Estimating evolution of δ(13)CH(4) during methanization of municipal solid waste based on chemical reactions, isotope accumulation in products and microbial ecology.

Natural isotopic composition in substrate may be used to reveal the metabolic pathways of substrate transformation by microbial community. In this paper, a change in δ(13)CH(4) during methanization of reconstituted municipal solid waste was described using a mathematical model based on stoichiometric chemical reactions, equation for the (13)C isotope accumulation in products at the low natural C(13)/C(12) ratio and microbial ecology. A set of experimental data used in the model was taken from Qu et al. (2009a). According to the model, during mesophilic municipal solid waste methanization initially hydrogenotrophic and further aceticlastic methanogenesis dominated. At the final stage hydrogenotrophic methanogenesis followed by acetate oxidation dominated again. In spite of rather high measured values of δ(13)C for CO(2) above -21‰, a sharp decrease in δ(13)CH(4) from -20‰ to -60‰ at the final stage was explained by a larger fractionation against (13)C during methanogenesis from H(2)/H(2)CO(3) due to a kinetic isotope effect when hydrogenotrophic methanogens preferentially take down light (12)C. The model also confirmed that in thermophilic conditions a comparatively stable value of δ(13)CH(4) about -60‰ measured earlier (Qu et al. 2009b) was due to a dominance of hydrogenotrophic methanogenesis during all methanization process of cardboard waste.