Enhanced Phototransformation of Tetracycline at Smectite Clay Surfaces under Simulated Sunlight via a Lewis-Base Catalyzed Alkalization Mechanism

As an important class of soil minerals and a key constituent of colloidal particles in surface aquifers, smectite clays can strongly retain tetracyclines due to their large surface areas and high cation exchange capacities. However, the research on phototransformation of tetracyclines at smectite clay surfaces is rarely studied. Here, the phototransformation kinetics of tetracycline preadsorbed on two model smectite clays (hectorite and montmorillonite) exchanged with Na+, K+, or Ca2+ suspended in aqueous solution under simulated sunlight was compared with that of tetracycline dissolved in water using batch experiments. Adsorption on clays accelerated tetracycline phototransformation (half-lives shortened by 1.1-5.3 times), with the most significant effects observed for Na+-exchanged clays. Regardless of the presence or absence of clay, the phototransformation of tetracycline was facilitated by increasing pH from 4 to 7. Inhibition or enhancement of photolysis-induced reactive species combined with their measurement using scavenger/probe chemicals indicate that the facilitated production of self photosensitized singlet oxygen (O-1(2)) was the key factor contributing to the clay-enhanced phototransformation of tetracycline. As evidenced by the red shifts and the increased molar absorptivity in the UV vis absorption spectra, the complexation of tetracycline with the negatively charged (Lewis base) sites on clay siloxane surfaces led to formation of the alkalized form, which has larger light absorption rate and is more readily to be oxidized compared to tetracycline in aqueous solution at equivalent pH. Our findings indicate a previously unrecognized, important phototransformation mechanism of tetracyclines catalyzed by smectite clays.