Molecular Dynamics Simulations of the Standard Leonardite Humic Acid: Microscopic Analysis of the Structure and Dynamics

Humic substances (HS) are abundant in the environment and play an important role in a number of biogeochemical processes including microbial activity, soil aggregation, plant growth, the retention and release of nutrients, the environmental fate of pollutants, and carbon storage. They are flexible, relatively small molecules forming supramolecular structures through weak interactions. Despite the great importance of understanding their behavior at the atomic level, computational modeling, a premier high-resolution technique providing great level of detail, has been surprisingly little-employed to study humic substances. Here, we use the recently developed Vienna Soil Organic-Matter Modeler to create representative models of a real HS sample, the standard Leonardite humic acid. Molecular dynamics simulations were used to probe the structure and dynamics of the system at a range of hydration levels. The studied systems were characterized in terms of their physicochemical properties, including density, dielectric properties, hydrogen bonding, etc. Moreover, the strength of sorption was estimated for three small organic compounds: benzaldehyde, propan-2-ol, and acetone. Strikingly, the HS models were validated against experimental data showing a remarkable agreement with calculated properties. Finally, we make the equilibrated models of the standard Leonardite humic acid, together with corresponding force-field parameters, available at the Vienna Soil Organic-Matter Modeler.