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.

Distribution of persistent free radicals in different molecular weight fractions from peat humic acids and their impact in reducing goethite.

Humic substances, the most abundant component of soil organic matter, play vital roles in the biogeochemical cycles and pollutant redox reactions. However, the knowledge regarding the distribution of persistent free radicals (PFRs) and redox capacity in different molecular weight fractions (MWF) of humic acid (HA) and their impact on the transformation of iron oxide minerals remains unknown. In this study, we separated bulk HA into various MWF using dialysis methods and systematically investigated their PFRs properties, redox capacity, and the impact in reducing goethite. The results showed that the PFRs in the low MWF (<3500, <7000, and <14,000 Da) can be assigned to oxygen-centered organic radicals while those in the bulk and high MWF (14000-retentate) were assigned to carbon-centered organic radicals. The PFRs concentrations of low MWF were 0.20-0.45 × 1016 spins/g, far less than those of bulk HA (3.04 × 1016 spins/g) and 14000-retentate (1.30 × 1016 spins/g). The total concentrations of reactive oxygen species (ROS) induced by PFRs in HA fractions ranged from 8.04 × 1016 (in 14000-retentate) to 32.35 × 1016 spins/g (in bulk HA). Compared with the low MWF, the 14000-retentate fractions had the higher reducing capacity, which was positively related to the content of PFRs and phenolic hydroxyl in HA. The results obtained provide valuable insight into the geochemistry processes of Fe-containing minerals during their interaction with HA in the natural environment. Overall, the results obtained provide valuable insight into the geochemical behaviors of HA-associated PFRs under natural conditions.