Energetics of product formation during anaerobic degradation of phthalate isomers and benzoate

Abstract

Methanogenic enrichment cultures grown on phthalate, isophthalate and terephthalate were incubated with the corresponding phthalate isomer on which they were grown, and a mixture of benzoate and the phthalate isomer. All cultures were incubated with bromoethanosulfonate to inactivate the methanogens in the mixed culture. Thus, product formation during fermentation of the aromatic substrates could be studied. It was found that reduction equivalents generated during oxidation of the aromatic substrates to acetate were incorporated in benzoate under formation of carboxycyclohexane. During fermentation of the phthalate isomers, small amounts of benzoate were detected, suggesting that the initial step in the anaerobic degradation of the phthalate isomers is decarboxylation to benzoate. Gibbs free energy analyses indicated that during degradation of the phthalate isomers, benzoate, carboxycyclohexane, acetate and molecular hydrogen accumulated in such amounts that both the reduction and oxidation of benzoate yielded a constant and comparable amount of energy of approximately 30 kJ mol −1. Based on these observations it is suggested that within narrow energetic limits, oxidation and reduction of benzoate may proceed simultaneously. Whether this is controlled by the Gibbs free energy change for carboxycyclohexane oxidation remains unclear.