Impact of Acid–Base Stimulation Sequence on Mineral Stability for Tight/Impermeable Unconventional Carbonate-Rich Rocks: A Delaware Basin Case Study

Spielman-Sun, Eleanor; Jew, Adam D.; Bargar, John R.

doi:10.1021/acs.energyfuels.1c04188

Impact of Acid–Base Stimulation Sequence on Mineral Stability for Tight/Impermeable Unconventional Carbonate-Rich Rocks: A Delaware Basin Case Study

Journal Article · Tue Apr 26 00:00:00 EDT 2022 · Energy and Fuels

DOI:https://doi.org/10.1021/acs.energyfuels.1c04188· OSTI ID:1876885

^[1]; ^[1]; ^[1]

SLAC National Accelerator Lab., Menlo Park, CA (United States)

We report mineral precipitation due to reactions with injected fluids during unconventional fracture stimulation is a well-recognized problem. The goal of this study is to evaluate secondary mineral precipitation and permeability attenuation under chemical injection scenarios specific to the Delaware basin. Whole cylindrical cores (2.54 cm diameter and 2.54 cm height) and ground shale (150–250 μm) from the carbonate-rich Bone Spring Formation, Delaware Basin TX (Leonardian), were reacted at 80 °C and 85 bar using a hydraulic fracturing fluid (HFF) recipe and an injection sequence typical of the Delaware Basin. The reacted shales and solutions were analyzed using a variety of laboratory- and synchrotron-based techniques to characterize both the chemical and spatial distributions of secondary mineral precipitation and identify changes in permeability and mineralogy. This carbonate-rich shale (>84% calcite) rapidly neutralized the acidic HFF. Synchrotron-based X-ray fluorescence mapping coupled with X-ray absorption spectroscopy (both bulk and micro) showed that most of the iron was in an oxidized form prior to exposure to HFF and that almost all iron(II) became fully oxidized after the reaction. Scanning electron microscopy images of the ground shale samples primarily identified iron(oxyhydr)oxide microcrystals on grain surfaces. A few small isolated iron-rich areas also contained sulfur, suggesting that some pyrite was preserved when isolated within a calcite crystal but that most was oxidized. The rapid neutralization of the acid spearhead in these carbonate-rich samples demonstrates that the acid spearhead is useful for initiating fractures in extremely calcite-rich rocks but does little to enhance rock permeability. This suggests that the impact of the acid spearhead is significantly smaller for carbonate-rich shales compared to clay-rich shales, which has broad implications for acidizing in carbonate-rich shale formations and iron transformations within these shales.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Fossil Energy (FE); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1876885

Journal Information:: Energy and Fuels, Journal Name: Energy and Fuels Journal Issue: 9 Vol. 36; ISSN 0887-0624

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (69)

Effect of advective flow in fractures and matrix diffusion on natural gas production Karra, Satish; Makedonska, Nataliia; Viswanathan, Hari S. Water Resources Research, Vol. 51, Issue 10 https://doi.org/10.1002/2014WR016829	journal	October 2015
A modified acid system to enhance carbonate matrix acid stimulation: An experimental study Zhu, Ding; Hill, Dan; Ugursal, Assiya The Canadian Journal of Chemical Engineering, Vol. 100, Issue 6 https://doi.org/10.1002/cjce.24251	journal	August 2021
The solubility of celestite and barite in electrolyte solutions and natural waters at 25°C: A thermodynamic study Monnin, Christophe; Galinier, Colette Chemical Geology, Vol. 71, Issue 4 https://doi.org/10.1016/0009-2541(88)90055-1	journal	December 1988
Geometry and mineral heterogeneity controls on precipitation in fractures: An X-ray micro-tomography and reactive transport modeling study Noiriel, Catherine; Seigneur, Nicolas; Le Guern, Pierre Advances in Water Resources, Vol. 152 https://doi.org/10.1016/j.advwatres.2021.103916	journal	June 2021
Induced mobility of inorganic and organic solutes from black shales using water extraction: Implications for shale gas exploitation Wilke, Franziska D. H.; Vieth-Hillebrand, Andrea; Naumann, Rudolf Applied Geochemistry, Vol. 63 https://doi.org/10.1016/j.apgeochem.2015.07.008	journal	December 2015
Experimental insights into geochemical changes in hydraulically fractured Marcellus Shale Marcon, Virginia; Joseph, Craig; Carter, Kimberly E. Applied Geochemistry, Vol. 76 https://doi.org/10.1016/j.apgeochem.2016.11.005	journal	January 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
Mineral dissolution and precipitation induced by hydraulic fracturing of a mudstone and a tight sandstone in the Powder River Basin, Wyoming, USA Herz-Thyhsen, Ryan J.; Kaszuba, John P.; Dewey, Janet C. Applied Geochemistry, Vol. 119 https://doi.org/10.1016/j.apgeochem.2020.104636	journal	August 2020
Dissolution kinetics of calcite, dolomite and magnesite at 25 °C and 0 to 50 atm pCO2 Pokrovsky, Oleg S.; Golubev, Sergey V.; Schott, Jacques Chemical Geology, Vol. 217, Issue 3-4 https://doi.org/10.1016/j.chemgeo.2004.12.012	journal	April 2005
Changes in porosity, permeability, water retention curve and reactive surface area during carbonate rock dissolution Rötting, Tobias S.; Luquot, Linda; Carrera, Jesus Chemical Geology, Vol. 403 https://doi.org/10.1016/j.chemgeo.2015.03.008	journal	May 2015
Characterization of Marcellus Shale and Huntersville Chert before and after exposure to hydraulic fracturing fluid via feature relocation using field-emission scanning electron microscopy Dieterich, Matthew; Kutchko, Barbara; Goodman, Angela Fuel, Vol. 182 https://doi.org/10.1016/j.fuel.2016.05.061	journal	October 2016
Predicting the potential for mineral scale precipitation in unconventional reservoirs due to fluid-rock and fluid mixing geochemical reactions Hakala, J. Alexandra; Paukert Vankeuren, Amelia N.; Scheuermann, Peter P. Fuel, Vol. 284 https://doi.org/10.1016/j.fuel.2020.118883	journal	January 2021
Geochemical element mobilisation by interaction of Bowland shale with acidic fluids Ji, Yukun; Hennissen, Jan A. I.; Hough, Edward Fuel, Vol. 289 https://doi.org/10.1016/j.fuel.2020.119914	journal	April 2021
Characterization of marl and interbedded limestone layers in the Eagle Ford Formation, DeWitt county, Texas Jiang, Shuxian; Mokhtari, Mehdi Journal of Petroleum Science and Engineering, Vol. 172 https://doi.org/10.1016/j.petrol.2018.09.094	journal	January 2019
Iron-framboids in the hydrocarbon-related Middle Devonian Hollard Mound of the Anti-Atlas mountain range in Morocco: Evidence of potential microbial biosignatures Cavalazzi, Barbara; Barbieri, Roberto; Cady, Sherry L. Sedimentary Geology, Vol. 263-264 https://doi.org/10.1016/j.sedgeo.2011.09.007	journal	July 2012
Micropetrographic characterization of a siliciclastic-rich chalk; Upper Cretaceous Austin Chalk Group along the onshore northern Gulf of Mexico, USA Loucks, Robert G.; Reed, Robert M.; Ko, Lucy T. Sedimentary Geology, Vol. 412 https://doi.org/10.1016/j.sedgeo.2020.105821	journal	February 2021
The mechanisms of pyrite oxidation and leaching: A fundamental perspective Chandra, A. P.; Gerson, A. R. Surface Science Reports, Vol. 65, Issue 9 https://doi.org/10.1016/j.surfrep.2010.08.003	journal	September 2010
Small-angle Neutron Scattering (SANS) Characterization of Clay- and Carbonate-rich Shale at Elevated Pressures Neil, Chelsea W.; Hjelm, Rex P.; Hawley, Marilyn E. Energy & Fuels, Vol. 34, Issue 7 https://doi.org/10.1021/acs.energyfuels.0c01009	journal	June 2020
Influence of Reactive Flow Conditions on Barite Scaling in Marcellus Shale during Stimulation and Shut-In Periods of Hydraulic Fracturing Xiong, Wei; Gill, Magdalena; Moore, Johnathan Energy & Fuels, Vol. 34, Issue 11 https://doi.org/10.1021/acs.energyfuels.0c02156	journal	October 2020
Multiphysics Investigation of Geochemical Alterations in Marcellus Shale Using Reactive Core-Floods Gundogar, Asli S.; Ross, Cynthia M.; Jew, Adam D. Energy & Fuels, Vol. 35, Issue 13 https://doi.org/10.1021/acs.energyfuels.1c00588	journal	June 2021
Ionic Strength and pH Effects on Water–Rock Interaction in an Unconventional Siliceous Reservoir: On the Use of Formation Water in Hydraulic Fracturing Bratcher, Jordan C.; Kaszuba, John P.; Herz-Thyhsen, Ryan J. Energy & Fuels, Vol. 35, Issue 22 https://doi.org/10.1021/acs.energyfuels.1c02322	journal	November 2021
Impact of Organics and Carbonates on the Oxidation and Precipitation of Iron during Hydraulic Fracturing of Shale Jew, Adam D.; Dustin, Megan K.; Harrison, Anna L. Energy & Fuels, Vol. 31, Issue 4 https://doi.org/10.1021/acs.energyfuels.6b03220	journal	March 2017
Shale Kerogen: Hydraulic Fracturing Fluid Interactions and Contaminant Release Dustin, Megan K.; Bargar, John R.; Jew, Adam D. Energy & Fuels, Vol. 32, Issue 9 https://doi.org/10.1021/acs.energyfuels.8b01037	journal	August 2018
Dissolution of Minerals and Precipitation of an Aluminosilicate Phase during Experimentally Simulated Hydraulic Fracturing of a Mudstone and a Tight Sandstone in the Powder River Basin, WY Herz-Thyhsen, Ryan J.; Kaszuba, John P.; Dewey, Janet C. Energy & Fuels, Vol. 33, Issue 5 https://doi.org/10.1021/acs.energyfuels.8b04443	journal	April 2019
Thicknesses of Chemically Altered Zones in Shale Matrices Resulting from Interactions with Hydraulic Fracturing Fluid Li, Qingyun; Jew, Adam D.; Kohli, Arjun Energy & Fuels, Vol. 33, Issue 8 https://doi.org/10.1021/acs.energyfuels.8b04527	journal	July 2019
A Critical Review of the Physicochemical Impacts of Water Chemistry on Shale in Hydraulic Fracturing Systems Khan, Hasan Javed; Spielman-Sun, Eleanor; Jew, Adam D. Environmental Science & Technology, Vol. 55, Issue 3 https://doi.org/10.1021/acs.est.0c04901	journal	January 2021
Mineral Reactions in Shale Gas Reservoirs: Barite Scale Formation from Reusing Produced Water As Hydraulic Fracturing Fluid Paukert Vankeuren, Amelia N.; Hakala, J. Alexandra; Jarvis, Karl Environmental Science & Technology, Vol. 51, Issue 16 https://doi.org/10.1021/acs.est.7b01979	journal	July 2017
Alteration and Erosion of Rock Matrix Bordering a Carbonate-Rich Shale Fracture Deng, Hang; Voltolini, Marco; Molins, Sergi Environmental Science & Technology, Vol. 51, Issue 15 https://doi.org/10.1021/acs.est.7b02063	journal	July 2017
Release of Particulate Iron Sulfide during Shale-Fluid Interaction Kreisserman, Yevgeny; Emmanuel, Simon Environmental Science & Technology, Vol. 52, Issue 2 https://doi.org/10.1021/acs.est.7b05350	journal	December 2017
Sulfur Speciation in Different Kerogens by XANES Spectroscopy Wiltfong, Roger; Mitra-Kirtley, Sudipa; Mullins, Oliver C. Energy & Fuels, Vol. 19, Issue 5 https://doi.org/10.1021/ef049753n	journal	July 2005
The Chemistry of Persulfate. I. The Kinetics and Mechanism of the Decomposition of the Persulfate Ion in Aqueous Medium ¹ Kolthoff, I. M.; Miller, I. K. Journal of the American Chemical Society, Vol. 73, Issue 7 https://doi.org/10.1021/ja01151a024	journal	July 1951
Rheology of guar and (hydroxypropyl) guar crosslinked by borate Kesavan, Subramanian; Prud'homme, Robert K. Macromolecules, Vol. 25, Issue 7 https://doi.org/10.1021/ma00033a029	journal	March 1992
Extracting Hydrocarbon From Shale: An Investigation of the Factors That Influence the Decline and the Tail of the Production Curve Lovell, A. E.; Srinivasan, S.; Karra, S. Water Resources Research, Vol. 54, Issue 5 https://doi.org/10.1029/2017WR022180	journal	May 2018
Replacement of pyrite framboids by magnetite in limestone and implications for palaeomagnetism Suk, D.; Peacor, D. R.; der Voo, R. Van Nature, Vol. 345, Issue 6276 https://doi.org/10.1038/345611a0	journal	June 1990
Chemical controls on the propagation rate of fracture in calcite Ilgen, A. G.; Mook, W. M.; Tigges, A. B. Scientific Reports, Vol. 8, Issue 1 https://doi.org/10.1038/s41598-018-34355-1	journal	November 2018
The MicroAnalysis Toolkit: X-ray Fluorescence Image Processing Software Webb, S. M.; McNulty, Ian; Eyberger, Catherine THE 10TH INTERNATIONAL CONFERENCE ON X-RAY MICROSCOPY, AIP Conference Proceedings https://doi.org/10.1063/1.3625338	conference	January 2011
The new mineral hexahydroborite, Ca[B(OH) ₄ ] ₂ · 2H ₂ O Simonov, M. A. International Geology Review, Vol. 21, Issue 4 https://doi.org/10.1080/00206818209467082	journal	April 1979
Impact of Water Chemistry on Element Mobilization from Eagle Ford Shale Wang, Lin; Fortner, John D.; Giammar, Daniel E. Environmental Engineering Science, Vol. 32, Issue 4 https://doi.org/10.1089/ees.2014.0342	journal	April 2015
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Petrological evidence supports the death mask model for the preservation of Ediacaran soft-bodied organisms in South Australia Liu, Alexander G.; McMahon, Sean; Matthews, Jack J. Geology, Vol. 47, Issue 3 https://doi.org/10.1130/G45918.1	journal	January 2019
Complex Fluids and Hydraulic Fracturing Barbati, Alexander C.; Desroches, Jean; Robisson, Agathe Annual Review of Chemical and Biomolecular Engineering, Vol. 7, Issue 1 https://doi.org/10.1146/annurev-chembioeng-080615-033630	journal	June 2016
SIXPack a Graphical User Interface for XAS Analysis Using IFEFFIT Webb, S. M. Physica Scripta https://doi.org/10.1238/Physica.Topical.115a01011	journal	January 2005
Facies variability within a mixed carbonate–siliciclastic sea-floor fan (upper Wolfcamp Formation, Permian, Delaware Basin, New Mexico) Kvale, Erik P.; Bowie, Christopher M.; Flenthrope, Chris AAPG Bulletin, Vol. 104, Issue 3 https://doi.org/10.1306/06121917225	journal	March 2020
Geochemical interactions of shale and brine in autoclave experiments—Understanding mineral reactions during hydraulic fracturing of Marcellus and Eagle Ford Shales Lu, Jiemin; Mickler, Patrick J.; Nicot, Jean-Philippe AAPG Bulletin, Vol. 101, Issue 10 https://doi.org/10.1306/11101616026	journal	October 2017
Effect of Acid on Productivity of Fractured Shale Reservoirs Pournik, Maysam; Tripathi, Divyendu Proceedings of the 2nd Unconventional Resources Technology Conference https://doi.org/10.15530/urtec-2014-1922960	conference	January 2014
Rapid Quantification of Mineralogy, Organic Matter, and Thermal Maturity of Cuttings With Diffuse Reflectance Infrared Fourier Transform Spectroscopy, Permian Basin Loan, MaryEllen L.; Herron, Michael M.; Matteson, Abigail Proceedings of the 5th Unconventional Resources Technology Conference https://doi.org/10.15530/urtec-2017-2671423	conference	January 2017
Mineralogical and Porosity Alteration Following Fracture Fluid-Shale Reaction Jew, Adam D.; Harrison, Anna L.; Dustin, Megan K. Proceedings of the 5th Unconventional Resources Technology Conference https://doi.org/10.15530/urtec-2017-2708858	conference	January 2017
Effects of Hydraulic Fracturing Fluid Chemistry on Shale Matrix Permeability Alalli, Abdulgader A.; Li, Qingyun; Jew, Adam Proceedings of the 6th Unconventional Resources Technology Conference https://doi.org/10.15530/urtec-2018-2881314	conference	January 2018
Imaging Pyrite Oxidation and Barite Precipitation in Gas and Oil Shales Li, Qingyun; Jew, Adam; Kiss, Andrew Proceedings of the 6th Unconventional Resources Technology Conference https://doi.org/10.15530/urtec-2018-2902747	conference	January 2018
Geochemical Modeling of Iron (Hydr)oxide Scale Formation During Hydraulic Fracturing Operations Li, Qingyun; Jew, Adam D.; Cercone, David Proceedings of the 7th Unconventional Resources Technology Conference https://doi.org/10.15530/urtec-2019-612	conference	January 2019
Second Bone Spring Sand Development Strategies Within the Delaware Basin, West Texas and Southeast New Mexico O'Toole, Timothy; Adebare, Adedeji; Wright, Sarah Proceedings of the 8th Unconventional Resources Technology Conference https://doi.org/10.15530/urtec-2020-2728	conference	January 2020
Strontium Behavior in Midland Basin Unconventional Reservoirs: The Importance of Base Fluids Jew, Adam; Bargar, John R.; Brownlow, Josh Proceedings of the 8th Unconventional Resources Technology Conference https://doi.org/10.15530/urtec-2020-3016	conference	January 2020
Synchrotron X-ray Imaging of Element Transport Resulting from Unconventional Stimulation Noël, Vincent; Spielman-Sun, Eleanor; Druhan, Jennifer L. Proceedings of the 8th Unconventional Resources Technology Conference https://doi.org/10.15530/urtec-2020-3295	conference	January 2020
Hydraulic Fracturing Geochemical Impact on Fluid Chemistry: Comparing Wolfcamp Shale and Marcellus Shale Xiong, Wei; Moore, Johnathan; Crandall, Dustin Proceedings of the 9th Unconventional Resources Technology Conference https://doi.org/10.15530/urtec-2021-5524	conference	January 2021
Hematite Framboids in the Negaunee Iron Formation, Michigan; evidence for Their Biogenic Origin Lougheed, M. S.; Mancuso, J. J. Economic Geology, Vol. 68, Issue 2 https://doi.org/10.2113/gsecongeo.68.2.202	journal	April 1973
The Texture of Acidized Fracture Surfaces: Implications for Acid Fracture Conductivity Malagon, C.; Pournik, M.; Hill, A. D. SPE Production & Operations, Vol. 23, Issue 03 https://doi.org/10.2118/102167-PA	journal	August 2008
A Comprehensive Model of High-Rate Matrix Acid Stimulation for Long Horizontal Wells in Carbonate Reservoirs Furui, K. .; Burton, R. C.; Burkhead, D. W. SPE Annual Technical Conference and Exhibition, All Days https://doi.org/10.2118/134265-MS	conference	September 2010
Acid Fracturing in Shales: Effect of Dilute Acid on Properties and Pore Structure of Shale Wu, Weiwei; Sharma, Mukul M. SPE Production & Operations, Vol. 32, Issue 01 https://doi.org/10.2118/173390-pa	journal	April 2016
The Combined Effect of Permeability and Pore Structure on Carbonate Matrix Acidizing Etten, J. .; Zhu, D. .; Hill, A. D. EUROPEC 2015, All Days https://doi.org/10.2118/174314-MS	conference	June 2015
An Overview of Formation Damage and Well Productivity in Oilfield Operations: An Update Krueger, R. F. SPE California Regional Meeting, All Days https://doi.org/10.2118/17459-MS	conference	March 1988
Character of the Avalon Shale (Bone Spring Formation) of the Delaware Basin, West Texas and Southeast New Mexico: Effect of Carbonate-Rich Sediment Gravity Flows Stolz, Dustin J.; Franseen, Evan K.; Goldstein, Robert H. Unconventional Resources Technology Conference https://doi.org/10.2118/178610-MS	conference	August 2015
Acid Fracturing Carbonate-Rich Shale: A Feasibility Investigation of Eagle Ford Formation Cash, Rachael; Zhu, Ding; Hill, A. D. SPE Asia Pacific Hydraulic Fracturing Conference, Day 3 Fri, August 26, 2016 https://doi.org/10.2118/181805-MS	conference	August 2016
Simulation Study of Scale Management During Hydraulic Fracturing in Unconventional Reservoirs Abouie, Ali; Sanaei, Alireza; Sepehrnoori, Kamy SPE International Conference on Oilfield Chemistry, Day 2 Tue, April 09, 2019 https://doi.org/10.2118/193570-MS	conference	April 2019
The Optimum Injection Rate for Matrix Acidizing of Carbonate Formations Wang, Y.; Hill, A. D.; Schechter, R. S. SPE Annual Technical Conference and Exhibition, All Days https://doi.org/10.2118/26578-MS	conference	October 1993
Reaction Rate and Fluid Loss: The Keys to Wormhole Initiation and Propagation in Carbonate Acidizing Huang, Tianping; Hill, A. D.; Schechter, R. S. SPE Journal, Vol. 5, Issue 03 https://doi.org/10.2118/65400-pa	journal	September 2000
Sodium-Calcium-Magnesium Exchange on Silver Hill Illite Sposito, Garrison; LeVesque, C. S. Soil Science Society of America Journal, Vol. 49, Issue 5 https://doi.org/10.2136/sssaj1985.03615995004900050016x	journal	September 1985
A compilation of rate parameters of water-mineral interaction kinetics for application to geochemical modeling Palandri, James L.; Kharaka, Yousif K. U.S. Geological Survey (USGS) https://doi.org/10.3133/ofr20041068	report	January 2004
Effects of Carbonate Minerals on Shale-Hydraulic Fracturing Fluid Interactions in the Marcellus Shale Ferguson, Brennan; Agrawal, Vikas; Sharma, Shikha Frontiers in Earth Science, Vol. 9 https://doi.org/10.3389/feart.2021.695978	journal	November 2021
Mineral Precipitation in Fractures and Nanopores within Shale Imaged Using Time-Lapse X-ray Tomography Godinho, Jose R. A.; Ma, Lin; Chai, Yuan Minerals, Vol. 9, Issue 8 https://doi.org/10.3390/min9080480	journal	August 2019

Similar Records

Geochemical Impact of Acid Spearhead and Slickwater Stimulation on Wolfcamp Shale from the Hydraulic Fracturing Test Site

Journal Article · Thu May 22 20:00:00 EDT 2025 · SPE Journal · OSTI ID:2569334

Reactive Transport Modeling of Shale–Fluid Interactions after Imbibition of Fracturing Fluids

Journal Article · Sun Apr 19 20:00:00 EDT 2020 · Energy and Fuels · OSTI ID:1638144

Related Subjects

58 GEOSCIENCES

Impact of Acid–Base Stimulation Sequence on Mineral Stability for Tight/Impermeable Unconventional Carbonate-Rich Rocks: A Delaware Basin Case Study

Citation Formats

References (69)

Similar Records

Related Subjects