Combined physical and chemical nonequilibrium transport model for solution conduits

Abstract

Solute transport in karst aquifers is primarily constrained to relatively complex and inaccessible solution conduits where transport is often rapid, turbulent, and at times constrictive. Breakthrough curves generated from tracer tests in solution conduits are typically positively-skewed with long tails evident. Physical nonequilibrium models to fit breakthrough curves for tracer tests in solution conduits are now routinely employed. Chemical nonequilibrium processes are likely important interactions, however. In addition to partitioning between different flow domains, there may also be equilibrium and nonequilibrium partitioning between the aqueous and solid phases. A combined physical and chemical nonequilibrium (PCNE) model was developed for an instantaneous release similar to that developed by Leij and Bradford (2009) for a pulse release. The PCNE model allows for partitioning open space in solution conduits into mobile and immobile flow regions with first-order mass transfer between the two regions to represent physical nonequilibrium in the conduit. Partitioning between the aqueous and solid phases proceeds either as an equilibrium process or as a first-order process and represents chemical nonequilibrium for both the mobile and immobile regions. Application of the model to three example breakthrough curves demonstrates the applicability of the combined physical and chemical nonequilibrium model to tracer tests conducted in karst aquifers, with exceptionally good model fits to the data. The three models, each from a different state in the United States, exhibit very different velocities, dispersions, and other transport properties with most of the transport occurring via the fraction of mobile water. Fitting the model suggests the potentially important interaction of physical and chemical nonequilibrium processes.