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Title: Influence of microstructure on replacement and porosity generation during experimental dolomitization of limestones

Abstract

Replacement reactions commonly alter the multiscale pore structures of rocks during fluid-rock interactions. Analysis of these processes in various model fluid-rock systems during controlled laboratory experiments provides insights into the origins of microstructures found in natural materials. This study focused on understanding the effects of initial starting material permeability and resultant differences in transport pathways on porosity and mineralogical changes during limestone dolomitization.A series of replacement experiments (32–317 days in duration) have been conducted in which 1.59 cm (5/8 in.) diameter cores of two different limestones were reacted with saturated MgCl2 solutions at 200 °C. The Texas Cream (Austin Chalk) is a high-porosity, high-permeability limestone, whereas both the porosity and permeability of the Carthage Marble (Burlington Limestone) are relatively low. Altered limestones were imaged using scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX), Time-of-Flight Secondary Ion Mass Spectrometry (ToF–SIMS) and electron microprobe analysis (EMPA). A representative grain boundary of the low-porosity limestone was targeted for a focused ion beam (FIB) lift-out and characterized using transmission electron microscopy (TEM). These results were coupled with analyses of radial changes in the porosity distribution of the core derived from X-ray and neutron small- and ultra-small angle scattering ((U)SANS/(U)SAXS).The high-porosity/permeability limestone showed a fourmore » times faster bulk replacement rate than the lower-porosity/permeability material, and a different mechanism of porosity development. For the low-porosity limestone, a two-stage replacement occurred, with the reacted region of the core consisting of an inner rim in which the limestone was replaced by two calcite-dolomite solid solutions, and an outer rim in which the dolomite was replaced by magnesite. Elongated pores formed along grain boundaries at the initial limestone/dolomite reaction interface, and additional nanometer-scale porosity was formed at the secondary magnesite replacement rim. Grain boundaries were identified as preferential pathways for transport leading to dolomitization and a grain boundary diffusion rate was calculated based on microstructural characterization. In contrast, replacement in the high-porosity limestone was accompanied by porosity generation through replacement of individual grains by dolomite throughout the sample and, in longer runs, magnesite in outer parts of the core. These observations emphasize that both the mechanisms of the replacement reaction and the microstructure and chemistry of the replaced product are contingent on the initial structure of the starting material.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2];  [3];  [4];  [5];  [6]; ORCiD logo [7];  [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
  2. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research; Univ. of Maryland, College Park, MD (United States). Dept. of Materials Science and Engineering
  3. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
  4. Univ. of Arizona, Tucson, AZ (United States). Lunar and Planetary Lab.
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
  6. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Div.
  7. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE
OSTI Identifier:
1797642
Alternate Identifier(s):
OSTI ID: 1782946
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Geochimica et Cosmochimica Acta
Additional Journal Information:
Journal Volume: 303; Journal Issue: -; Journal ID: ISSN 0016-7037
Publisher:
Elsevier; The Geochemical Society; The Meteoritical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 58 GEOSCIENCES; Small-angle scattering; Porosity analyses; Replacement reactions; Limestone; Dolomite; Dolomitization; Neutron; Magnesite; Grain boundary diffusion

Citation Formats

Weber, Juliane, Cheshire, Michael C., Bleuel, Markus, Mildner, David, Chang, Yao-Jen, Ievlev, Anton, Littrell, Ken C., Ilavsky, Jan, Stack, Andrew G., and Anovitz, Lawrence M. Influence of microstructure on replacement and porosity generation during experimental dolomitization of limestones. United States: N. p., 2021. Web. doi:10.1016/j.gca.2021.03.029.
Weber, Juliane, Cheshire, Michael C., Bleuel, Markus, Mildner, David, Chang, Yao-Jen, Ievlev, Anton, Littrell, Ken C., Ilavsky, Jan, Stack, Andrew G., & Anovitz, Lawrence M. Influence of microstructure on replacement and porosity generation during experimental dolomitization of limestones. United States. https://doi.org/10.1016/j.gca.2021.03.029
Weber, Juliane, Cheshire, Michael C., Bleuel, Markus, Mildner, David, Chang, Yao-Jen, Ievlev, Anton, Littrell, Ken C., Ilavsky, Jan, Stack, Andrew G., and Anovitz, Lawrence M. 2021. "Influence of microstructure on replacement and porosity generation during experimental dolomitization of limestones". United States. https://doi.org/10.1016/j.gca.2021.03.029.
@article{osti_1797642,
title = {Influence of microstructure on replacement and porosity generation during experimental dolomitization of limestones},
author = {Weber, Juliane and Cheshire, Michael C. and Bleuel, Markus and Mildner, David and Chang, Yao-Jen and Ievlev, Anton and Littrell, Ken C. and Ilavsky, Jan and Stack, Andrew G. and Anovitz, Lawrence M.},
abstractNote = {Replacement reactions commonly alter the multiscale pore structures of rocks during fluid-rock interactions. Analysis of these processes in various model fluid-rock systems during controlled laboratory experiments provides insights into the origins of microstructures found in natural materials. This study focused on understanding the effects of initial starting material permeability and resultant differences in transport pathways on porosity and mineralogical changes during limestone dolomitization.A series of replacement experiments (32–317 days in duration) have been conducted in which 1.59 cm (5/8 in.) diameter cores of two different limestones were reacted with saturated MgCl2 solutions at 200 °C. The Texas Cream (Austin Chalk) is a high-porosity, high-permeability limestone, whereas both the porosity and permeability of the Carthage Marble (Burlington Limestone) are relatively low. Altered limestones were imaged using scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX), Time-of-Flight Secondary Ion Mass Spectrometry (ToF–SIMS) and electron microprobe analysis (EMPA). A representative grain boundary of the low-porosity limestone was targeted for a focused ion beam (FIB) lift-out and characterized using transmission electron microscopy (TEM). These results were coupled with analyses of radial changes in the porosity distribution of the core derived from X-ray and neutron small- and ultra-small angle scattering ((U)SANS/(U)SAXS).The high-porosity/permeability limestone showed a four times faster bulk replacement rate than the lower-porosity/permeability material, and a different mechanism of porosity development. For the low-porosity limestone, a two-stage replacement occurred, with the reacted region of the core consisting of an inner rim in which the limestone was replaced by two calcite-dolomite solid solutions, and an outer rim in which the dolomite was replaced by magnesite. Elongated pores formed along grain boundaries at the initial limestone/dolomite reaction interface, and additional nanometer-scale porosity was formed at the secondary magnesite replacement rim. Grain boundaries were identified as preferential pathways for transport leading to dolomitization and a grain boundary diffusion rate was calculated based on microstructural characterization. In contrast, replacement in the high-porosity limestone was accompanied by porosity generation through replacement of individual grains by dolomite throughout the sample and, in longer runs, magnesite in outer parts of the core. These observations emphasize that both the mechanisms of the replacement reaction and the microstructure and chemistry of the replaced product are contingent on the initial structure of the starting material.},
doi = {10.1016/j.gca.2021.03.029},
url = {https://www.osti.gov/biblio/1797642}, journal = {Geochimica et Cosmochimica Acta},
issn = {0016-7037},
number = -,
volume = 303,
place = {United States},
year = {2021},
month = {3}
}

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