Evaluating degradation rates of chlorinated organics in groundwater using analytical models

Abstract

The persistence and fate of organic contaminants in the environment largely depends on their rate of degradation. Most studies of degradation rate are performed in the lab where chemical conditions can be controlled precisely. Unfortunately, literature values for lab degradation studies often are orders of magnitude higher than for field-generated studies, calling into question the relevance of lab-generated values for characterizing the persistence of organic contaminants in the environment. Complicating analysis of this ostensible disparity between lab and field degradation values, field-generated values often do not account for effects of adsorption. Modeling with a newly derived analytical solution for first-order degradation coupled with advective losses and adsorption to solve for degradation constants is insensitive to uncertainties in field properties. Application to field data shows that accounting for advection and adsorption greatly affects the value of calculated degradation constants compared to disappearance constants, which do not account for these phenomena. In fact, degradation constants, calculated using these analytical solutions and field data, are in the range reported for lab-generated data. Using these analytical solutions, for the sulfate-reducing field conditions documented for this site, perchloroethene, trichloroethene, 1,1,1-trichloroethane, 1,1-dichloroethane, and chloroethane all degraded with half-lives ranging from 5 to 115 d. Consistent with other studies of sulfate-reducing conditions, cis-1,2-dichloroethene did not chemically degrade at a measurable rate. When nonaqueous phase 1,1-dichloroethane is present, down-gradient concentrations vary in an annual sinusoidal pattern, apparently because of seasonal variation in dilution from groundwater recharge.