The Effects of Montmorillonite–Humic Acid Composite Particles on the Photolysis of Tetracycline in Water

Suspended particulate matter (SPM) is an important component of natural water bodies and can significantly influence the photolytic behavior of water pollutants. A comprehensive understanding of the photochemical behavior of water pollutants in natural waters requires consideration of the presence of SPM. In this study, montmorillonite–humic acid (MMT-HA) composite particles were synthesized to simulate SPM in natural waters and their effects on the photolysis of tetracycline (TC) were investigated. The results demonstrated that the presence of MMT-HA composite particles in water significantly enhanced the photolysis of TC, with the photolytic kinetics following a pseudo-first-order model. Electron spin resonance spectra and free radical quenching experiments indicated that the photoactive components (MMT and humic acids) in the composite particles induced the generation of reactive oxygen species under light exposure, further contributing to the enhanced photolysis of TC. Comparative analysis of the free radical signals and adsorption experiments revealed that the accelerated photolysis of TC was also related to the interfacial interaction between the MMT in the composite particles and the TC molecules. The formation of surface complexes between TC molecules and the negatively charged sites on the MMT surface facilitated light absorption and electron transfer, thereby accelerating the photolysis of TC. Photoproduct analysis indicated that the primary degradation pathways of TC in the composite particle systems included the addition of hydroxyl radicals to the aromatic ring, as well as demethylation, deamination and dehydration in the side chains. This study shows that SPM in water bodies can affect the photochemical behavior of pollutants and should be taken into account when assessing the phototransformation of pollutants in natural waters.