New insights into the mechanism of phosphate release during particulate organic matter photodegradation based on optical and molecular signatures.

Phosphate release from particulate organic matter (POM) dominates phosphorus (P) cycling in aquatic ecosystems. However, the mechanisms underlying P release from POM remain poorly understood because of complex fractionation and analytical challenges. In this study, the release of dissolved inorganic phosphate (DIP) during POM photodegradation was assessed using excitation-emission matrix (EEM) fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). POM in suspension was significantly photodegraded under light irradiation, concomitantly with the production and release of DIP in the aqueous solution. Chemical sequential extraction revealed that organic phosphorus (OP) in POM participated in photochemical reactions. Moreover, FT-ICR MS analysis revealed that the average molecular weight of P-containing formulas decreased from 374.2 to 340.1 Da. Formulas containing P with a lower oxidation degree and unsaturation were preferentially photodegraded, generating oxygen-enriched and saturated formula compounds, such as protein- and carbohydrate-like P-containing formulas, benefiting further utilization of P by organisms. Reactive oxygen species played an important role in the photodegradation of POM, and excited triplet state chromophoric dissolved organic matter (3CDOM*) was mainly responsible for POM photodegradation. These results provide new insights into the P biogeochemical cycle and POM photodegradation in aquatic ecosystems.