On the photodegradation of azithromycin, erythromycin and tylosin and their transformation products – A kinetic study

In this study, the photo-induced degradation of azithromycin (Azi), erythromycin (Ery) and tylosin (Tyl) was investigated. The three macrolides are regularly found in different kinds of water, and are thus considered a potential environmental risk. In search of efficient ways for elimination, the compounds were systematically irradiated with a polychromatic UVC light source emitting 185, 254 and discretely further up to 580 nm. Due to their specific structural features, the macrolides possess different optical absorption characteristics leading to photodegradation pathways with dissimilar kinetic properties. Hence, the photodegradation products and their kinetics were analyzed using high-performance liquid chromatography (HPLC) coupled to high-resolution time-of-flight mass spectrometry. Among the degradants, i.e. the products formed during UV irradiation, both sugar moieties and lactone macrocycles were observed. Applying a first order kinetic model, the half-life of Azi was determined as 1.0−3.7 min, that of Ery as 1.0−14.2 min depending on the reaction conditions. The two compounds possess much lower absorption cross-sections than Tyl, in particular at 254 nm. Their half-lives appeared at least three times higher than that of Tyl that has t1/2 of 0.2−1.0 min. Based on quantum efficiency considerations, it was assumed that the degradation of Ery and Azi was mainly due to hydroxyl radical formation, which originated from water irradiation below 200 nm, whereas Tyl experienced predominantly photo induced degradation. The photodegradants of Azi exhibited half-lives of over 200 min, whereas most of the photo-products of Ery and Tyl showed half-lives of less than 10 min. Photodegradation processes were investigated at pH 3, pH 7 and pH 9 and in the presence of hydrogen peroxide. Both the educts and the photo-products were degraded more rapidly under neutral and acid conditions.