Hydrolysis of Chloramphenicol Catalyzed by Clay Minerals under Nonaqueous Conditions

Soil contamination with antibiotics has raised great environmental concerns, while the abiotic degradation of antibiotics on drought soil particles has been largely ignored. In this study, we examined the transformation of chloramphenicol (CAP) on phyllosilicates under nonaqueous conditions. A significant hydrolysis of CAP mediated by kaolinite occurred under moderate relative humidities (RH: 33-76%) with the half-lives of 10-20 days. By contrast, incubation with montmorillonite did not result in detectable degradation of CAP. Infrared and Raman spectroscopies together with density functional theory calculations suggested that the surface-catalyzed CAP hydrolysis was mainly attributed to the basal plane hydroxyl groups of kaolinite, which formed hydrogen-bond interactions with the carbonyl of CAP such that the hydrolysis activation energy of CAP was greatly reduced. Neither the Bronsted nor the Lewis acidity was the determinant for the hydrolysis reaction. The surface moisture content played an essential role in CAP hydrolysis. Specifically, water facilitated the mass transfer of CAP over the low-RH range, whereas excessive water competed for the reactive hydroxyl sites. These results highlight an important but long-overlooked abiotic transformation pathway for antibiotics in field soil, where the soil moisture is low and the microbial activity is suppressed.