Polarizability and Spin Density Correlate with the Relative Anaerobic Biodegradability of Alkylaromatic Hydrocarbons

Polarizability (<alpha >) and spin density (SD) of benzyl radical intermediates calculated using Gaussian 03 were correlated with the extent of anaerobic biodegradation for 17 C-1 to C-4 parent alkylbenzenes. The percent anaerobic biodegradation of the hydrocarbon series was determined in a previous study using an inoculum from a gas condensate-contaminated aquifer incubated under sulfate-reducing conditions. Many of the parent compounds are known to be biodegraded in the absence of oxygen by fumarate addition reactions. Percent biodegradation over a 100 day incubation (predicted) = -1.044 <alpha > + 908.271SD - 586.197 (R-2 = 0.839; all p-values <= 0.058). This correlation suggests that compounds forming more stable alkylbenzyl radical intermediates biodegrade by fumarate addition more slowly than their counterparts forming less stable radicals. More highly substituted molecules including isopropyl benzene, 1-ethyl-2,6-dimethylbenzene and 1-ethyl-3,4-dlimethylbenzene did not fit the model, The assumption of biodegradation by fumarate addition reaction was independently verified with several substrates. These findings help form a basis for predicting the relative rate of alkylbenzene metabolism in anaerobic environments.