Rate constants of dissolution derived from the measurements of mass balance in hydrological catchments

The experimental rate constant of dissolution of oligoclase, 1.7 × 10 ^{? 2} mol · m^?2 · s^?1 (Busenberg and Clemency, 1976), is compared with rate constants, 5.2 × 10^?15 to 6.8 × 10^?13 mol · m^?2· s^?1, derived from mass-balance measurements of sodium in hydrological catchments. The wide range of the field-based rate constants mainly reflects the uncertainty in the evaluation of the specific wetted surface of rock in aquifer. The most probable order of magnitude of the field rate constant is 10^?14 mol · m^?2· s^?1. The difference between the experimental and field rate constant is only partly caused by lower temperature and lowerP_CO2 in the aquifer. The main reason for the discrepancy is the diverse history of the mineral surfaces undergoing reaction.It is suggested that the feldspar surfaces in an aquifer are old, compared to those of feldspars utilized in laboratory experiments. They have fewer defects and are smooth. The fresh surfaces of feldspars studied in the laboratory consist of many kinks and ledges and small-area terraces which dissolve faster.The differences in rate constants derived from field data on several specific catchments indicate that the anthropogenic processes which have operated during this century in Central Europe speed up the rate of dissolution by a factor of three. Modern agricultural practices speed up the rate by a factor of five.