Spatio-temporal distribution, photoreactivity and environmental control of dissolved organic matter in the sea-surface microlayer of the eastern marginal seas of China

As the boundary interface between the atmosphere and ocean, the sea-surface microlayer (SML) plays a significant role in the biogeochemical cycles of dissolved organic matter (DOM) and macronutrients in marine environments. In our study, the optical properties of DOM were compared between the sub-surface water (SSW) and the SML during spring, summer and winter in the East China Sea (ECS) and the Yellow Sea (YS). In addition, photoexposure experiments were designed to compare photochemical degradation processes of DOM between the SML and the SSW. Chromophoric DOM (CDOM), fluorescent DOM, dissolved organic carbon, chlorophyll a (Chl a), picoplankton, nutrients and bacteria were frequently enriched in the SML. The enrichment factors (EFs) of tryptophan-like component 4 were significantly higher than other fluorescence components; the longer wavelength absorption values of CDOM showed higher EFs in the SML, and a more significant relationship between CDOM and Chl a in the SML, indicating that autochthonous DOM was more strongly enriched in the SML than the terrestrial DOM. Higher EFs were generally observed in the SML in the off-shore regions than in the coastal regions, and CDOM in the SML was photobleached more after relatively strong irradiation, as also indicated by the lower percentages of humic-like DOM and lower specific UV absorbance values (SUVA254) in the SML than the SSW. Compared to the SSW, the elevated nutrients may stimulate phytoplankton growth, biological activity and then production of abundant fresh autochthonous DOM in the SML. Our results revealed a new enrichment model for exploring the air-sea interface environment, which can explain the more autochthonous properties of DOM in the SML than the SSW.