Humic substances have a potential role in the fate and transport of toxic metal ions in the environment due to their colloidal characteristics and abundant surface functional groups. Batch techniques (DLS, EPM, FT-IR and fluorescence EEM) were developed to assess the aggregation mechanisms of humic acid (HA) reacting with Cs+ or Co2+ electrolyte ions in this work. The kinetic experimental results indicated that a much lower Co2+ ion concentration (0.03–1.50 mmol/L) induced rapid aggregation of HA compared to that of Cs+ (3.0–15 mmol/L), and the divalent Co2+ ion was far more effective in enhancing HA aggregation than monovalent Cs+. The aggregation kinetics of HA were also found to be pH-dependent, and a much lower pH condition (pH 5.0) caused more rapid aggregation (the largest hydrodynamic diameter of ~3000 nm) compared to those at pH 7.0 (the largest hydrodynamic diameter of ~2000 nm). Positively charged metal ions in the solution can lower the electrostatic repulsive force between HA molecules through charge neutralization, thus leading to the rapid aggregation of HA aggregates. Furthermore, the carboxylic and phenolic groups on the HA surface were also involved in the aggregation reaction to form inner complexes and accelerate the aggregation process.
