Transforming contaminant ligands at water–solid interfaces via trivalent metal coordination

In environmental matrices, the migration and distribution of contaminants at water–solid interfaces play a crucial role in their capture or dissemination. Scientists working in environmental remediation and wastewater treatment are increasingly aware of metal–contaminant coordination; however, interfacial behaviors remain underexplored. Here, we show that trivalent metal ions (e.g. Al3+ and Fe3+) mediate the migration of pollutant ligands (e.g. tetracycline (TC) and ofloxacin) to the organic solid interface. In the absence of Al3+, humic acid (HA) colloids (50 mg/L) capture 26.1 % of the TC in water (initial concentration: 10 mg/L) via weak intermolecular interactions (binding energy: −5.71 kcal/mol). Adding Al3+ (2.5 mg/L) significantly enhances the binding of TC to an impressive 94.2 % via Al3+ mediated coordination (binding energy: −84.89 kcal/mol). The significant increase in binding energy results in superior interfacial immobilization. However, excess free Al3+ competes for TC binding via direct binary coordination, as confirmed based on the unique fluorescence of Al3+–TC complexes. Density functional theory calculations reveal the intricate process of HA–Al3+ binding via carboxyl and phenolic hydroxyl sites. The HA–Al3+ flocs then leverage the remaining coordination capacity of Al3+ to chelate with TC. As well as providing insights into the pivotal role of metal ion on the self-purification of natural water bodies, our findings on the interfacial behavior of metal–contaminant coordination will propel coagulation technology to the capture of microscale pollutants.