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The effect of iron on montmorillonite stability. (II) Experimental investigation

The effect of iron on montmorillonite stability. (II) Experimental investigation
The effect of iron on montmorillonite stability. (II) Experimental investigation
Several designs proposed for high-level nuclear waste (HLW) repositories include steel waste canisters surrounded by montmorillonite clay. This work investigates montmorillonite stability in the presence of native Fe, magnetite and aqueous solutions under hydrothermal conditions. Two series of experiments were conducted. In the first, mixtures of Na-montmorillonite, magnetite, native Fe, calcite, and NaCl solutions were reacted at 250 degrees C, P-sat for between 93 and 114 days. In the second series, the starting mixtures included Na-montmorillonite, native Fe and solutions of FeCl2 Which were reacted at temperatures of 80, 150, and 250 degrees C, P-sat, for 90-92 days. Experiments were analysed using XRD, FT-IR, TEM, ICP-AES, and ICP-MS. In the first series of experiments, native Fe oxidised to produce magnetite and the starting montmorillonite material was transformed to Fe-rich smectite only when the Fe was added predominantly as Fe metal rather than Fe oxide (magnetite). The Fe-rich smectite was initially Fe(II)-rich, which oxidised to produce an Fe(III)-rich form on exposure to air. The expansion of this material on ethylene glycol solvation was much reduced compared to the montmorillonite starting material. TEM imaging shows that partial loss of tetrahedral sheets occurred during transformation of the montmorillonite, resulting in adjacent layers becoming H-bonded with a 7 Å repeat. The reduced swelling property of the Fe-smectite product may be due predominantly to the structural disruption of smectite layers and the formation of H-bonds. Solute activities corresponded to the approximate stability field calculated for hypothetical Fe(II)-saponite. In the second series of experiments, significant smectite alteration was only observed at 250 degrees C and the product contained a small proportion of a 7 Å repeat structure, observable by XRD. In these experiments, solute activities coincide with berthierine. The experiments indicate that although bentonite is still a desirable choice of backfill material for HLW repositories, some loss of expandability may result if montmorillonite is altered to Fe-rich smectite at the interface between steel canisters and bentonite.
ferruginous smectite, nontronite, fe, mossbauer, temperatures, adsorption, reduction, minerals, chlorite, saponite
0016-7037
323-336
Wilson, James
aec7fd40-41c6-4f44-a1b0-ff60f03676b5
Cressey, Gordon
d268e134-86d0-467c-ac34-ce6e6916fd36
Cressey, Barbara
55c72b25-9179-4338-ac8f-c71f7613d44e
Cuadros, Javier
46076ae2-ede2-49a6-84c5-b2d7b3402aa7
Ragnarsdottir, K. Vala
57404743-7b8a-4bc4-bc76-9ca53e0396a6
Savage, David
540d892d-13b0-43ca-b0d5-0444e7e43fdc
Shibata, Masahiro
c019ac7f-68f2-40b7-a2c6-a16b5f51137f
Wilson, James
aec7fd40-41c6-4f44-a1b0-ff60f03676b5
Cressey, Gordon
d268e134-86d0-467c-ac34-ce6e6916fd36
Cressey, Barbara
55c72b25-9179-4338-ac8f-c71f7613d44e
Cuadros, Javier
46076ae2-ede2-49a6-84c5-b2d7b3402aa7
Ragnarsdottir, K. Vala
57404743-7b8a-4bc4-bc76-9ca53e0396a6
Savage, David
540d892d-13b0-43ca-b0d5-0444e7e43fdc
Shibata, Masahiro
c019ac7f-68f2-40b7-a2c6-a16b5f51137f

Wilson, James, Cressey, Gordon, Cressey, Barbara, Cuadros, Javier, Ragnarsdottir, K. Vala, Savage, David and Shibata, Masahiro (2006) The effect of iron on montmorillonite stability. (II) Experimental investigation. Geochimica et Cosmochimica Acta, 70 (2), 323-336. (doi:10.1016/j.gca.2005.09.023).

Record type: Article

Abstract

Several designs proposed for high-level nuclear waste (HLW) repositories include steel waste canisters surrounded by montmorillonite clay. This work investigates montmorillonite stability in the presence of native Fe, magnetite and aqueous solutions under hydrothermal conditions. Two series of experiments were conducted. In the first, mixtures of Na-montmorillonite, magnetite, native Fe, calcite, and NaCl solutions were reacted at 250 degrees C, P-sat for between 93 and 114 days. In the second series, the starting mixtures included Na-montmorillonite, native Fe and solutions of FeCl2 Which were reacted at temperatures of 80, 150, and 250 degrees C, P-sat, for 90-92 days. Experiments were analysed using XRD, FT-IR, TEM, ICP-AES, and ICP-MS. In the first series of experiments, native Fe oxidised to produce magnetite and the starting montmorillonite material was transformed to Fe-rich smectite only when the Fe was added predominantly as Fe metal rather than Fe oxide (magnetite). The Fe-rich smectite was initially Fe(II)-rich, which oxidised to produce an Fe(III)-rich form on exposure to air. The expansion of this material on ethylene glycol solvation was much reduced compared to the montmorillonite starting material. TEM imaging shows that partial loss of tetrahedral sheets occurred during transformation of the montmorillonite, resulting in adjacent layers becoming H-bonded with a 7 Å repeat. The reduced swelling property of the Fe-smectite product may be due predominantly to the structural disruption of smectite layers and the formation of H-bonds. Solute activities corresponded to the approximate stability field calculated for hypothetical Fe(II)-saponite. In the second series of experiments, significant smectite alteration was only observed at 250 degrees C and the product contained a small proportion of a 7 Å repeat structure, observable by XRD. In these experiments, solute activities coincide with berthierine. The experiments indicate that although bentonite is still a desirable choice of backfill material for HLW repositories, some loss of expandability may result if montmorillonite is altered to Fe-rich smectite at the interface between steel canisters and bentonite.

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Published date: 2006
Keywords: ferruginous smectite, nontronite, fe, mossbauer, temperatures, adsorption, reduction, minerals, chlorite, saponite

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Local EPrints ID: 44567
URI: http://eprints.soton.ac.uk/id/eprint/44567
ISSN: 0016-7037
PURE UUID: 2c31c961-dbd8-4277-8caf-774e06fe3dba

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Date deposited: 07 Mar 2007
Last modified: 13 Mar 2019 21:07

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Contributors

Author: James Wilson
Author: Gordon Cressey
Author: Barbara Cressey
Author: Javier Cuadros
Author: K. Vala Ragnarsdottir
Author: David Savage
Author: Masahiro Shibata

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