Molecular characteristics, proton dissociation properties, and metal binding properties of soil organic matter: A theoretical study

Highlights: • An a priori method was developed to carry out a detailed, molecular analysis of SOM. • SOM models by molecular modeling using elemental composition information were used. • The proton binding constants of SOM were predicted. • The metal binding constants of SOM were sequentially calculated for various metals. • The method links the composition of SOM to its molecular properties. -- Abstract: Soil organic matter (SOM) is a key soil sorbent with a large number of reactive binding sites that may complex with metals, controlling their fate, transport, and bioavailability in soil. However, due to the complex and heterogeneous nature of SOM, it is not easy to probe its physical and chemical properties at the molecular level. In this study, an a priori method was developed to predict the molecular properties of SOM, which incorporated computational molecular modeling, SPARC Performs Automated Reasoning in Chemistry's (SPARC's) chemical reactivity models, and linear free energy relationships (LFERs). Specifically, the method uses SOM models simulated by molecular dynamics modeling based on the experimental elemental composition and functional group information of SOM. For the molecular characteristics, the molecular H/C and O/C ratios, molecular weight, aromatic index, and double bond equivalence of the SOM molecules were calculated. For the proton binding constants, the SPARC was used to calculate the microscopic pK_a values of every binding sites of individual molecules of the SOM model. Based on the pK_a values, the metal binding constants for individual monodentate binding sites were calculated using the Irving-Rossotti LFERs for different heavy metals. The results agreed reasonably with the default values used in the Windermere Humic Aqueous Model (WHAM) (VI) for the investigated metals. The theoretical SOM models, to some extent, represented the average properties of the investigated SOM. Overall, this study gives new quantitative and molecular insight into the structure and chemical properties of SOM. Detailed deprotonation and metal-SOM complexation information was gained for individual SOM binding sites. Such feasible and straightforward predictive scheme is useful to assess the risk of heavy metals in various aquatic and terrestrial environment involving heterogeneous natural organic matter.