Smectites are one of the most important groups of phyllositicates found in soils and sediments, and certainly one of the most difficult to study. New information about the formation mechanisms, impact of structural features on surface properties, and long-term stability of smectites can best be gained from the systematic study of single-phase specimens. In most instances, these specimens can only be obtained through synthesis under controlled conditions. Syntheses of smectites have been attempted (1) at ambient pressure and low-temperature ( 1000~ or pressures >10 kbars), and (4) in the presence of fluoride. Of these approaches, syntheses performed under moderate hydrother- mal conditions are the most numerous and the most successful in terms of smectite yield and phase- purity. Using hydrothermal techniques, high phase-purity can be obtained for beidellites and several transition-metal smectites. However, synthesis of montmorillonite in high purity remains difficult. Starting materials for hydrothermal syntheses include gels, glasses, and other aluminosilicate minerals. The pres- ence of Mg 2+ seems to be essential for the formation of smectites, even for phases such as montmorillonite which contain low amounts of Mg. Highly crystalline smectites can be obtained when extreme temper- atures or pressures are used, but other crystalline impurities are always present. Although the correlation between synthesis stability fields and thermodynamic stability fields is good in many instances, metastable phases are often formed. Few studies, however, include the additional experiments (approach from under- and over-saturation, reversal experiments) needed to ascertain the conditions for formation of thermody- namically stable phases. Thorough characterization of synthetic products by modern instrumental and molecular-scale techniques is also needed to better understand the processes leading to smectite formation.

Synthesis of smectite clay minerals; a critical review

Modelling the interaction of bentonite with hyperalkaline fluids

A simple hydrothermal approach to modify palygorskite for high-efficient adsorption of Methylene blue and Cu(II) ions

Adsorption of basic dye from aqueous solutions by modified sepiolite: Equilibrium, kinetics and thermodynamics study

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.

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

The instability of palygorskite and sepiolite under soil conditions was investigated to determine if these fibrous minerals transform directly to smectite under laboratory conditions. The treatment of 100 mg (0.12 mmole) of palygorskite with 1 mmole of NaOH solution (17 ml) at 150~ for 24 hr yielded a smectite. Analcime and smectite were formed when -> 3 mmole of NaOH was used. The addition of - 8 mmole NaOH, sepiolite altered to an X-ray amorphous material. In the presence of A1 and Si, however, it transformed to smectite and analcime. Transmission electron microscopy, cation-exchange capacity, and X-ray powder diffraction studies of the products suggest that alteration was (1) via solution, or (2) by a structural reorganization wherein the basic 2:1 silicate structural units were unchanged. Key Wards--Alteration, Analcime, Cation-exchange capacity, Palygorskite, Sepiolite, Smectite, Sodium hydroxide.

L. A. Kippenberger

Papers

Palygorskite and sepiolite alteration to smectite under alkaline conditions