Photodegradation of the pharmaceutical drug diclofenac in a lake:: Pathway, field measurements, and mathematical modeling

Vertical concentration profiles of diclofenac were measured in Lake Greifensee (Switzerland) under mixed (February/December) and stratified (July) lake conditions. The concentrations ranged from 1 to 12 ng/L and were lower in summer than in winter, especially near the lake surface, pointing to an efficient elimination of diclofenac by photodegradation in the lake. Laboratory experiments confirmed the rapid photodegradation of diclofenac in water when exposed to sunlight. First-order reaction rates varied seasonally according to actual solar radiation (half-lives, tau = 0.2-1.7 h). The initial photoproduct was 8-chlorocarbazole-1-acetic acid, which photodegraded even faster than the parent compound. Carbazole-1-acetic acid, previously reported as the main photoproduct, was only formed in the presence of a H-source, such as methanol. In the absence of a H-source and of air, hydroxycarbazole-1-acetic acid was formed. However, hydroxycarbazole-1-acetic acid was not observed in the presence of air and, thus, under conditions similar to those in a lake, likely because of its rapid further photooxidation. Computer simulations using a one-dimensional lake model taking actual solar radiation and flushing data of the lake into account confirmed that photolysis is the predominant elimination pathway for diclofenac in Lake Greifensee. These calculations further showed that the expected concentrations of the photoproduct 8-chlorocarbazole-1-acetic acid are less than the current detection limits of approximately 3 ng/L.