry, Vol. 18, Issue 7
Experimental evaluation of mixed fluid reactions between supercritical carbon dioxide and NaCl brine: Relevance to the integrity of a geologic carbon repository
journal, April 2005
- Kaszuba, John P.; Janecky, David R.; Snow, Marjorie G.
- Chemical Geology, Vol. 217, Issue 3-4
Metal Release from Sandstones under Experimentally and Numerically Simulated CO 2 Leakage Conditions
journal, January 2014
- Kirsch, Katie; Navarre-Sitchler, Alexis K.; Wunsch, Assaf
- Environmental Science & Technology, Vol. 48, Issue 3
Reduction and analysis of SANS and USANS data using IGOR Pro
journal, November 2006
- Kline, Steven R.
- Journal of Applied Crystallography, Vol. 39, Issue 6, p. 895-900
Clayey cap-rock behavior in H<SUB>2</SUB>O-CO<SUB>2</SUB> media at low pressure and temperature conditions: an experimental approach
journal, October 2009
- Kohler, Eric; Parra, Teddy; Vidal, Olivier
- Clays and Clay Minerals, Vol. 57, Issue 5
CO2 mineral sequestration mechanisms and capacity of saline aquifers of the Upper Silesian Coal Basin (Central Europe) - Modeling and experimental verification
journal, August 2011
- Labus, Krzysztof; Bujok, Petr
- Energy, Vol. 36, Issue 8
CO2 Geological storage in saline aquifers: Paraná Basin caprock and reservoir chemical reactivity
journal, January 2011
- Lima, Viviane de; Einloft, Sandra; Ketzer, João Marcelo
- Energy Procedia, Vol. 4
The United States Department of Energy's Regional Carbon Sequestration Partnerships Program Validation Phase
journal, January 2008
- Litynski, John T.; Plasynski, Sean; McIlvried, Howard G.
- Environment International, Vol. 34, Issue 1, p. 127-138
Small‐angle scattering of shaley rocks with fractal pore interfaces
journal, May 1986
- Mildner, D. F. R.; Rezvani, R.; Hall, P. L.
- Applied Physics Letters, Vol. 48, Issue 19
How Porosity Increases During Incipient Weathering of Crystalline Silicate Rocks
journal, January 2015
- Navarre-Sitchler, Alexis; Brantley, Susan L.; Rother, Gernot
- Reviews in Mineralogy and Geochemistry, Vol. 80, Issue 1
Porosity and surface area evolution during weathering of two igneous rocks
journal, May 2013
- Navarre-Sitchler, Alexis K.; Cole, David R.; Rother, Gernot
- Geochimica et Cosmochimica Acta, Vol. 109
Elucidating geochemical response of shallow heterogeneous aquifers to CO2 leakage using high-performance computing: Implications for monitoring of CO2 sequestration
journal, March 2013
- Navarre-Sitchler, Alexis K.; Maxwell, Reed M.; Siirila, Erica R.
- Advances in Water Resources, Vol. 53
Ferric iron-bearing sediments as a mineral trap for CO2 sequestration: Iron reduction using sulfur-bearing waste gas
journal, April 2005
- Palandri, James L.; Kharaka, Yousif K.
- Chemical Geology, Vol. 217, Issue 3-4
Small-Angle Neutron Scattering and the Microstructure of Rocks
journal, January 2006
- Radlinski, A. P.
- Reviews in Mineralogy and Geochemistry, Vol. 63, Issue 1
Fractal Geometry of Rocks
journal, April 1999
- Radliński, A. P.; Radlińska, E. Z.; Agamalian, M.
- Physical Review Letters, Vol. 82, Issue 15
Experimental investigation of CO2–brine–rock interactions at elevated temperature and pressure: Implications for CO2 sequestration in deep-saline aquifers
journal, October 2005
- Rosenbauer, Robert J.; Koksalan, Tamer; Palandri, James L.
- Fuel Processing Technology, Vol. 86, Issue 14-15
Is the bet equation applicable to microporous adsorbents?
book, September 2007
- Rouquerol, J.; Llewellyn, P.; Rouquerol, F.
- Studies in Surface Science and Catalysis
Carbon dioxide-water phase equilibria results from the Wong-Sandler combining rules
journal, April 1997
- Shyu, Guor-Shiarn; Hanif, Nishawn S. M.; Hall, Kenneth R.
- Fluid Phase Equilibria, Vol. 130, Issue 1-2
Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Provisional)
journal, January 1982
- Sing, K. S. W.
- Pure and Applied Chemistry, Vol. 54, Issue 11
The binary system H 2 O-CO 2 at high temperatures and pressures
journal, November 1964
- Takenouchi, S.; Kennedy, G. C.
- American Journal of Science, Vol. 262, Issue 9
Petrophysical and Mineralogical Research on the Influence of CO 2 Injection on Mesozoic Reservoir and Caprocks from the Polish Lowlands
journal, January 2011
- Tarkowski, R.; Wdowin, M.
- Oil & Gas Science and Technology – Revue d’IFP Energies nouvelles, Vol. 66, Issue 1
Works referencing / citing this record:
A review of geochemical–mechanical impacts in geological carbon storage reservoirs
journal, May 2019
- Akono, Ange‐Therese; Druhan, Jennifer L.; Dávila, Gabriela
- Greenhouse Gases: Science and Technology, Vol. 9, Issue 3