Multi-scale modeling of natural organic matter–heavy metal cations interactions: Aggregation and stabilization mechanisms

Interaction between natural organic matters (NOM) and heavy metal cations in aqueous environment are of great significance for maintaining stability of organic carbon and restraining transport of heavy metal contaminants in (bio)geochemical processes. We systematically explore the aggregation process and complexation between NOM and heavy metal cations (Ag+, Cd2+, Pb2+, Zn2+, Eu3+) under different pH condition by molecular dynamics (MD) simulations, umbrella sampling method, and quantum chemistry calculations. The character of molecular structures NOM-heavy metal complexes and association are quantified. In acidic pH condition, aggregation proceeds via H-bonding and π-π interactions between NOM fragments. In neutral condition, Ag+, Cd2+, Pb2+, and Eu3+ can form inner-sphere complexes with the surface carboxylic groups and therefore reduce intermolecular charge repulsion, eventually leading to NOM aggregation, and it shows that even without direct binding, the outer-sphere adsorbed Zn2+ can also result in the formation of NOM assemble through H-bonding. Consequently, these heavy metals are capable of promoting NOM aggregation regardless of the complexing ways. Complexing free energy calculations characterized the dynamic processes of cations binding to the carboxylic groups of NOM fragment and the related energy landscape. This study provides quantitative insights for understanding the environmental processes of heavy metals and cycle of C in aquatic ecosystem, and contributes to developing environment-friendly strategies for controlling heavy metal contaminants.