Mechanistic Insights into Dissolved Organic Sulfur Photomineralization through the Study of Cysteine Sulfinic Acid

Abstract

Photochemical reactions convert dissolved organic matter (DOM) into inorganic and low-molecular-weight organic products, contributing to its cycling across environmental compartments. However, knowledge on the formation mechanisms of these products is still scarce. In this work, we investigate the triplet-sensitized photodegradation of cysteine sulfinic acid, a (photo)degradation product of cysteine, to sulfate (SO₄^2-). We use kinetic analysis, targeted experiments, and previous literature from several fields of chemistry to explain the elementary steps that lead to the release of sulfate. Our analysis indicates that triplet sensitizers act as one-electron oxidants on the sulfinate S lone pair. The resulting radical undergoes C-S fragmentation to form SO₂, which becomes hydrated to sulfite/bisulfite (S(IV)). S(IV) is further oxidized to SO₄^2- in the presence of triplet sensitizers and oxygen. We point out that the reaction sequence SO₂ ⇌ S(IV) → SO₄^2- is valid independently of the chemical structure of the model compound and might represent a sulfate photoproduction mechanism with general validity for DOS. Our mechanistic investigation revealed that amino acids in general might also be photochemical precursors of CO₂, ammonia, acetaldehyde, and H₂O₂ and that reaction byproducts can influence the rate and mechanism of S(IV) (photo)oxidation.