Determination of mineral dissolution regimes using flow-through time-resolved analysis (FT-TRA) and numerical simulation
Abstract
Flow-through time resolved analysis (FT-TRA) involves subjecting small mineral samples (< 10 mg) inserted in a miniature flow-through cell (50 μL) to controlled flows of eluent analyzed on-line by ICP-MS. In this study, FT-TRA is used to empirically determine the dissolution regimes for the two well-studied minerals forsterite and calcite, representing minerals with relatively slow and fast dissolution kinetics. A proportional increase in steady-state effluent [Mg, Si] concentrations with increasing flow-through cell eluent residence times confirms a dominantly surface-controlled dissolution regime for a powdered forsterite sample at pH 2.3, implying that transport limitations are negligible. In contrast, the relationship between flow rates and dissolution rates for single grain calcite samples at pH 2.3-4 reveals that transport limitations affect the rate of calcite dissolution. In order to provide a quantitative and process-based assessment of the effect of diffusive transport limitations, simulations of the calcite experiments were performed with a high resolution, pore-scale model that considers the geometry of the calcite grain and the FT-TRA flow-through reactor. The pore-scale model reproduces the observed effluent [Ca] concentrations for all experimental conditions using a single set of surface kinetic parameters, by accounting for the formation of a diffusive boundary layer (DBL) that varies inmore »
- Authors:
-
[1];
- University of British Columbia, Vancouver, BC (Canada)
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1474951
- Alternate Identifier(s):
- OSTI ID: 1358933
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemical Geology
- Additional Journal Information:
- Journal Volume: 430; Journal Issue: C; Related Information: © 2016 Elsevier B.V.; Journal ID: ISSN 0009-2541
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 58 GEOSCIENCES; dissolution regime; flow-through; mineral dissolution; dissolution rates; forsterite dissolution; calcite dissolution
Citation Formats
De Baere, Bart, Molins, Sergi, Mayer, K. Ulrich, and François, Roger. Determination of mineral dissolution regimes using flow-through time-resolved analysis (FT-TRA) and numerical simulation. United States: N. p., 2016.
Web. doi:10.1016/j.chemgeo.2016.03.014.
De Baere, Bart, Molins, Sergi, Mayer, K. Ulrich, & François, Roger. Determination of mineral dissolution regimes using flow-through time-resolved analysis (FT-TRA) and numerical simulation. United States. https://doi.org/10.1016/j.chemgeo.2016.03.014
De Baere, Bart, Molins, Sergi, Mayer, K. Ulrich, and François, Roger. Mon .
"Determination of mineral dissolution regimes using flow-through time-resolved analysis (FT-TRA) and numerical simulation". United States. https://doi.org/10.1016/j.chemgeo.2016.03.014. https://www.osti.gov/servlets/purl/1474951.
@article{osti_1474951,
title = {Determination of mineral dissolution regimes using flow-through time-resolved analysis (FT-TRA) and numerical simulation},
author = {De Baere, Bart and Molins, Sergi and Mayer, K. Ulrich and François, Roger},
abstractNote = {Flow-through time resolved analysis (FT-TRA) involves subjecting small mineral samples (< 10 mg) inserted in a miniature flow-through cell (50 μL) to controlled flows of eluent analyzed on-line by ICP-MS. In this study, FT-TRA is used to empirically determine the dissolution regimes for the two well-studied minerals forsterite and calcite, representing minerals with relatively slow and fast dissolution kinetics. A proportional increase in steady-state effluent [Mg, Si] concentrations with increasing flow-through cell eluent residence times confirms a dominantly surface-controlled dissolution regime for a powdered forsterite sample at pH 2.3, implying that transport limitations are negligible. In contrast, the relationship between flow rates and dissolution rates for single grain calcite samples at pH 2.3-4 reveals that transport limitations affect the rate of calcite dissolution. In order to provide a quantitative and process-based assessment of the effect of diffusive transport limitations, simulations of the calcite experiments were performed with a high resolution, pore-scale model that considers the geometry of the calcite grain and the FT-TRA flow-through reactor. The pore-scale model reproduces the observed effluent [Ca] concentrations for all experimental conditions using a single set of surface kinetic parameters, by accounting for the formation of a diffusive boundary layer (DBL) that varies in thickness as a function of flow rates. These results demonstrate that combining FT-TRA with pore-scale modeling makes it possible to obtain unprecedented insights not achievable by either method separately, including quantification of DBL thicknesses and the determination of transport controls as a function of pH, flow velocity and residence times.},
doi = {10.1016/j.chemgeo.2016.03.014},
journal = {Chemical Geology},
number = C,
volume = 430,
place = {United States},
year = {Mon Mar 21 00:00:00 EDT 2016},
month = {Mon Mar 21 00:00:00 EDT 2016}
}
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