The sequence of mineral reactions involving zeolites and other authigenic phases in tuffaceous sedimentary rocks can be explained by growth- and dissolution-reaction kinetics. Kinetic factors may determine the specific authigenic phases which form and the temporal and spatial constraints on the solution composition during irreversible dissolution and growth reactions in glass-bearing rocks. The glass phase generates a high level of supersaturation with respect to a variety of aluminosilicates in the pore fluid. The sequence of assemblages formed during a series of metastable reactions resembles an Ostwald step sequence. Metastable reactions occur because formation of less stable phases such as gels, clays, and disordered zeolites may lower the total free energy of the glass-bearing system faster than the growth of the stable assemblage including ordered feldspars, quartz, and micas. Eventually, after a series of steps, the most stable silicate assemblage for the bulk composition, temperature, and pressure may form. However, the formation of intermediate metastable phases can delay the attainment of equilibrium by as much as tens of millions of years.

Experiments to explore the dissolution behaviour of Pb-rich orthoclase (1% PbO) and quartz have been carried out in the presence of pH buffered and unbuffered potassium acetate and lithium acetate solutions at 150°C and 50 MPa (500 bars). In pH-unbuffered potassium acetate solutions Pb and Na solubilities (and pH) increase with increasing fluid acetate content, reflecting increased bulk dissolution of the feldspar; silica solubility decreases despite an increase in measured pH from 7.5 to 8.9. Similarly, in experiments at pH 6 using a potassium acetate pH buffer, quartz solubility decreases with increasing acetate content. The use of lithium acetate pH buffers (pH 6 at 25°C) in experiments with orthoclase plus quartz results in the precipitation of the lithium chlorite cookeite, complicating interpretation of the fluid chemistry. It is also apparent that in the presence of orthoclase plus quartz (but not albite alone) acetate decarboxylation takes place at much higher rates than expected for the experimental configuration used. The observed effects are unlikely to be due to the presence of acetate alone; the influence of species produced by acetate decay (especially carbonate) must also be considered. This study provides little support for models which call upon acetate to enhance the solubility of aluminosilicate minerals, and suggests that acetate decarboxylation in nature may limit its involvement in dissolution processes. It emphasises the potential of feldspars as sources of elements for mineralisation, such as Pb.