The smectites present in some bentonites from the Island of Milos, Greece, derived from acidic rocks, have been examined by XRD and electron microprobe. The possible influence of loss of alkalis during analysis and contamination by fine grained Si-phases on microanalyses has also been evaluated. Smectites are closely associated with opal-CT and their composition ranges from beidellite to Tatatilla-type montmorillonite. Their chemistry is dominated by negative relationships between Mg and Al vi and Si and total Al. However, it cannot be resolved whether there is a solid-solution between the smectites or whether the variation observed is due to mechanical mixing of domains with different composition. The role of Fe is of minor importance reflecting an inherited factor imposed by the parent rock, but the role of the fluid phase is also important. Beidellite occurs in the rims, while Tatatilla-type montmorillonite, often associated with free opal-CT, is formed in the interior of the altered shards, indicating a variable degree of Si release during glass dissolution. The formation of beidellite is not necessarily associated with Mg uptake.

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