Photochemical behavior of dissolved and colloidal organic matter in estuarine and oceanic waters

- errestrially derived DOM was more susceptible to irradiation than autochthonous DOM.
- Photo‐induced synthetic reaction transformed the LMW matters to polysaccharides.
- Photo‐induced degradation reaction decomposed the HMW DOM to monosaccharides.
- Stable compositions of THAA significantly accumulated during irradiation.
- Labile compositions of THAA were prone to photodegradation.

Chromophoric dissolved organic matter (CDOM), carbohydrates, and amino acids were analyzed to investigate the photochemistry of total dissolved (< 0.22 μm) organic matter (DOM), high-molecular-weight (HMW, 1 kDa-0.22 μm) DOM and low-molecular-weight (LMW, < 1 kDa) DOM at stations in the Yangtze River and its coastal area, and in the Western Pacific Ocean. Results revealed that the humic-like and tryptophan-like CDOM fluorescent components in riverine, coastal, and oceanic surface waters were photodegraded during irradiation. However, the photochemical behavior of tyrosine-like component was obscured by the excessive fluorescence intensities of humic- and tryptophan-like fluorescent components. Light sensitivity varied depending on the source material; terrestrially derived DOM was more susceptible to irradiation than autochthonous DOM. In contrast to the expected photodegradation of CDOM, photo-induced synthetic reaction transformed the LMW matters to polysaccharides (PCHO) and degradation reaction decomposed the HMW DOM to Monosaccharides. Colloidal DOM preferentially underwent photodegradation, whereas permeate DOM mainly photosynthesized PCHO. The total hydrolysable amino acid (THAA) pool changed because of the additional input by the photodegradation of DOM or THAA itself. The compositions of THAA changed during the irradiation experiments, indicating that the different photochemical behavior of individual amino acids were related to their different original photoreactivities; the relatively stable amino acids (e.g., Ser and Gly) significantly accumulated during irradiation, whereas photo-active aromatic amino acids (e.g. Tyr and His) were prone to photodegradation. The data presented here demonstrated that irradiation significantly influence the conversion between dissolved and colloid organic matter. These results can promote the understanding of irradiation effect on the carbon and nitrogen cycle in riverine, estuarine and oceanic ecosystems.

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