Rate-Limited Desorption of Volatile Organic Compounds from Soils and Implications for the Remediation of a Louisiana Superfund Site

The rates of desorption of trichloroethylene (TCE) and 1,3-dichlorobenzene (DCB) from a silty soil at a Superfund site and a silty-clayey soil from an uncontaminated bottomland hardwoodswamp in Baton Rouge, Louisiana were studied in laboratory batchsystems. The effect of the age of soil contamination was studiedusing a laboratory-spiked soil incubated for 3 days, 3 months and5 months. An empirical non-linear model was used to describe thebi-phasic nature of desorption with one fraction (labile) beingreleased in relatively short periods of time (typically 24–100 hr) and a second fraction (non-labile or irreversible) beingresistant to desorption. The non-linear model parameters, viz.,the fraction of the chemical released rapidly (F), and the firstorder desorption rate coefficients, k ₁ and k ₂respectively for the labile and slowly released fractions weredetermined by fitting the experimental data to the model. Thedata fit the model well as indicated by the high r ² values.The estimate of k ₁ was good. However, the values of k ₂are known with less precision due to the limited duration of theexperiment and number of samples taken at long times. In addition, desorption kinetics of 3 and 5-month old contaminatedsoils showed that progressively less amount of contaminant was available for facile desorption (lower F) compared to freshly contaminated soil. The labile fraction had desorption rate constants of the order of 10^-1 h^-1, whereas the slowlyreleased fraction had rate constants of the order of 10^-4 h^-1 in accord with literature reported values for a varietyof other compounds and soils. Possible mechanisms describing these rates and implications for the site clean up are discussed.