Effects of Rate-Limited Mass Transfer on Modeling Vapor Intrusion with Aerobic Biodegradation.

Most of the models for simulating vapor intrusion accept the local equilibrium assumption for multiphase concentration distributions, that is, concentrations in solid, liquid and vapor phases are in equilibrium. For simulating vapor transport with aerobic biodegradation controlled by counter-diffusion processes, the local equilibrium assumption combined with dual-Monod kinetics and biomass decay may yield near-instantaneous behavior at steady state. The present research investigates how predicted concentration profiles and fluxes change as interphase mass transfer resistances are increased for vapor intrusion with aerobic biodegradation. Our modeling results indicate that the attenuation coefficients for cases with and without mass transfer limitations can be significantly different by orders of magnitude. Rate-limited mass transfer may lead to larger overlaps of contaminant vapor and oxygen concentrations, which cannot be simulated by instantaneous reaction models with local equilibrium mass transfer. In addition, the contaminant flux with rate-limited mass transfer is much smaller than that with local equilibrium mass transfer, indicating that local equilibrium mass transfer assumption may significantly overestimate the biodegradation rate and capacity for mitigating vapor intrusion through the unsaturated zone. Our results indicate a strong research need for field tests to examine the validity of local equilibrium mass transfer, a widely accepted assumption in modeling vapor intrusion.