Wavelength-dependent direct and indirect photochemical transformations of organic pollutants

Sunlight-induced photochemical transformations greatly affect the persistence of organic pollutants in natural environment. Whereas sunlight intensity is well-known to affect pollutant phototransformation rates, the reliance of pollutant phototransformation kinetics on sunlight spectrum remains poorly understood, which may greatly vary under different spatial-temporal, water matrix, and climatic conditions. Here, we systematically assessed the wavelength-dependent direct and indirect phototransformations of 12 organic pollutants. Their phototransformation rates dramatically decreased with light wavelength increasing from 375 to 632 nm, with direct photolysis displaying higher wavelength-dependence than indirect photolysis. Remarkably, UV light dominated both direct (90.4-99.5 %) and indirect (64.6-98.7 %) photochemical transformations of all investigated organic pollutants, despite its minor portion in sunlight spectrum (e.g., 6.5 % on March 20 at the equator). Based on wavelength-dependent rate constant spectrum, the predicted phototransformation rate of chloramphenicol (4.5 ± 0.7 × 10^-4 s^-1) agreed well with the observed rate under outdoor sunlight irradiation (4.3 ± 0.0 × 10^-4 s^-1), and there is no significant difference between the predicted rate and the observed rate (p-value = 0.132). Moreover, rate constant and quantum yield coefficient (QYC) spectrum could be applied for facilely investigate the influence of spectral changes on the phototransformation of pollutants under varying spatial-temporal (e.g., season, latitude) and climatic conditions (e.g., cloud cover). Our study highlights the wavelength-dependence of both direct and indirect phototransformation of pollutants, and the UV part of natural sunlight plays a decisive role in the phototransformation of pollutants.