Nonideal transport of reactive contaminants in heterogeneous porous media: 7. distributed-domain model incorporating immiscible-liquid dissolution and rate-limited sorption/desorption.
The purpose of this work is to present a distributed-domain mathematical model incorporating the primary mass-transfer processes that mediate the transport of immiscible organic liquid constituents in water-saturated, locally heterogeneous porous media. Specifically, the impact of grain/pore-scale heterogeneity on immiscible-liquid dissolution and sorption/desorption is represented in the model by describing the system as comprising a continuous distribution of mass-transfer domains. With this conceptualization, the distributions of the initial dissolution rate coefficient and the sorption/desorption rate coefficient are represented as probability density functions. Several sets of numerical experiments are conducted to examine the effects of heterogeneous dissolution and sorption/desorption on contaminant transport and elution. Four scenarios with different combinations of uniform/heterogeneous rate-limited dissolution and uniform/heterogeneous rate-limited sorption/desorption are evaluated. The results show that both heterogeneous rate-limited sorption/desorption and heterogeneous rate-limited dissolution can significantly increase the time or pore volumes required to elute immiscible-liquid constituents from a contaminated porous medium. However, sorption/desorption has minimal influence on elution behavior until essentially all of the immiscible liquid has been removed. For typical immiscible-liquid constituents that have relatively low sorption, the asymptotic elution tailing produced by heterogeneous rate-limited sorption/desorption begins at effluent concentrations that are several orders of magnitude below the initial steady-state concentrations associated with dissolution of the immiscible liquid. Conversely, the enhanced elution tailing associated with heterogeneous rate-limited dissolution begins at concentrations that are approximately one-tenth of the initial steady-state concentrations. Hence, dissolution may generally control elution behavior of immiscible-liquid constituents in cases wherein grain/pore-scale heterogeneity significantly influences both dissolution and sorption/desorption.
Zhang
Zhihui
Z
Department of Soil, Water, and Environmental Science, The University of Arizona, 429 Shantz Building, 38, Tucson, AZ 85721, USA.
Brusseau
Mark L
ML
D000327:Adsorption; D007700:Kinetics; D008962:Models, Theoretical; D010316:Particle Size; D016062:Porosity; D012989:Soil Pollutants / Q000032:analysis*; D012995:Solubility; D013499:Surface Properties; D014872:Water Movements; D014873:Water Pollutants / Q000032:analysis*
D012989:Soil Pollutants; D014873:Water Pollutants