Abstract
The presence of solute concentration fluctuations at spatial scales much
below the working scale is a major challenge for modeling reactive
transport in porous media. Overlooking small-scale fluctuations, which
is the usual procedure, often results in strong disagreements between
field observations and model predictions, including, but not limited to,
the overestimation of effective reaction rates. Existing innovative
approaches that account for local reactant segregation do not provide a
general mathematical formulation for the generation, transport and decay
of these fluctuations and their impact on chemical reactions. We propose
a Lagrangian formulation based on the random motion of fluid particles
whose departure from the local mean concentration is relaxed through
multi-rate interaction by exchange with the mean (MRIEM). We derive and
analyze the macroscopic description of the local concentration
covariance that emerges from the model and show that mixing-limited
processes can be properly simulated. The action of hydrodynamic
dispersion on coarse-scale concentration gradients is responsible for
the production of local concentration covariance, whereas covariance
destruction stems from the local mixing process represented by the MRIEM
formulation. The temporal evolution of integrated mixing metrics in two
simple scenarios shows the trends that characterize fully-resolved
physical systems, such as a late-time power-law decay of the relative
importance of incomplete mixing with respect to the total mixing.
Experimental observations of mixing-limited reactive transport are
successfully reproduced by the model.