Molecular simulation of humic substance–Ca-montmorillonite complexes

Abstract

An understanding of the processes that lead to long-term stabilization of organic matter in soils is essential to the effective implementation of strategies designed to mitigate CO 2 loss from the soil carbon reservoir in temperate climatic zones. Decomposition studies indicate that montmorillonite, a smectite that often forms with interlayers rich in Ca 2+, greatly retards the microbial mineralization of soil organic matter. We performed a series of atomistic simulations designed to identify favorable molecular-scale organo-mineral interactions within nanoscale, hydrated complexes consisting of a humic substance and Ca-montmorillonite. Both protonated and Ca-saturated forms of the model humic molecule, representing acidic and circumneutral solution conditions, respectively, were studied within the hydrated interlayer region of a rigid-atom model of Ca-montmorillonite. The protonated humic substance formed direct hydrophobic and hydrogen bonding (H-bonding) interactions with the clay mineral. A few polar organic groups adsorbed via water bridging interactions. The Ca-saturated humic substance adsorbed via numerous cation bridges, less numerous water bridges, and indirect H-bonding interactions mediated by water molecules. Application of molecular modeling techniques to this complex organo-mineral system thus allowed identification of interactions favorable to carbon sequestration under both acidic and circumneutral conditions.