Probing multiscale dissolution dynamics in natural rocks through microfluidics and compositional analysis

Ling, Bowen; Sodwatana, Mo; Kohli, Arjun; Ross, Cynthia M.; Jew, Adam; Kovscek, Anthony R.; Battiato, Ilenia

doi:10.1073/pnas.2122520119

Probing multiscale dissolution dynamics in natural rocks through microfluidics and compositional analysis

Journal Article · Wed Aug 03 00:00:00 EDT 2022 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.2122520119· OSTI ID:2345062

^[1]; ^[2]; Kohli, Arjun ^[2]; ^[2]; Jew, Adam ^[3]; ^[2]; Battiato, Ilenia ^[2]

Stanford Univ., CA (United States); Chinese Academy of Sciences (CAS), Beijing (China). Institute of Mechanics; Stanford University
Stanford Univ., CA (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Mineral dissolution significantly impacts many geological systems. Carbon released by diagenesis, carbon sequestration, and acid injection are examples where geochemical reactions, fluid flow, and solute transport are strongly coupled. The complexity in these systems involves interplay between various mechanisms that operate at timescales ranging from microseconds to years. Current experimental techniques characterize dissolution processes using static images that are acquired with long measurement times and/or low spatial resolution. These limitations prevent direct observation of how dissolution reactions progress within an intact rock with spatially heterogeneous mineralogy and morphology. We utilize microfluidic cells embedded with thin rock samples to visualize dissolution with significant temporal resolution (100 ms) in a large observation window (3 × 3 mm). Here we injected acidic fluid into eight shale samples ranging from 8 to 86 wt % carbonate. The pre- and postreaction microstructures are characterized at the scale of pores (0.1 to 1 µm) and fractures (1 to 1,000 µm). We observe that nonreactive particle exposure, fracture morphology, and loss of rock strength are strongly dependent on both the relative volume of reactive grains and their distribution. Time-resolved images of the rock unveil the spatiotemporal dynamics of dissolution, including two-phase flow effects in real time and illustrate the changes in the fracture interface across the range of compositions. Moreover, the dynamical data provide an approach for characterizing reactivity parameters of natural heterogeneous samples when porous media effects are not negligible. The platform and workflow provide real-time characterization of geochemical reactions and inform various subsurface engineering processes.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Mechanistic Control of Unconventional Formations (CMC-UF); Stanford Univ., CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019165

OSTI ID:: 2345062

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 32 Vol. 119; ISSN 0027-8424

Publisher:: National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

References (40)

Investigation of mineral composition of oil shale Wang, Dong‐Mei; Xu, Ying‐Mei; He, De‐Min Asia-Pacific Journal of Chemical Engineering, Vol. 4, Issue 5 https://doi.org/10.1002/apj.319	journal	September 2009
Microfluidic devices containing thin rock sections for oil recovery studies Gerold, Chase T.; Krummel, Amber T.; Henry, Charles S. Microfluidics and Nanofluidics, Vol. 22, Issue 7 https://doi.org/10.1007/s10404-018-2096-7	journal	July 2018
Simulation of mineral dissolution at the pore scale with evolving fluid-solid interfaces: review of approaches and benchmark problem set Molins, Sergi; Soulaine, Cyprien; Prasianakis, Nikolaos I. Computational Geosciences https://doi.org/10.1007/s10596-019-09903-x	journal	January 2020
Interaction between hydraulic fractures and natural fractures: current status and prospective directions Kolawole, Oladoyin; Ispas, Ion Journal of Petroleum Exploration and Production Technology, Vol. 10, Issue 4 https://doi.org/10.1007/s13202-019-00778-3	journal	September 2019
Scanning electron microscopy for materials characterization Joy, David C. Current Opinion in Solid State and Materials Science, Vol. 2, Issue 4 https://doi.org/10.1016/S1359-0286(97)80091-5	journal	August 1997
Modeling variability in porescale multiphase flow experiments Ling, Bowen; Bao, Jie; Oostrom, Mart Advances in Water Resources, Vol. 105 https://doi.org/10.1016/j.advwatres.2017.04.005	journal	July 2017
Multi-scale multi-dimensional microstructure imaging of oil shale pyrolysis using X-ray micro-tomography, automated ultra-high resolution SEM, MAPS Mineralogy and FIB-SEM Saif, Tarik; Lin, Qingyang; Butcher, Alan R. Applied Energy, Vol. 202 https://doi.org/10.1016/j.apenergy.2017.05.039	journal	September 2017
Element release and reaction-induced porosity alteration during shale-hydraulic fracturing fluid interactions Harrison, Anna L.; Jew, Adam D.; Dustin, Megan K. Applied Geochemistry, Vol. 82 https://doi.org/10.1016/j.apgeochem.2017.05.001	journal	July 2017
The impact of mineral reactive surface area variation on simulated mineral reactions and reaction rates Qin, Fanqi; Beckingham, Lauren E. Applied Geochemistry, Vol. 124 https://doi.org/10.1016/j.apgeochem.2020.104852	journal	January 2021
A microfluidic experiment and pore scale modelling diagnostics for assessing mineral precipitation and dissolution in confined spaces Poonoosamy, Jenna; Westerwalbesloh, Christoph; Deissmann, Guido Chemical Geology, Vol. 528 https://doi.org/10.1016/j.chemgeo.2019.07.039	journal	December 2019
Complementary neutron scattering, mercury intrusion and SEM imaging approaches to micro- and nano-pore structure characterization of tight rocks: A case study of the Bakken shale Zhang, Yuxiang; Barber, Troy J.; Hu, Qinhong International Journal of Coal Geology, Vol. 212 https://doi.org/10.1016/j.coal.2019.103252	journal	August 2019
Evaluation of mineral reactive surface area estimates for prediction of reactivity of a multi-mineral sediment Beckingham, Lauren E.; Mitnick, Elizabeth H.; Steefel, Carl I. Geochimica et Cosmochimica Acta, Vol. 188 https://doi.org/10.1016/j.gca.2016.05.040	journal	September 2016
A review of non-invasive imaging methods and applications in contaminant hydrogeology research Werth, Charles J.; Zhang, Changyong; Brusseau, Mark L. Journal of Contaminant Hydrology, Vol. 113, Issue 1-4 https://doi.org/10.1016/j.jconhyd.2010.01.001	journal	April 2010
Gas transport and storage capacity in shale gas reservoirs – A review. Part A: Transport processes Gensterblum, Yves; Ghanizadeh, Amin; Cuss, Robert J. Journal of Unconventional Oil and Gas Resources, Vol. 12 https://doi.org/10.1016/j.juogr.2015.08.001	journal	December 2015
The importance of shale composition and pore structure upon gas storage potential of shale gas reservoirs Ross, Daniel J. K.; Marc Bustin, R. Marine and Petroleum Geology, Vol. 26, Issue 6 https://doi.org/10.1016/j.marpetgeo.2008.06.004	journal	June 2009
Mineral dissolution and wormholing from a pore-scale perspective Soulaine, Cyprien; Roman, Sophie; Kovscek, Anthony Journal of Fluid Mechanics, Vol. 827 https://doi.org/10.1017/jfm.2017.499	journal	August 2017
Where Lower Calcite Abundance Creates More Alteration: Enhanced Rock Matrix Diffusivity Induced by Preferential Dissolution Wen, Hang; Li, Li; Crandall, Dustin Energy & Fuels, Vol. 30, Issue 5 https://doi.org/10.1021/acs.energyfuels.5b02932	journal	December 2015
Interpreting Pore Dimensions in Gas Shales Using a Combination of SEM Imaging, Small-Angle Neutron Scattering, and Low-Pressure Gas Adsorption Vishal, Vikram; Chandra, Debanjan; Bahadur, Jitendra Energy & Fuels, Vol. 33, Issue 6 https://doi.org/10.1021/acs.energyfuels.9b00442	journal	April 2019
Reactive Transport Modeling of Shale–Fluid Interactions after Imbibition of Fracturing Fluids Li, Qingyun; Jew, Adam D.; Brown, Gordon E. Energy & Fuels, Vol. 34, Issue 5 https://doi.org/10.1021/acs.energyfuels.9b04542	journal	April 2020
Acid Erosion of Carbonate Fractures and Accessibility of Arsenic-Bearing Minerals: In Operando Synchrotron-Based Microfluidic Experiment Deng, Hang; Fitts, Jeffrey P.; Tappero, Ryan V. Environmental Science & Technology, Vol. 54, Issue 19 https://doi.org/10.1021/acs.est.0c03736	journal	August 2020
Effect of CO₂ Phase States and Flow Rate on Salt Precipitation in Shale Caprocks—A Microfluidic Study Nooraiepour, Mohammad; Fazeli, Hossein; Miri, Rohaldin Environmental Science & Technology, Vol. 52, Issue 10 https://doi.org/10.1021/acs.est.8b00251	journal	April 2018
Pore-Scale Analysis of Calcium Carbonate Precipitation and Dissolution Kinetics in a Microfluidic Device Yoon, Hongkyu; Chojnicki, Kirsten N.; Martinez, Mario J. Environmental Science & Technology, Vol. 53, Issue 24 https://doi.org/10.1021/acs.est.9b01634	journal	November 2019
Microfluidic Study of Fracture Dissolution in Carbonate-Rich Caprocks Subjected to CO ₂ -Charged Brine Fazeli, Hossein; Nooraiepour, Mohammad; Hellevang, Helge Industrial & Engineering Chemistry Research, Vol. 59, Issue 1 https://doi.org/10.1021/acs.iecr.9b06048	journal	December 2019
Flow pattern variability in natural fracture intersections Kosakowski, Georg; Berkowitz, Brian Geophysical Research Letters, Vol. 26, Issue 12 https://doi.org/10.1029/1999GL900344	journal	June 1999
Impact of coating development on the hydraulic and transport properties in argillaceous limestone fracture: DISSOLUTION IN ARGILLACEOUS LIMESTONE FRACTURE Noiriel, Catherine; Madé, Benoît; Gouze, Philippe Water Resources Research, Vol. 43, Issue 9 https://doi.org/10.1029/2006WR005379	journal	September 2007
Carbonate dissolution during subduction revealed by diamond-bearing rocks from the Alps Frezzotti, M. L.; Selverstone, J.; Sharp, Z. D. Nature Geoscience, Vol. 4, Issue 10 https://doi.org/10.1038/ngeo1246	journal	September 2011
Mineral dissolution and reprecipitation mediated by an amorphous phase Konrad-Schmolke, Matthias; Halama, Ralf; Wirth, Richard Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-03944-z	journal	April 2018
An invisible soil acidification: Critical role of soil carbonate and its impact on heavy metal bioavailability Wang, Cheng; Li, Wei; Yang, Zhongfang Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep12735	journal	July 2015
Mechanisms of multiphase reactive flow using biogenically calcite-functionalized micromodels Song, Wen; Ogunbanwo, Folake; Steinsbø, Marianne Lab on a Chip, Vol. 18, Issue 24 https://doi.org/10.1039/C8LC00793D	journal	January 2018
Current CaCO ₃ dissolution at the seafloor caused by anthropogenic CO ₂ Sulpis, Olivier; Boudreau, Bernard P.; Mucci, Alfonso Proceedings of the National Academy of Sciences, Vol. 115, Issue 46 https://doi.org/10.1073/pnas.1804250115	journal	October 2018
Dissolution-Driven Permeability Reduction of a Fractured Carbonate Caprock Ellis, Brian R.; Fitts, Jeffrey P.; Bromhal, Grant S. Environmental Engineering Science, Vol. 30, Issue 4 https://doi.org/10.1089/ees.2012.0337	journal	April 2013
Natural Fractures in shale: A review and new observations Gale, Julia F. W.; Laubach, Stephen E.; Olson, Jon E. AAPG Bulletin, Vol. 98, Issue 11 https://doi.org/10.1306/08121413151	journal	November 2014
Laboratory-Scale Studies on Chemical Reactions Between Fracturing Fluid and Shale Core From the Marcellus Shale Energy and Environmental Laboratory (MSEEL) Site Hakala, Alexandra; Crandall, Dustin; Moore, Johnathan Proceedings of the 5th Unconventional Resources Technology Conference https://doi.org/10.15530/urtec-2017-2670856	conference	January 2017
Nano-Imaging of Shale using Electron Microscopy Techniques Froute, Laura; Kovscek, Anthony R. Proceedings of the 8th Unconventional Resources Technology Conference https://doi.org/10.15530/urtec-2020-3283	conference	January 2020
Surface Reactive Fluid's Effect on Shale Grieser, Bill; Wheaton, Bill; Magness, Bill All Days https://doi.org/10.2118/106815-MS	conference	March 2007
Improving Hydraulic Fracturing of Shale Formations by Acidizing Morsy, Samiha; Sheng, J. J.; Soliman, M. Y. All Days https://doi.org/10.2118/165688-MS	conference	August 2013
How Natural Fractures Could Affect Hydraulic-Fracture Geometry Dahi Taleghani, Arash; Olson, Jon E. SPE Journal, Vol. 19, Issue 01 https://doi.org/10.2118/167608-PA	journal	February 2013
Multiscale Imaging of Gas Storage in Shales Aljamaan, Hamza; Ross, Cynthia M.; Kovscek, Anthony R. SPE Journal, Vol. 22, Issue 06 https://doi.org/10.2118/185054-PA	journal	August 2017
Caprock Fracture Dissolution and CO2 Leakage Fitts, J. P.; Peters, C. A. Reviews in Mineralogy and Geochemistry, Vol. 77, Issue 1 https://doi.org/10.2138/rmg.2013.77.13	journal	January 2013
Multi-Scale Microfluidics for Transport in Shale Fabric Ling, Bowen; Khan, Hasan J.; Druhan, Jennifer L. Energies, Vol. 14, Issue 1 https://doi.org/10.3390/en14010021	journal	December 2020

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