The competition of humic acid aggregation and adsorption on clay particles and its role in retarding heavy metal ions

Humic acid (HA) is of great importance in controlling the fate of heavy metals (HMs), however, the pivotal influence of HA aggregation within the HA-clay-HM ternary system on retarding HM mobility remains obscure. This study performed molecular dynamics simulations to delve into the consequences of HA aggregation on the environmental behavior of Cd2+ and Pb2+ (0.1–0.6 M) in the co-existence of illite particles. HA can readily aggregate into clusters, adhering to the illite surface or freely dispersing in the solution. These HA clusters significantly modulate HM mobility, contingent upon their location, arrangement, and interaction with illite. Consequently, HA exhibited a pronounced retardation effect on HM migration, stemming from the competition between HA aggregation and its adsorption on illite. Additionally, the retardation effect of HA aggregation was more obvious for Cd2+ (as compared to Pb2+), owing to its stronger interaction with the functional groups of HA. These findings contribute to the development of potential HA-based strategies for remediation of heavy metal-contaminated sites. [Display omitted] •TNB wins the competition for HM through the TNB aggregation and its adsorption on illite.•The mobility of TNB clusters mainly depends on their location and arrangement.•The mobility of TNB directly linked that of HM ions through the formation of TNB clusters.•The local structure of TNB and HM whether on the illite surface or in bulk solution is disclosed.•In the presence of illite the retarding effect of TNB is more obvious on Cd2+ than Pb2+.