Role of ultra-violet radiation, mercury and copper on the stability of dissolved glutathione in natural and artificial freshwater and saltwater

The behavior and stability of dissolved reduced glutathione (GSH), an environmental antioxidant and metal transporter, is poorly known in natural waters. Glutathione oxidation rates were determined in both fresh- and brackish waters artificially submitted to different radiation wavebands. Photo-oxidation of GSH followed pseudo-first order kinetics, with half-lives ranging from 4 to 30 h in natural freshwater, and from 1.6 to 7 h in saltwater, with generally shorter persistence in UV-irradiated surface waters than in dark treatments. Chloride was shown to indirectly promote GSH photo-oxidation, probably through its role in the formation of radicals. The addition of Cu(II) to synthetic waters resulted in the rapid oxidation of GSH. The addition of Hg(II), a metal with strong affinity for thiols, protected GSH from oxidation by Cu(II) in the dark, but not under UV radiation. We conclude that UV-induced photo-oxidation is a key process altering the fate of GSH in natural waters. Also, the formation of stable GSH–Hg complexes could increase the bioavailability of Hg towards microorganisms in aquatic systems.