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Alteration of bentonite by hyperalkaline fluids : a review of the role of secondary minerals

By David Savage, Colin Walker, Randy Arthur, Christopher Rochelle, Chie Oda and Hiro Takase


Data concerning potential solid products of the interaction of cement pore fluids with bentonite have been reviewed with respect to accurate prediction of bentonite alteration in the long-term. Calcium (aluminium) silicate hydrates (C(A)SH), zeolites, feldspars, hydroxides, carbonates, polymorphs of silica, and some sheet silicates (all of varying degrees of crystallinity) are potential products of cement–bentonite interaction. Evidence from natural systems and laboratory studies suggests that most, or all of these phases, may precipitate on timescales of interest to safety assessment of the geological disposal of radioactive wastes. These data indicate that growth kinetics of secondary minerals is equally as important as thermodynamic stability in controlling occurrence. C(A)SH show variable Ca/Si ratio and Al contents. At high pH (>11), the growth of C(A)SH minerals provides a means by which OH− ions from cement pore fluids may be titrated. Although thermodynamic data exist for a number of naturally-occurring crystalline C(A)SH minerals, they are of doubtful quality and should be applied with caution in predictive modelling. Zeolites are likely to form at lower pH than for C(A)SH, with the Si/Al ratio of the zeolite decreasing with increasing pH of the fluid. Zeolite stability is also strongly dependent upon silica activity in the fluid phase. Although silica activity in bentonite pore fluids will be spatially (and temporally) variable as hyperalkaline alteration proceeds, it is likely that minerals which could form would be those stable in quartz-saturated or supersaturated fluids. Currently available thermodynamic data for zeolites tend to overestimate their stability, leading to inaccurate predictions of their occurrence. Notwithstanding this uncertainty, it is considered that the following secondary minerals are the most likely to form in low temperature cement–bentonite systems: calcite, dolomite, chalcedony, C(A)SH of variable Ca/Si ratio, K-feldspar, illite, phillipsite, analcime, clinoptilolite, and heulandite. The relatively more siliceous zeolites (clinoptilolite, phillipsite) are likely to form at lower pH (distal regions of migrating cement pore fluids), whereas C(A)SH, illite, feldspars, and the more aluminous zeolites (analcime, heulandite) are more likely to form at higher pH and hence, the more proximal regions of migrating cement pore fluids. Predominantly Na-, K-bearing solids will be transformed to those dominated by Ca as the composition of cement pore fluids evolves with time

Topics: Earth Sciences
Publisher: Pergamon
Year: 2007
DOI identifier: 10.1016/j.pce.2005.08.048
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