Effect of co-existing Co~(2+) ions on the aggregation of humic acid in aquatic environment: Aggregation kinetics, dynamic properties and fluorescence spectroscopic study

摘要

The fate and transport of humic substances in the aquatic environments depend significantly on their interactions with co-existing ions. Herein, we employed dynamic light scattering (DLS) measurement, molecular dynamic (MD) simulation and fluorescence spectrometry to investigate the aggregation of humic acid (HA) in the presence of Co2+ ions. The aggregation kinetics was depicted by hydrodynamic diameter (D-h) and the attachment efficiency (alpha) of HA aggregates. alpha increases gradually in the reaction-limited (slow) regime due to the decrease of the double layer repulsion, and the energy barrier is eliminated to a certain extent in the diffusion-limited reaction while alpha close to unity. The complexation between functional groups (i.e. carboxylic and phenolic groups) of HA and Co2+ ions contributes significantly to the aggregation process of HA. MD simulation and density functional theory (DFT) calculation demonstrate that the aggregation process of HA can be promoted by Co2+ through several inter- or intra-molecular interactions between HA and the Co2+ ions. The results provide a pathway for insight into the interactions between HA and metal ions, which is important for deeply understanding the environmental behaviors of HA in natural aqueous systems. (C) 2019 Elsevier B.V. All rights reserved.