Influence of Matrix Diffusion and Exchange Reactions on Radiocarbon Ages in Fissured Carbonate Aquifers

The parallel fissure model coupled with the equation of diffusion into the matrix and with exchange reaction equations has been used to derive a simple formula for estimating the influence of matrix porosity and reaction parameters on the determination of radiocarbon ages in fissured carbonate rocks. Examples of evidently too great radiocarbon ages in carbonate formations, which are not explainable by models for the initial 14C corrections, can easily be explained by this formula. Parameters obtained for a chalk formation from a known multitracer experiment combined with a pumping test suggest a possibility of 14C ages more than three orders of magnitude greater than the ages which would be observed if the radiocarbon transport took place only in the mobile water in the fissures. It is shown that contrary to the solute movement on a small scale and with a variable input, the large‐scale movement, characteristic for the 14C dating, does not necessarily require the knowledge of kinetic parameters, because they may be replaced by the distribution coefficient. Discordant tritium and 14C concentrations are commonly interpreted as a proof of mixing either in the aquifer or at the discharge site. For fissured carbonate formations, however, an alternative explanation is given by the derived model showing a considerable delay of 14C with respect to nonsorbable tracers.