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A Geo‐Structurally Based Correction Factor for Apparent Dissolution Rates in Fractured Media
Field measurements of apparent geochemical weathering reaction rates in subsurface fractured porous media are known to deviate from laboratory measurements by multiple orders of magnitude. To date, there is no geologically based explanation for this discrepancy that can be used to predict reaction r...
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Published in: | Geophysical research letters 2022-08, Vol.49 (15), p.n/a |
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description | Field measurements of apparent geochemical weathering reaction rates in subsurface fractured porous media are known to deviate from laboratory measurements by multiple orders of magnitude. To date, there is no geologically based explanation for this discrepancy that can be used to predict reaction rates in field systems. Proposed correction factors are typically based on ad hoc characterizations related to geochemical kinetic models. Through a series of high‐fidelity reactive transport simulations of mineral dissolution within explicit 3D discrete fracture networks, we are able to link the geo‐structural attributes with reactive transport observations. We develop a correction factor to linear transition state theory for the prediction of the apparent dissolution rate based on measurable geological properties. The modified rate law shows excellent agreement with numerical simulations, indicating that geological structure could be a primary reason for the discrepancy between laboratory and field observations of apparent dissolution rates in fractured media.
Plain Language Summary
Fractures are the principal conduits for fluid flow through low permeability rock in the Earth's subsurface. In many of these systems, fluids passing through the fractures are out of equilibrium with the resident minerals, and various reactions, such as dissolution and precipitation, occur. These geochemical processes change the fracture permeability and drive fracture propagation, thereby dynamically changing flows. Field measurements of apparent geochemical weathering reaction rates are lower than laboratory measurements by multiple orders of magnitude, which makes predictions of geochemical reaction rates highly uncertain. These slow apparent dissolution rates are particularly pronounced in fracture networks where geo‐structural attributes, for example, the network connectivity and fracture geometry, determine the flow field structure and dictate transport. Through a series of high‐fidelity reactive transport simulations of mineral dissolution in fractured media, we uncovered a new link between the geo‐structural attributes of the underlying fracture network with reactive transport observations. Guided by this information, we develop a correction factor to linear transition state theory to predict the apparent dissolution rate that is based on these geological attributes. The excellent agreement of the proposed model with our numerical simulations indicates that geological struct |
doi_str_mv | 10.1029/2022GL099513 |
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Plain Language Summary
Fractures are the principal conduits for fluid flow through low permeability rock in the Earth's subsurface. In many of these systems, fluids passing through the fractures are out of equilibrium with the resident minerals, and various reactions, such as dissolution and precipitation, occur. These geochemical processes change the fracture permeability and drive fracture propagation, thereby dynamically changing flows. Field measurements of apparent geochemical weathering reaction rates are lower than laboratory measurements by multiple orders of magnitude, which makes predictions of geochemical reaction rates highly uncertain. These slow apparent dissolution rates are particularly pronounced in fracture networks where geo‐structural attributes, for example, the network connectivity and fracture geometry, determine the flow field structure and dictate transport. Through a series of high‐fidelity reactive transport simulations of mineral dissolution in fractured media, we uncovered a new link between the geo‐structural attributes of the underlying fracture network with reactive transport observations. Guided by this information, we develop a correction factor to linear transition state theory to predict the apparent dissolution rate that is based on these geological attributes. The excellent agreement of the proposed model with our numerical simulations indicates that geological structure could be one of the reasons for the commonly observed discrepancy.
Key Points
Observations of apparent reaction rates in fractured media are orders of magnitude lower than those measured in laboratory conditions
Reactive transport simulations are used to characterize the influence of 3D fracture network structure on apparent dissolution rates
A geo‐structurally based modification to linear transition state theory for the prediction of the apparent dissolution rate is presented</description><identifier>ISSN: 0094-8276</identifier><identifier>EISSN: 1944-8007</identifier><identifier>DOI: 10.1029/2022GL099513</identifier><language>eng</language><publisher>Washington: John Wiley & Sons, Inc</publisher><subject>Accuracy ; apparent dissolution rates ; Crack propagation ; Dissolution ; Dissolving ; Fluid dynamics ; Fluid flow ; Fluids ; Fracture mechanics ; fracture network ; Fracture permeability ; Geochemistry ; Geological structures ; Geology ; GEOSCIENCES ; Laboratories ; Mathematical models ; Minerals ; Numerical simulations ; Permeability ; Porous media ; reactive transport modeling ; Simulation ; subsurface flow and transport ; Transport ; Weathering</subject><ispartof>Geophysical research letters, 2022-08, Vol.49 (15), p.n/a</ispartof><rights>2022. The Authors.</rights><rights>2022. This article is published under http://creativecommons.org/licenses/by-nc-nd/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a3942-9350d42126f6e9008cf90e89347de4fac5f51269feddc54f09ba7bf9df056f763</citedby><cites>FETCH-LOGICAL-a3942-9350d42126f6e9008cf90e89347de4fac5f51269feddc54f09ba7bf9df056f763</cites><orcidid>0000-0001-7847-6293 ; 0000-0002-5160-4176 ; 0000-0002-4224-2847 ; 0000-0002-1980-4020 ; 0000-0002-0851-0094 ; 0000-0001-8488-2925 ; 0000-0002-1178-9647 ; 0000000242242847 ; 0000000208510094 ; 0000000211789647 ; 0000000178476293 ; 0000000219804020 ; 0000000251604176 ; 0000000184882925</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1029%2F2022GL099513$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1029%2F2022GL099513$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>230,314,776,780,881,11493,27901,27902,46443,46867</link.rule.ids><backlink>$$Uhttps://www.osti.gov/biblio/1881360$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Hyman, Jeffrey D.</creatorcontrib><creatorcontrib>Navarre‐Sitchler, Alexis</creatorcontrib><creatorcontrib>Andrews, Elizabeth</creatorcontrib><creatorcontrib>Sweeney, Matthew R.</creatorcontrib><creatorcontrib>Karra, Satish</creatorcontrib><creatorcontrib>Carey, J. William</creatorcontrib><creatorcontrib>Viswanathan, Hari S.</creatorcontrib><creatorcontrib>Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)</creatorcontrib><title>A Geo‐Structurally Based Correction Factor for Apparent Dissolution Rates in Fractured Media</title><title>Geophysical research letters</title><description>Field measurements of apparent geochemical weathering reaction rates in subsurface fractured porous media are known to deviate from laboratory measurements by multiple orders of magnitude. To date, there is no geologically based explanation for this discrepancy that can be used to predict reaction rates in field systems. Proposed correction factors are typically based on ad hoc characterizations related to geochemical kinetic models. Through a series of high‐fidelity reactive transport simulations of mineral dissolution within explicit 3D discrete fracture networks, we are able to link the geo‐structural attributes with reactive transport observations. We develop a correction factor to linear transition state theory for the prediction of the apparent dissolution rate based on measurable geological properties. The modified rate law shows excellent agreement with numerical simulations, indicating that geological structure could be a primary reason for the discrepancy between laboratory and field observations of apparent dissolution rates in fractured media.
Plain Language Summary
Fractures are the principal conduits for fluid flow through low permeability rock in the Earth's subsurface. In many of these systems, fluids passing through the fractures are out of equilibrium with the resident minerals, and various reactions, such as dissolution and precipitation, occur. These geochemical processes change the fracture permeability and drive fracture propagation, thereby dynamically changing flows. Field measurements of apparent geochemical weathering reaction rates are lower than laboratory measurements by multiple orders of magnitude, which makes predictions of geochemical reaction rates highly uncertain. These slow apparent dissolution rates are particularly pronounced in fracture networks where geo‐structural attributes, for example, the network connectivity and fracture geometry, determine the flow field structure and dictate transport. Through a series of high‐fidelity reactive transport simulations of mineral dissolution in fractured media, we uncovered a new link between the geo‐structural attributes of the underlying fracture network with reactive transport observations. Guided by this information, we develop a correction factor to linear transition state theory to predict the apparent dissolution rate that is based on these geological attributes. The excellent agreement of the proposed model with our numerical simulations indicates that geological structure could be one of the reasons for the commonly observed discrepancy.
Key Points
Observations of apparent reaction rates in fractured media are orders of magnitude lower than those measured in laboratory conditions
Reactive transport simulations are used to characterize the influence of 3D fracture network structure on apparent dissolution rates
A geo‐structurally based modification to linear transition state theory for the prediction of the apparent dissolution rate is presented</description><subject>Accuracy</subject><subject>apparent dissolution rates</subject><subject>Crack propagation</subject><subject>Dissolution</subject><subject>Dissolving</subject><subject>Fluid dynamics</subject><subject>Fluid flow</subject><subject>Fluids</subject><subject>Fracture mechanics</subject><subject>fracture network</subject><subject>Fracture permeability</subject><subject>Geochemistry</subject><subject>Geological structures</subject><subject>Geology</subject><subject>GEOSCIENCES</subject><subject>Laboratories</subject><subject>Mathematical models</subject><subject>Minerals</subject><subject>Numerical simulations</subject><subject>Permeability</subject><subject>Porous media</subject><subject>reactive transport modeling</subject><subject>Simulation</subject><subject>subsurface flow and transport</subject><subject>Transport</subject><subject>Weathering</subject><issn>0094-8276</issn><issn>1944-8007</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><recordid>eNp9kM1KAzEUhYMoWKs7H2DQraM3P_OTZa12FCpC1a0hzSQ4ZZzUJIN05yP4jD6JqePClYvLvXC-ezgchI4xnGMg_IIAIdUcOM8w3UEjzBlLS4BiF40AeLxJke-jA-9XAECB4hF6niSVtl8fnw_B9Sr0TrbtJrmUXtfJ1DqnVWhsl8ykCtYlJs5kvZZOdyG5ary3bf-jL2TQPmki6OTWJX7f6bqRh2jPyNbro989Rk-z68fpTTq_r26nk3kqKWck5TSDmhFMcpNrDlAqw0GXnLKi1sxIlZksitzoulYZM8CXslgaXhvIclPkdIxOBl_rQyO8aoJWL8p2XcwvcFlimkOETgdo7exbr30QK9u7LuYSpIjVEVwwHKmzgVLOeu-0EWvXvEq3ERjEtmbxt-aIkwF_b1q9-ZcV1WKeszwj9BvG834X</recordid><startdate>20220816</startdate><enddate>20220816</enddate><creator>Hyman, Jeffrey D.</creator><creator>Navarre‐Sitchler, Alexis</creator><creator>Andrews, Elizabeth</creator><creator>Sweeney, Matthew R.</creator><creator>Karra, Satish</creator><creator>Carey, J. William</creator><creator>Viswanathan, Hari S.</creator><general>John Wiley & Sons, Inc</general><general>American Geophysical Union (AGU)</general><scope>24P</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TG</scope><scope>7TN</scope><scope>8FD</scope><scope>F1W</scope><scope>FR3</scope><scope>H8D</scope><scope>H96</scope><scope>KL.</scope><scope>KR7</scope><scope>L.G</scope><scope>L7M</scope><scope>OTOTI</scope><orcidid>https://orcid.org/0000-0001-7847-6293</orcidid><orcidid>https://orcid.org/0000-0002-5160-4176</orcidid><orcidid>https://orcid.org/0000-0002-4224-2847</orcidid><orcidid>https://orcid.org/0000-0002-1980-4020</orcidid><orcidid>https://orcid.org/0000-0002-0851-0094</orcidid><orcidid>https://orcid.org/0000-0001-8488-2925</orcidid><orcidid>https://orcid.org/0000-0002-1178-9647</orcidid><orcidid>https://orcid.org/0000000242242847</orcidid><orcidid>https://orcid.org/0000000208510094</orcidid><orcidid>https://orcid.org/0000000211789647</orcidid><orcidid>https://orcid.org/0000000178476293</orcidid><orcidid>https://orcid.org/0000000219804020</orcidid><orcidid>https://orcid.org/0000000251604176</orcidid><orcidid>https://orcid.org/0000000184882925</orcidid></search><sort><creationdate>20220816</creationdate><title>A Geo‐Structurally Based Correction Factor for Apparent Dissolution Rates in Fractured Media</title><author>Hyman, Jeffrey D. ; Navarre‐Sitchler, Alexis ; Andrews, Elizabeth ; Sweeney, Matthew R. ; Karra, Satish ; Carey, J. William ; Viswanathan, Hari S.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a3942-9350d42126f6e9008cf90e89347de4fac5f51269feddc54f09ba7bf9df056f763</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><topic>Accuracy</topic><topic>apparent dissolution rates</topic><topic>Crack propagation</topic><topic>Dissolution</topic><topic>Dissolving</topic><topic>Fluid dynamics</topic><topic>Fluid flow</topic><topic>Fluids</topic><topic>Fracture mechanics</topic><topic>fracture network</topic><topic>Fracture permeability</topic><topic>Geochemistry</topic><topic>Geological structures</topic><topic>Geology</topic><topic>GEOSCIENCES</topic><topic>Laboratories</topic><topic>Mathematical models</topic><topic>Minerals</topic><topic>Numerical simulations</topic><topic>Permeability</topic><topic>Porous media</topic><topic>reactive transport modeling</topic><topic>Simulation</topic><topic>subsurface flow and transport</topic><topic>Transport</topic><topic>Weathering</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Hyman, Jeffrey D.</creatorcontrib><creatorcontrib>Navarre‐Sitchler, Alexis</creatorcontrib><creatorcontrib>Andrews, Elizabeth</creatorcontrib><creatorcontrib>Sweeney, Matthew R.</creatorcontrib><creatorcontrib>Karra, Satish</creatorcontrib><creatorcontrib>Carey, J. William</creatorcontrib><creatorcontrib>Viswanathan, Hari S.</creatorcontrib><creatorcontrib>Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)</creatorcontrib><collection>Open Access: Wiley-Blackwell Open Access Journals</collection><collection>CrossRef</collection><collection>Meteorological & Geoastrophysical Abstracts</collection><collection>Oceanic Abstracts</collection><collection>Technology Research Database</collection><collection>ASFA: Aquatic Sciences and Fisheries Abstracts</collection><collection>Engineering Research Database</collection><collection>Aerospace Database</collection><collection>Aquatic Science & Fisheries Abstracts (ASFA) 2: Ocean Technology, Policy & Non-Living Resources</collection><collection>Meteorological & Geoastrophysical Abstracts - Academic</collection><collection>Civil Engineering Abstracts</collection><collection>Aquatic Science & Fisheries Abstracts (ASFA) Professional</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>OSTI.GOV</collection><jtitle>Geophysical research letters</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Hyman, Jeffrey D.</au><au>Navarre‐Sitchler, Alexis</au><au>Andrews, Elizabeth</au><au>Sweeney, Matthew R.</au><au>Karra, Satish</au><au>Carey, J. William</au><au>Viswanathan, Hari S.</au><aucorp>Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A Geo‐Structurally Based Correction Factor for Apparent Dissolution Rates in Fractured Media</atitle><jtitle>Geophysical research letters</jtitle><date>2022-08-16</date><risdate>2022</risdate><volume>49</volume><issue>15</issue><epage>n/a</epage><issn>0094-8276</issn><eissn>1944-8007</eissn><abstract>Field measurements of apparent geochemical weathering reaction rates in subsurface fractured porous media are known to deviate from laboratory measurements by multiple orders of magnitude. To date, there is no geologically based explanation for this discrepancy that can be used to predict reaction rates in field systems. Proposed correction factors are typically based on ad hoc characterizations related to geochemical kinetic models. Through a series of high‐fidelity reactive transport simulations of mineral dissolution within explicit 3D discrete fracture networks, we are able to link the geo‐structural attributes with reactive transport observations. We develop a correction factor to linear transition state theory for the prediction of the apparent dissolution rate based on measurable geological properties. The modified rate law shows excellent agreement with numerical simulations, indicating that geological structure could be a primary reason for the discrepancy between laboratory and field observations of apparent dissolution rates in fractured media.
Plain Language Summary
Fractures are the principal conduits for fluid flow through low permeability rock in the Earth's subsurface. In many of these systems, fluids passing through the fractures are out of equilibrium with the resident minerals, and various reactions, such as dissolution and precipitation, occur. These geochemical processes change the fracture permeability and drive fracture propagation, thereby dynamically changing flows. Field measurements of apparent geochemical weathering reaction rates are lower than laboratory measurements by multiple orders of magnitude, which makes predictions of geochemical reaction rates highly uncertain. These slow apparent dissolution rates are particularly pronounced in fracture networks where geo‐structural attributes, for example, the network connectivity and fracture geometry, determine the flow field structure and dictate transport. Through a series of high‐fidelity reactive transport simulations of mineral dissolution in fractured media, we uncovered a new link between the geo‐structural attributes of the underlying fracture network with reactive transport observations. Guided by this information, we develop a correction factor to linear transition state theory to predict the apparent dissolution rate that is based on these geological attributes. The excellent agreement of the proposed model with our numerical simulations indicates that geological structure could be one of the reasons for the commonly observed discrepancy.
Key Points
Observations of apparent reaction rates in fractured media are orders of magnitude lower than those measured in laboratory conditions
Reactive transport simulations are used to characterize the influence of 3D fracture network structure on apparent dissolution rates
A geo‐structurally based modification to linear transition state theory for the prediction of the apparent dissolution rate is presented</abstract><cop>Washington</cop><pub>John Wiley & Sons, Inc</pub><doi>10.1029/2022GL099513</doi><tpages>12</tpages><orcidid>https://orcid.org/0000-0001-7847-6293</orcidid><orcidid>https://orcid.org/0000-0002-5160-4176</orcidid><orcidid>https://orcid.org/0000-0002-4224-2847</orcidid><orcidid>https://orcid.org/0000-0002-1980-4020</orcidid><orcidid>https://orcid.org/0000-0002-0851-0094</orcidid><orcidid>https://orcid.org/0000-0001-8488-2925</orcidid><orcidid>https://orcid.org/0000-0002-1178-9647</orcidid><orcidid>https://orcid.org/0000000242242847</orcidid><orcidid>https://orcid.org/0000000208510094</orcidid><orcidid>https://orcid.org/0000000211789647</orcidid><orcidid>https://orcid.org/0000000178476293</orcidid><orcidid>https://orcid.org/0000000219804020</orcidid><orcidid>https://orcid.org/0000000251604176</orcidid><orcidid>https://orcid.org/0000000184882925</orcidid><oa>free_for_read</oa></addata></record> |
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subjects | Accuracy apparent dissolution rates Crack propagation Dissolution Dissolving Fluid dynamics Fluid flow Fluids Fracture mechanics fracture network Fracture permeability Geochemistry Geological structures Geology GEOSCIENCES Laboratories Mathematical models Minerals Numerical simulations Permeability Porous media reactive transport modeling Simulation subsurface flow and transport Transport Weathering |
title | A Geo‐Structurally Based Correction Factor for Apparent Dissolution Rates in Fractured Media |
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