Evaporite Caprock Integrity. An experimental study of reactive mineralogy and pore-scale heterogeneity during brine-CO2 exposure

Smith, Megan M.; Sholokhova, Yelena; Hao, Yue; Carroll, Susan A.

doi:10.1021/es3012723

Title: Evaporite Caprock Integrity. An experimental study of reactive mineralogy and pore-scale heterogeneity during brine-CO₂ exposure

Abstract

Characterization and geochemical data are presented from a core-flooding experiment on a sample from the Three Fingers evaporite unit forming the lower extent of caprock at the Weyburn-Midale reservoir, Canada. This low-permeability sample was characterized in detail using X-ray computed microtomography before and after exposure to CO ₂-acidified brine, allowing mineral phase and voidspace distributions to be quantified in three dimensions. Solution chemistry indicated that CO ₂-acidified brine preferentially dissolved dolomite until saturation was attained, while anhydrite remained unreactive. Dolomite dissolution contributed to increases in bulk permeability through the formation of a localized channel, guided by microfractures as well as porosity and reactive phase distributions aligned with depositional bedding. An indirect effect of carbonate mineral reactivity with CO ₂-acidified solution is voidspace generation through physical transport of anhydrite freed from the rock matrix following dissolution of dolomite. The development of high permeability fast pathways in this experiment highlights the role of carbonate content and potential fracture orientations in evaporite caprock formations considered for both geologic carbon sequestration and CO ₂-enhanced oil recovery operations.

Authors:

Smith, Megan M. ^[1]; Sholokhova, Yelena ^[1]; Hao, Yue ^[1]; Carroll, Susan A. ^[1]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Publication Date:: Wed Jul 25 00:00:00 EDT 2012

Research Org.:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1237526

Report Number(s):: LLNL-JRNL-544136
Journal ID: ISSN 0013-936X

Grant/Contract Number:: AC52-07NA27344

Resource Type:: Accepted Manuscript

Journal Name:: Environmental Science and Technology

Additional Journal Information:: Journal Volume: 47; Journal Issue: 1; Journal ID: ISSN 0013-936X

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 20 FOSSIL-FUELED POWER PLANTS; 54 ENVIRONMENTAL SCIENCES; 58 GEOSCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 02 PETROLEUM; geologic carbon sequestration; caprock stability; evaporate; anhydrite; dolomite; fracture; x-ray tomography; enhanced oil recovery

Citation Formats


                    Smith, Megan M., Sholokhova, Yelena, Hao, Yue, and Carroll, Susan A. Evaporite Caprock Integrity. An experimental study of reactive mineralogy and pore-scale heterogeneity during brine-CO2 exposure.  United States: N. p., 2012. 
Web.  doi:10.1021/es3012723.

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                    Smith, Megan M., Sholokhova, Yelena, Hao, Yue, & Carroll, Susan A. Evaporite Caprock Integrity. An experimental study of reactive mineralogy and pore-scale heterogeneity during brine-CO2 exposure.  United States.  https://doi.org/10.1021/es3012723

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                    Smith, Megan M., Sholokhova, Yelena, Hao, Yue, and Carroll, Susan A. Wed .  
"Evaporite Caprock Integrity. An experimental study of reactive mineralogy and pore-scale heterogeneity during brine-CO2 exposure".  United States.  https://doi.org/10.1021/es3012723.  https://www.osti.gov/servlets/purl/1237526.

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@article{osti_1237526,

  title        = {Evaporite Caprock Integrity. An experimental study of reactive mineralogy and pore-scale heterogeneity during brine-CO2 exposure},

  author       = {Smith, Megan M. and Sholokhova, Yelena and Hao, Yue and Carroll, Susan A.},

  abstractNote = {Characterization and geochemical data are presented from a core-flooding experiment on a sample from the Three Fingers evaporite unit forming the lower extent of caprock at the Weyburn-Midale reservoir, Canada. This low-permeability sample was characterized in detail using X-ray computed microtomography before and after exposure to CO 2-acidified brine, allowing mineral phase and voidspace distributions to be quantified in three dimensions. Solution chemistry indicated that CO 2-acidified brine preferentially dissolved dolomite until saturation was attained, while anhydrite remained unreactive. Dolomite dissolution contributed to increases in bulk permeability through the formation of a localized channel, guided by microfractures as well as porosity and reactive phase distributions aligned with depositional bedding. An indirect effect of carbonate mineral reactivity with CO 2-acidified solution is voidspace generation through physical transport of anhydrite freed from the rock matrix following dissolution of dolomite. The development of high permeability fast pathways in this experiment highlights the role of carbonate content and potential fracture orientations in evaporite caprock formations considered for both geologic carbon sequestration and CO 2-enhanced oil recovery operations.},

  doi          = {10.1021/es3012723},

  journal      = {Environmental Science and Technology},

  number       = 1,

  volume       = 47,

  place        = {United States},

  year         = {Wed Jul 25 00:00:00 EDT 2012},

  month        = {Wed Jul 25 00:00:00 EDT 2012}

}

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Works referenced in this record:

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
DOI: 10.1016/j.fuproc.2005.01.011

CO2 sequestration in depleted oil and gas reservoirs—caprock characterization and storage capacity
journal, July 2006

Li, Zhaowen; Dong, Mingzhe; Li, Shuliang
Energy Conversion and Management, Vol. 47, Issue 11-12
DOI: 10.1016/j.enconman.2005.08.023

Numerical modeling of self-limiting and self-enhancing caprock alteration induced by CO2 storage in a depleted gas reservoir
journal, September 2007

Gherardi, Fabrizio; Xu, Tianfu; Pruess, Karsten
Chemical Geology, Vol. 244, Issue 1-2
DOI: 10.1016/j.chemgeo.2007.06.009

Experimental determination of porosity and permeability changes induced by injection of CO2 into carbonate rocks
journal, July 2009

Luquot, L.; Gouze, P.
Chemical Geology, Vol. 265, Issue 1-2
DOI: 10.1016/j.chemgeo.2009.03.028

On the ability of a Darcy-scale model to capture wormhole formation during the dissolution of a porous medium
journal, April 2002

Golfier, F.; Zarcone, C.; Bazin, B.
Journal of Fluid Mechanics, Vol. 457
DOI: 10.1017/S0022112002007735

Chemical dissolution of a porous medium by a reactive fluid—II. Convection vs reaction, behavior diagram
journal, January 1993

Daccord, G.; Liétard, O.; Lenormand, R.
Chemical Engineering Science, Vol. 48, Issue 1
DOI: 10.1016/0009-2509(93)80294-Z

Monitoring of fluid–rock interaction and CO₂ storage through produced fluid sampling at the Weyburn CO₂-injection enhanced oil recovery site, Saskatchewan, Canada
journal, June 2005

Emberley, S.; Hutcheon, I.; Shevalier, M.
Applied Geochemistry, Vol. 20, Issue 6, p. 1131-1157
DOI: 10.1016/j.apgeochem.2005.02.007

Analysis and performance of oil well cement with 30 years of CO2 exposure from the SACROC Unit, West Texas, USA
journal, April 2007

Carey, J. William; Wigand, Marcus; Chipera, Steve J.
International Journal of Greenhouse Gas Control, Vol. 1, Issue 1
DOI: 10.1016/S1750-5836(06)00004-1

Experimental percolation of supercritical CO2 through a caprock
journal, February 2009

Angeli, Matthieu; Soldal, Magnus; Skurtveit, Elin
Energy Procedia, Vol. 1, Issue 1
DOI: 10.1016/j.egypro.2009.02.123

Influence of transport and reaction on wormhole formation in porous media
journal, September 1998

Fredd, Christopher N.; Fogler, H. Scott
AIChE Journal, Vol. 44, Issue 9
DOI: 10.1002/aic.690440902

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
DOI: 10.1002/ghg.25

From pore scale to wellbore scale: Impact of geometry on wormhole growth in carbonate acidization
journal, June 2008

Cohen, Charles Edouard; Ding, Didier; Quintard, Michel
Chemical Engineering Science, Vol. 63, Issue 12
DOI: 10.1016/j.ces.2008.03.021

Changes in seal capacity of fractured claystone caprocks induced by dissolved and gaseous CO ₂ seepage
journal, January 2008

Andreani, M.; Gouze, P.; Luquot, L.
Geophysical Research Letters, Vol. 35, Issue 14
DOI: 10.1029/2008GL034467

Using Chemical and Isotopic Data to Quantify Ionic Trapping of Injected Carbon Dioxide in Oil Field Brines
journal, November 2006

Raistrick, Mark; Mayer, Bernhard; Shevalier, Maurice
Environmental Science & Technology, Vol. 40, Issue 21
DOI: 10.1021/es060551a

A review of studies on CO2 sequestration and caprock integrity
journal, October 2010

Shukla, Richa; Ranjith, Pathegama; Haque, Asadul
Fuel, Vol. 89, Issue 10
DOI: 10.1016/j.fuel.2010.05.012

Accessibilities of reactive minerals in consolidated sedimentary rock: An imaging study of three sandstones
journal, July 2009

Peters, Catherine A.
Chemical Geology, Vol. 265, Issue 1-2
DOI: 10.1016/j.chemgeo.2008.11.014

Geochemical Modeling of the Madison Aquifer in Parts of Montana, Wyoming, and South Dakota
journal, September 1990

Plummer, L. Niel; Busby, John F.; Lee, Roger W.
Water Resources Research, Vol. 26, Issue 9
DOI: 10.1029/WR026i009p01981

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
DOI: 10.1016/j.chemgeo.2004.12.014

Mechanical behavior of anhydrite caprock and implications for CO ₂ sealing capacity
journal, January 2010

Hangx, Suzanne J. T.; Spiers, Christopher J.; Peach, Colin J.
Journal of Geophysical Research, Vol. 115, Issue B7
DOI: 10.1029/2009JB006954

Pore evolution and channel formation during flow and reaction in porous media
journal, January 1988

Hoefner, M. L.; Fogler, H. S.
AIChE Journal, Vol. 34, Issue 1
DOI: 10.1002/aic.690340107

Experimental study on water–rock interactions during CO2 flooding in the Tensleep Formation, Wyoming, USA
journal, March 2000

Shiraki, Ryoji; Dunn, Thomas L.
Applied Geochemistry, Vol. 15, Issue 3
DOI: 10.1016/S0883-2927(99)00048-7

Works referencing / citing this record:

Permeability impairment of a limestone reservoir triggered by heterogeneous dissolution and particles migration during CO ₂ -rich injection: DISSOLUTION-INDUCED PARTICLE MIGRATION
journal, September 2013

Mangane, Papa O.; Gouze, Philippe; Luquot, Linda
Geophysical Research Letters, Vol. 40, Issue 17
DOI: 10.1002/grl.50595

Permeability of Wellbore-Cement Fractures Following Degradation by Carbonated Brine
journal, December 2012

Walsh, Stuart D. C.; Du Frane, Wyatt L.; Mason, Harris E.
Rock Mechanics and Rock Engineering, Vol. 46, Issue 3
DOI: 10.1007/s00603-012-0336-9

Reactive Transport Simulation of Fracture Channelization and Transmissivity Evolution
journal, January 2019

Deng, Hang; Peters, Catherine A.
Environmental Engineering Science, Vol. 36, Issue 1
DOI: 10.1089/ees.2018.0244

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
DOI: 10.1002/ghg.1870

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Title: Evaporite Caprock Integrity. An experimental study of reactive mineralogy and pore-scale heterogeneity during brine-CO2 exposure

Abstract

Citation Formats

Experimental investigation of CO2–brine–rock interactions at elevated temperature and pressure: Implications for CO2 sequestration in deep-saline aquifers journal, October 2005

CO2 sequestration in depleted oil and gas reservoirs—caprock characterization and storage capacity journal, July 2006

Numerical modeling of self-limiting and self-enhancing caprock alteration induced by CO2 storage in a depleted gas reservoir journal, September 2007

Experimental determination of porosity and permeability changes induced by injection of CO2 into carbonate rocks journal, July 2009

On the ability of a Darcy-scale model to capture wormhole formation during the dissolution of a porous medium journal, April 2002

Chemical dissolution of a porous medium by a reactive fluid—II. Convection vs reaction, behavior diagram journal, January 1993

Monitoring of fluid–rock interaction and CO2 storage through produced fluid sampling at the Weyburn CO2-injection enhanced oil recovery site, Saskatchewan, Canada journal, June 2005

Analysis and performance of oil well cement with 30 years of CO2 exposure from the SACROC Unit, West Texas, USA journal, April 2007

Experimental percolation of supercritical CO2 through a caprock journal, February 2009

Influence of transport and reaction on wormhole formation in porous media journal, September 1998

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

From pore scale to wellbore scale: Impact of geometry on wormhole growth in carbonate acidization journal, June 2008

Changes in seal capacity of fractured claystone caprocks induced by dissolved and gaseous CO 2 seepage journal, January 2008

Using Chemical and Isotopic Data to Quantify Ionic Trapping of Injected Carbon Dioxide in Oil Field Brines journal, November 2006

A review of studies on CO2 sequestration and caprock integrity journal, October 2010

Accessibilities of reactive minerals in consolidated sedimentary rock: An imaging study of three sandstones journal, July 2009

Geochemical Modeling of the Madison Aquifer in Parts of Montana, Wyoming, and South Dakota journal, September 1990

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

Mechanical behavior of anhydrite caprock and implications for CO 2 sealing capacity journal, January 2010

Pore evolution and channel formation during flow and reaction in porous media journal, January 1988

Experimental study on water–rock interactions during CO2 flooding in the Tensleep Formation, Wyoming, USA journal, March 2000

Permeability impairment of a limestone reservoir triggered by heterogeneous dissolution and particles migration during CO 2 -rich injection: DISSOLUTION-INDUCED PARTICLE MIGRATION journal, September 2013

Permeability of Wellbore-Cement Fractures Following Degradation by Carbonated Brine journal, December 2012

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A review of geochemical–mechanical impacts in geological carbon storage reservoirs journal, May 2019

Title: Evaporite Caprock Integrity. An experimental study of reactive mineralogy and pore-scale heterogeneity during brine-CO₂ exposure

Experimental investigation of CO2–brine–rock interactions at elevated temperature and pressure: Implications for CO2 sequestration in deep-saline aquifers
journal, October 2005

CO2 sequestration in depleted oil and gas reservoirs—caprock characterization and storage capacity
journal, July 2006

Numerical modeling of self-limiting and self-enhancing caprock alteration induced by CO2 storage in a depleted gas reservoir
journal, September 2007

Experimental determination of porosity and permeability changes induced by injection of CO2 into carbonate rocks
journal, July 2009

On the ability of a Darcy-scale model to capture wormhole formation during the dissolution of a porous medium
journal, April 2002

Chemical dissolution of a porous medium by a reactive fluid—II. Convection vs reaction, behavior diagram
journal, January 1993

Monitoring of fluid–rock interaction and CO₂ storage through produced fluid sampling at the Weyburn CO₂-injection enhanced oil recovery site, Saskatchewan, Canada
journal, June 2005

Analysis and performance of oil well cement with 30 years of CO2 exposure from the SACROC Unit, West Texas, USA
journal, April 2007

Experimental percolation of supercritical CO2 through a caprock
journal, February 2009

Influence of transport and reaction on wormhole formation in porous media
journal, September 1998

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

From pore scale to wellbore scale: Impact of geometry on wormhole growth in carbonate acidization
journal, June 2008

Changes in seal capacity of fractured claystone caprocks induced by dissolved and gaseous CO ₂ seepage
journal, January 2008

Using Chemical and Isotopic Data to Quantify Ionic Trapping of Injected Carbon Dioxide in Oil Field Brines
journal, November 2006

A review of studies on CO2 sequestration and caprock integrity
journal, October 2010

Accessibilities of reactive minerals in consolidated sedimentary rock: An imaging study of three sandstones
journal, July 2009

Geochemical Modeling of the Madison Aquifer in Parts of Montana, Wyoming, and South Dakota
journal, September 1990

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

Mechanical behavior of anhydrite caprock and implications for CO ₂ sealing capacity
journal, January 2010

Pore evolution and channel formation during flow and reaction in porous media
journal, January 1988

Experimental study on water–rock interactions during CO2 flooding in the Tensleep Formation, Wyoming, USA
journal, March 2000

Permeability impairment of a limestone reservoir triggered by heterogeneous dissolution and particles migration during CO ₂ -rich injection: DISSOLUTION-INDUCED PARTICLE MIGRATION
journal, September 2013

Permeability of Wellbore-Cement Fractures Following Degradation by Carbonated Brine
journal, December 2012

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