Comparison of approaches for simulating reactive solute transport involving organic degradation reactions by multiple terminal electron acceptors

Abstract

Reactive solute transport models are useful tools for analyzing complex geochemical behavior resulting from biodegradation of organic compounds by multiple terminal electron acceptors (TEAPs). The usual approach of simulating the reactions of multiple TEAPs by an irreversible Monod rate law was compared with simulations that assumed a partial local equilibrium or kinetically controlled reactions subject to the requirement that the Gibbs free energy of reaction (Δ G) was either less than zero or less than a threshold value. Simulations were performed using a single organic substrate and O 2 , FeOOH, SO 4 -2 and CO 2 as the terminal electron acceptors. It was assumed that the organic substrate was slowly and completely fermented to CO 2 and H 2 and the H 2 was oxidized by the TEAPs. Simulations using the Monod approach showed that this irreversible rate law forced the reduction of both FeOOH and CO 2 to proceed even when Δ G was positive. This resulted in an over prediction in amount of FeOOH reduced to Fe(II) in parts of the domain and it resulted in large errors in pH. Simulations using mass action kinetics agreed with equilibrium simulations for the case of large rate constants. The extent of reductive dissolution of FeOOH was strongly dependent on the thermodynamic stability of the FeOOH phase. Transport simulations performed assuming that the reactions of the TEAPs stopped when Δ G exceeded a threshold value showed that only simulated H 2 concentrations were affected if the threshold value was the same for each TEAP. Simulated H2 concentrations were controlled by the fastest reaction of the TEAP, but it was common for reactions to occur concomitantly rather than sequentially.