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Title: Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

Abstract

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium (U) concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this work, the dissolution rates of K- and Na-compreignacite (K2(UO2)6O4(OH)6·8H2O and Na2(UO2)6O4(OH)6·8H2O, respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved carbonate concentration (ca. 0.2 and 2.8 mmol L-1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area, and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disorderedmore » K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58–87% of total U mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved U was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates (normalized to specific surface area) were 2.5–3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57 · 10-10 vs. 1.28 · 10-13 mol m-2 s-1[log R = -9.81 and -12.89] and 5.79 · 10-10 vs. 3.71 · 10-13 mol m-2 s-1[log R = -9.24 and -12.43] for K- and Na-compreignacite, respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for U mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. This study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as U in porous geomedia.« less

Authors:
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Publication Date:
Research Org.:
Univ. of Arizona, Tucson, AZ (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Contributing Org.:
Univ. of California, Merced, CA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
OSTI Identifier:
1349074
Alternate Identifier(s):
OSTI ID: 1397796; OSTI ID: 1468341
Grant/Contract Number:  
SC0006781; SBR-DE-SC0006781; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Geochimica et Cosmochimica Acta
Additional Journal Information:
Journal Volume: 207; Journal Issue: C; Journal ID: ISSN 0016-7037
Publisher:
The Geochemical Society; The Meteoritical Society
Country of Publication:
United States
Language:
English
Subject:
58 GEOSCIENCES; Uranyl oxyhydroxides; compreignacite; dissolution rate; reactive transport; EXAFS

Citation Formats

Reinoso-Maset, Estela, Steefel, Carl I., Um, Wooyong, Chorover, Jon, and O'Day, Peggy A. Rates and mechanisms of uranyl oxyhydroxide mineral dissolution. United States: N. p., 2017. Web. doi:10.1016/j.gca.2017.03.009.
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Reinoso-Maset, Estela, Steefel, Carl I., Um, Wooyong, Chorover, Jon, & O'Day, Peggy A. Rates and mechanisms of uranyl oxyhydroxide mineral dissolution. United States. https://doi.org/10.1016/j.gca.2017.03.009
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Reinoso-Maset, Estela, Steefel, Carl I., Um, Wooyong, Chorover, Jon, and O'Day, Peggy A. Thu . "Rates and mechanisms of uranyl oxyhydroxide mineral dissolution". United States. https://doi.org/10.1016/j.gca.2017.03.009. https://www.osti.gov/servlets/purl/1349074.
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@article{osti_1349074,
title = {Rates and mechanisms of uranyl oxyhydroxide mineral dissolution},
author = {Reinoso-Maset, Estela and Steefel, Carl I. and Um, Wooyong and Chorover, Jon and O'Day, Peggy A.},
abstractNote = {Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium (U) concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this work, the dissolution rates of K- and Na-compreignacite (K2(UO2)6O4(OH)6·8H2O and Na2(UO2)6O4(OH)6·8H2O, respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved carbonate concentration (ca. 0.2 and 2.8 mmol L-1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area, and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58–87% of total U mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved U was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates (normalized to specific surface area) were 2.5–3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57 · 10-10 vs. 1.28 · 10-13 mol m-2 s-1[log R = -9.81 and -12.89] and 5.79 · 10-10 vs. 3.71 · 10-13 mol m-2 s-1[log R = -9.24 and -12.43] for K- and Na-compreignacite, respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for U mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. This study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as U in porous geomedia.},
doi = {10.1016/j.gca.2017.03.009},
journal = {Geochimica et Cosmochimica Acta},
number = C,
volume = 207,
place = {United States},
year = {Thu Jun 01 00:00:00 EDT 2017},
month = {Thu Jun 01 00:00:00 EDT 2017}
}
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https://doi.org/10.1016/j.gca.2017.03.009
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