Selective Photochemical Oxidation of Reduced Dissolved Organic Sulfur to Inorganic Sulfate

The chemical nature and stability of reduced dissolved organic sulfur (DOS_Red) have implications on the biogeochemical cycling of trace and major elements across fresh and marine aquatic environments, but the underlying processes governing DOS_Red stability remain obscure. Here, dissolved organic matter (DOM) was isolated from a sulfidic wetland, and laboratory experiments quantified dark and photochemical oxidation of DOS_Red using atomic-level measurement of sulfur X-ray absorption near-edge structure (XANES) spectroscopy. DOS_Red was completely resistant to oxidation by molecular oxygen in the dark and underwent rapid and quantitative oxidation to inorganic sulfate (SO₄^2-) in the presence of sunlight. The rate of DOS_Red oxidation to SO₄^2- greatly exceeded that of DOM photomineralization, resulting in a 50% loss of total DOS and 78% loss of DOS_Red over 192 h of irradiance. Sulfonates (DOS_SO3) and other minor oxidized DOS functionalities were not susceptible to photochemical oxidation. The observed susceptibility of DOS_Red to photodesulfurization, which has implications on carbon, sulfur, and mercury cycling, should be comprehensively evaluated across diverse aquatic environments of differing DOM composition.