Coagulation behavior of humic acid in aqueous solutions containing Cs⁺, Sr²⁺ and Eu³⁺: DLS, EEM and MD simulations

The coagulation behaviors of humic acid (HA) with Cs⁺ (10-500 mM), Sr²⁺ (0.8-10.0 mM) and Eu³⁺ (0.01-1.0 mM) at different pH values (2.8, 7.1 and 10.0) were acquired through a dynamic light scattering (DLS) technique combined with spectroscopic analysis and molecular dynamic (MD) simulations. The coagulation rate and the average hydrodynamic diameter (h>) increased significantly as the concentration of nuclides increased. h> could be scaled to time t as h>∝ t^a at higher Sr²⁺ concentrations, which shows that HA coagulation is consistent with the diffusion-limited colloid aggregation (DLCA) model. Trivalent Eu³⁺ induced HA coagulation at a much lower concentration than bivalent Sr²⁺ and monovalent Cs⁺. The coagulation value ratio of Sr²⁺ and Eu³⁺ to Cs⁺ is almost proportional to Z^-6, indicating that the HA coagulation process is generally consistent with the Schulze-Hardy rule. Spectroscopic analysis indicated that the complexation between nuclides and carboxylic/phenolic groups of HA molecules played important roles in the coagulation of HA. MD modelling suggested that Sr²⁺ and Eu³⁺ ions increased the coagulation process through the formation of intra- or inter-molecular bridges between negatively charged HA molecules, whereas for Cs⁺, no inter-molecular bridges were formed. This work offers new insight into the interactions between HA and radionuclides and provides a prediction for the roles of HA in the transportation and elimination of radionuclides in severely polluted environments.