Influence of heterogeneity and sampling method on aqueous concentrations associated with NAPL dissolution

The purpose of this work is to examine the effects of nonuniform distributi ons of nonaqueous-phase liquid (NAPL) saturation, porous-media heterogeneit y, and sampling method on the magnitude of aqueous concentrations measured under dynamic conditions of flow and transport. Dissolution experiments wer e conducted in an intermediate-scale flow cell packed with sand in which tw o zones of residual trichloroethene (TCE) saturation were placed. One was c reated in the same medium-grained sand as used for the flow cell matrix (zo ne 2), and the other was created in finer sand (zone 1), Aqueous samples we re collected using depth-specific sampling ports, vertically integrated sam pling ports, and at the fully screened extraction well. A dual-energy gamma -radiation system was used to measure TCE saturation before and after the e xperiment. The results indicate that mass removal occurred relatively unifo rmly across the upgradient edge of zone 2 and continued progressively along the longitudinal axis of the zone throughout the course of flushing. Conve rsely, mass removal was confined primarily to the perimeter of zone 1. The magnitude of the aqueous-phase TCE concentrations varied as a function of l ocation and sampling method. The concentrations measured at the point-sampl ing ports downgradient of zone 2 were close to the value of aqueous solubil ity. Conversely, the concentrations measured at the point-sampling ports do wngradient of zone 1 were about one-fourth of solubility. The TCE concentra tions measured at the vertically integrated ports and at the extraction wel l were significantly less than the concentrations measured at the point-sam pling ports. Given that substantial TCE saturation remained at the end of t he experiment, the less than solubility concentrations observed for zone 1 and for the extraction well appear to reflect in part a steady-state dynami c equilibrium with the physical heterogeneity-induced nonuniform flow field . The less than solubility concentrations, especially for the integrated po rts and the extraction well, were also influenced significantly by sampling -associated dilution related to the nonuniform NAPL distribution. These obs ervations are supported by the results of a nonreactive tracer test, by the results of a dye-tracer test, and by a quantitative analysis of flow and t racer transport obtained using a three-dimensional mathematical model.