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[1] Liquid-liquid equilibrium experiments indicate that there is a strong thermodynamic driving force for the reversible sequestration of cis-dichloroethene (DCE) within microbially active dense nonaqueous phase liquid (DNAPL) source zones containing chlorinated ethene solvents. Assessment of the importance of degradation product sequestration, however, requires accurate description of the mass transfer kinetics. Partitioning kinetics of cis-DCE were assessed in a series of transport experiments conducted in sandy columns containing uniformly entrapped tetrachloroethene (PCE)-nonaqueous phase liquids (NAPL). Effluent data from these experiments were simulated using an analytical solution adapted from the sorption literature. The solution permits interrogation of the relative importance of mass transfer resistance in the aqueous phase and NAPL. Column data and simulations suggest that the kinetic exchange of cis-DCE may be described with mass transfer correlations developed for the dissolution of pure component NAPLs. Diffusive transport within the entrapped ganglia was relatively fast, offering limited resistance to mass exchange. These results (1) establish the applicability of dissolution-based mass transfer correlations for modeling both absorption and dissolution of degradation products, (2) quantify the thermodynamic driving force for the partitioning of cis-DCE in PCE-NAPL by assessing the ternary phase behavior, and (3) guide incorporation and deployment of partitioning kinetics into multiphase compositional simulators when assessing or designing metabolic reductive dechlorination within DNAPL source zones. While focus is placed on examining degradation product partitioning in DNAPL source zones, results may also be useful when considering rate limitations in other liquid-liquid partitioning processes, such as partitioning tracer tests.

Analysis of partitioning tracer tests conducted in dense nonaqueous phase liquid (DNAPL) source zones relies on conceptual models that describe mass exchange between the DNAPL and aqueous phases. Such analysis, however, is complicated by the complex distribution of entrapped DNAPL mass and formation heterogeneity. Due to parameter uncertainty in heterogeneous regions and the desire to reduce model complexity, the effect of mass transfer limitations is often neglected, and an equilibrium-based model is typically used to interpret test results. This work explores the consequences of that simplifying assumption on test data interpretation and develops an alternative upscaled modeling approach to quantify effective mass transfer rates. To this end, a series of partitioning tracer tests is numerically simulated in heterogeneous two-dimensional PCE-DNAPL source zones, representative of a range of hydraulic conductivity and DNAPL mass distribution characteristics. The effective mass transfer coefficient corresponding to each test is determined by fitting an upscaled model to the simulated data, and regression analysis is performed to explore the correlation between various source zone metrics and the effective mass transfer coefficient. Results suggest that vertical DNAPL spreading, Reynolds number, pool fraction, and the effective organic phase saturation are the most significant parameters controlling tracer partitioning rates. Finally, a correlation for prediction of the effective (upscaled) mass transfer coefficient is proposed and verified using existing experimental data. The developed upscaled model incorporates the influence of physical heterogeneity on the rate of tracer partitioning and, thus, can be used for the estimation of source zone mass distribution characteristics from tracer test results.

In response to new coal combustion residuals (CCR) disposal regulations, many coal‐fired utilities have closed existing unlined surface impoundments (SIs) that were traditionally used for disposal of CCR. The two primary closure options are closure‐in‐place (CIP), which involves dewatering and capping, and closure‐by‐removal (CBR), which includes excavation, transportation, and disposal of the CCR into a lined landfill. This article provides a methodology and a case study of how green and sustainable remediation concepts, including accounting for the life cycle environmental footprints and the physical risks to workers and community members, can be incorporated into the closure decision‐making process. The environmental impacts, occupational risks, and traffic‐related fatalities and injuries to workers and community members were calculated and compared for closure alternatives at a hypothetical site. The results demonstrated that the adverse impacts of the CBR option were significantly greater than those of the CIP option with respect to the analyzed impact pathways.