{"id":{"repo_id":"wustl","oai_identifier":"oai:openscholarship.wustl.edu:etd-2136"},"canonical_url":"https://search.dev.ndltd.org/etd/wustl/oai:openscholarship.wustl.edu:etd-2136","repository":{"repo_id":"wustl","name":"Washington University in St. Louis","base_url":"https://openscholarship.wustl.edu/do/oai/"},"display":{"title":"Roles of Nano- and Micro-Scale Subsurface Geochemical Reactions on Environmentally Sustainable Geologic CO2 Sequestration","abstract":"<p>Geologic CO<sub>2</sub> sequestration: GCS) is a promising approach to reduce anthropogenic CO<sub>2</sub> emissions into the atmosphere. At GCS sites, injected CO<sub>2</sub> is kept in formation rock by an overlying low permeability caprock. During and after CO<sub>2</sub> injection, geochemical reactions can affect the porosity, permeability, and pollutant transport in aquifers. Despite their importance, nano- and micro-scale subsurface geochemical reactions are far from well-understood.</p><p>Clay mobilization has been reported to decrease aquifer permeability during water flooding, and clay minerals are abundant in caprock. Thus, we studied CO<sub>2</sub>-brine-clay interactions under varied conditions relevant to different GCS sites: at 35-95&deg;C and under 35-120 atm CO<sub>2</sub>, in water, NaCl, MgCl<sub>2</sub>, or CaCl<sub>2</sub> solutions). Biotite, Fe-bearing mica, was used as a model clay mineral. We observed numerous fibrous illite precipitates on mica after reaction for only 3 h, which had not been previously reported. A few hours later, the mica surface cracked and fibrous illite detached. The mobilization of fibrous illite can decrease the aquifer's permeability greatly and affect the safety and efficiency of GCS. Mechanisms related to ion exchange, mica swelling, and CO<sub>2</sub> intercalation were explored. Oriented aggregation of illite nanoparticles forming the fibrous illite was directly observed, suggesting a new mechanism for fibrous illite formation. Interestingly, besides the pH effect, aqueous CO<sub>2</sub> enhances mica cracking over N<sub>2</sub>. These findings can help to achieve safer subsurface operations.</p><p>At GCS field sites, Fe concentration increased near the injection sites and originally adsorbed pollutants were released. As the brine flows, Fe re-precipitated because of pH increase. To better predict the fate and transport of aqueous pollutants, the nucleation and growth of Fe(III): hydr)oxides were studied. New information about sizes and volumes of the Fe(III): hydr)oxide nanoparticles precipitated in solution and on quartz, mica, and sapphire were provided using small angle X-ray scattering, in the presence of different ions: Al<super>3+</super>, Cl<super>-</super>, NO<sub>3</sub><super>-</super>, and SO<sub>4</sub><super>2-</super>). Using complementary techniques, the controlling mechanisms related to surface charge, bond formation, and interfacial energies were explored. These new findings can help better predict pollutant transport in aquifers not only at GCS sites, but also in managed aquifer recharge and acid mine drainage sites.</p>","abstract_html":"&lt;p&gt;Geologic CO&lt;sub&gt;2&lt;/sub&gt; sequestration: GCS) is a promising approach to reduce anthropogenic CO&lt;sub&gt;2&lt;/sub&gt; emissions into the atmosphere. At GCS sites, injected CO&lt;sub&gt;2&lt;/sub&gt; is kept in formation rock by an overlying low permeability caprock. During and after CO&lt;sub&gt;2&lt;/sub&gt; injection, geochemical reactions can affect the porosity, permeability, and pollutant transport in aquifers. Despite their importance, nano- and micro-scale subsurface geochemical reactions are far from well-understood.&lt;/p&gt;&lt;p&gt;Clay mobilization has been reported to decrease aquifer permeability during water flooding, and clay minerals are abundant in caprock. Thus, we studied CO&lt;sub&gt;2&lt;/sub&gt;-brine-clay interactions under varied conditions relevant to different GCS sites: at 35-95&amp;deg;C and under 35-120 atm CO&lt;sub&gt;2&lt;/sub&gt;, in water, NaCl, MgCl&lt;sub&gt;2&lt;/sub&gt;, or CaCl&lt;sub&gt;2&lt;/sub&gt; solutions). Biotite, Fe-bearing mica, was used as a model clay mineral. We observed numerous fibrous illite precipitates on mica after reaction for only 3 h, which had not been previously reported. A few hours later, the mica surface cracked and fibrous illite detached. The mobilization of fibrous illite can decrease the aquifer&#x27;s permeability greatly and affect the safety and efficiency of GCS. Mechanisms related to ion exchange, mica swelling, and CO&lt;sub&gt;2&lt;/sub&gt; intercalation were explored. Oriented aggregation of illite nanoparticles forming the fibrous illite was directly observed, suggesting a new mechanism for fibrous illite formation. Interestingly, besides the pH effect, aqueous CO&lt;sub&gt;2&lt;/sub&gt; enhances mica cracking over N&lt;sub&gt;2&lt;/sub&gt;. These findings can help to achieve safer subsurface operations.&lt;/p&gt;&lt;p&gt;At GCS field sites, Fe concentration increased near the injection sites and originally adsorbed pollutants were released. As the brine flows, Fe re-precipitated because of pH increase. To better predict the fate and transport of aqueous pollutants, the nucleation and growth of Fe(III): hydr)oxides were studied. New information about sizes and volumes of the Fe(III): hydr)oxide nanoparticles precipitated in solution and on quartz, mica, and sapphire were provided using small angle X-ray scattering, in the presence of different ions: Al&lt;super&gt;3+&lt;/super&gt;, Cl&lt;super&gt;-&lt;/super&gt;, NO&lt;sub&gt;3&lt;/sub&gt;&lt;super&gt;-&lt;/super&gt;, and SO&lt;sub&gt;4&lt;/sub&gt;&lt;super&gt;2-&lt;/super&gt;). Using complementary techniques, the controlling mechanisms related to surface charge, bond formation, and interfacial energies were explored. These new findings can help better predict pollutant transport in aquifers not only at GCS sites, but also in managed aquifer recharge and acid mine drainage sites.&lt;/p&gt;","abstract_has_math":false,"creators":["Hu, Yandi"],"institution":null,"degree_name":"Doctor of Philosophy (PhD)","degree_level":"Dissertation","degree_discipline":"Energy, Environmental and Chemical Engineering","degree_department":null,"school":null,"contributors":["Young-Shin Jun"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2013,"date_issued":"2013-05-28T07:00:00Z","date_published":"2013-05-28T07:00:00Z","updated_at":"2026-07-24T06:13:14Z","subjects":[],"languages":["English (en)"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier.doi","label":"DOI","values":["https://doi.org/10.7936/K73776S1"],"render_values":[{"text":"https://doi.org/10.7936/K73776S1","href":"https://doi.org/10.7936/K73776S1","code":true}]}]},"links":{"outbound_url":"https://openscholarship.wustl.edu/etd/1136","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Young-Shin Jun"]},{"key":"dc:creator","label":"Author","values":["Hu, Yandi"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.available","label":"Dc Date Available","values":["2014-03-19T07:00:00Z"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Energy, Environmental and Chemical Engineering"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctor of Philosophy (PhD)"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["English (en)"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://openscholarship.wustl.edu/etd/1136"]},{"key":"dc:identifier.doi","label":"DOI","values":["https://doi.org/10.7936/K73776S1"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["<p>Geologic CO<sub>2</sub> sequestration: GCS) is a promising approach to reduce anthropogenic CO<sub>2</sub> emissions into the atmosphere. At GCS sites, injected CO<sub>2</sub> is kept in formation rock by an overlying low permeability caprock. During and after CO<sub>2</sub> injection, geochemical reactions can affect the porosity, permeability, and pollutant transport in aquifers. Despite their importance, nano- and micro-scale subsurface geochemical reactions are far from well-understood.</p><p>Clay mobilization has been reported to decrease aquifer permeability during water flooding, and clay minerals are abundant in caprock. Thus, we studied CO<sub>2</sub>-brine-clay interactions under varied conditions relevant to different GCS sites: at 35-95&deg;C and under 35-120 atm CO<sub>2</sub>, in water, NaCl, MgCl<sub>2</sub>, or CaCl<sub>2</sub> solutions). Biotite, Fe-bearing mica, was used as a model clay mineral. We observed numerous fibrous illite precipitates on mica after reaction for only 3 h, which had not been previously reported. A few hours later, the mica surface cracked and fibrous illite detached. The mobilization of fibrous illite can decrease the aquifer's permeability greatly and affect the safety and efficiency of GCS. Mechanisms related to ion exchange, mica swelling, and CO<sub>2</sub> intercalation were explored. Oriented aggregation of illite nanoparticles forming the fibrous illite was directly observed, suggesting a new mechanism for fibrous illite formation. Interestingly, besides the pH effect, aqueous CO<sub>2</sub> enhances mica cracking over N<sub>2</sub>. These findings can help to achieve safer subsurface operations.</p><p>At GCS field sites, Fe concentration increased near the injection sites and originally adsorbed pollutants were released. As the brine flows, Fe re-precipitated because of pH increase. To better predict the fate and transport of aqueous pollutants, the nucleation and growth of Fe(III): hydr)oxides were studied. New information about sizes and volumes of the Fe(III): hydr)oxide nanoparticles precipitated in solution and on quartz, mica, and sapphire were provided using small angle X-ray scattering, in the presence of different ions: Al<super>3+</super>, Cl<super>-</super>, NO<sub>3</sub><super>-</super>, and SO<sub>4</sub><super>2-</super>). Using complementary techniques, the controlling mechanisms related to surface charge, bond formation, and interfacial energies were explored. These new findings can help better predict pollutant transport in aquifers not only at GCS sites, but also in managed aquifer recharge and acid mine drainage sites.</p>"]},{"key":"dc:title","label":"Title","values":["Roles of Nano- and Micro-Scale Subsurface Geochemical Reactions on Environmentally Sustainable Geologic CO2 Sequestration"]}]}],"canonical_facts":{"dc:contributor":["Young-Shin Jun"],"dc:creator":["Hu, Yandi"],"dc:date.available":["2014-03-19T07:00:00Z"],"dc:description.abstract":["<p>Geologic CO<sub>2</sub> sequestration: GCS) is a promising approach to reduce anthropogenic CO<sub>2</sub> emissions into the atmosphere. At GCS sites, injected CO<sub>2</sub> is kept in formation rock by an overlying low permeability caprock. During and after CO<sub>2</sub> injection, geochemical reactions can affect the porosity, permeability, and pollutant transport in aquifers. Despite their importance, nano- and micro-scale subsurface geochemical reactions are far from well-understood.</p><p>Clay mobilization has been reported to decrease aquifer permeability during water flooding, and clay minerals are abundant in caprock. Thus, we studied CO<sub>2</sub>-brine-clay interactions under varied conditions relevant to different GCS sites: at 35-95&deg;C and under 35-120 atm CO<sub>2</sub>, in water, NaCl, MgCl<sub>2</sub>, or CaCl<sub>2</sub> solutions). Biotite, Fe-bearing mica, was used as a model clay mineral. We observed numerous fibrous illite precipitates on mica after reaction for only 3 h, which had not been previously reported. A few hours later, the mica surface cracked and fibrous illite detached. The mobilization of fibrous illite can decrease the aquifer's permeability greatly and affect the safety and efficiency of GCS. Mechanisms related to ion exchange, mica swelling, and CO<sub>2</sub> intercalation were explored. Oriented aggregation of illite nanoparticles forming the fibrous illite was directly observed, suggesting a new mechanism for fibrous illite formation. Interestingly, besides the pH effect, aqueous CO<sub>2</sub> enhances mica cracking over N<sub>2</sub>. These findings can help to achieve safer subsurface operations.</p><p>At GCS field sites, Fe concentration increased near the injection sites and originally adsorbed pollutants were released. As the brine flows, Fe re-precipitated because of pH increase. To better predict the fate and transport of aqueous pollutants, the nucleation and growth of Fe(III): hydr)oxides were studied. New information about sizes and volumes of the Fe(III): hydr)oxide nanoparticles precipitated in solution and on quartz, mica, and sapphire were provided using small angle X-ray scattering, in the presence of different ions: Al<super>3+</super>, Cl<super>-</super>, NO<sub>3</sub><super>-</super>, and SO<sub>4</sub><super>2-</super>). Using complementary techniques, the controlling mechanisms related to surface charge, bond formation, and interfacial energies were explored. These new findings can help better predict pollutant transport in aquifers not only at GCS sites, but also in managed aquifer recharge and acid mine drainage sites.</p>"],"dc:identifier":["https://openscholarship.wustl.edu/etd/1136"],"dc:identifier.doi":["https://doi.org/10.7936/K73776S1"],"dc:language":["English (en)"],"dc:title":["Roles of Nano- and Micro-Scale Subsurface Geochemical Reactions on Environmentally Sustainable Geologic CO2 Sequestration"],"thesis:degree_discipline":["Energy, Environmental and Chemical Engineering"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Doctor of Philosophy (PhD)"]},"updated_at":"2026-07-24T06:13:14Z"}