Abstract. Dissolved organic carbon (DOC) concentration in the Pearl River estuary (PRE) of China was measured in May, August, and October 2015 and January 2016. Chromophoric and fluorescent dissolved organic matter (CDOM and FDOM) in the latter three seasons were characterized by absorption and fluorescence spectroscopy. CDOM and FDOM exhibited negligible seasonal variations, while DOC displayed a significant seasonality, with the average concentration being highest in May (156 µmol L−1), lowest in November (87 µmol L−1), and comparable between January (118 µmol L−1) and August (112 µmol L−1). Although DOC, CDOM, and FDOM in surface water were generally higher than in bottom water, the difference between the two layers was statistically insignificant. DOC showed little cross-estuary variations in all seasons, while CDOM and FDOM in January were higher on the west side of the estuary than on the east side. All three variables showed rapid drawdowns in the head region of the estuary (salinity <5); their dynamics in the main estuary were primarily controlled by conservative mixing, leading to linearly declining or relatively constant (for DOC in May and November only) contents with increasing salinity. The decrease in FDOM with salinity was 5 %–35 % faster than that of CDOM, which in turn was 2–3 times quicker than that of DOC. Salinity and CDOM absorption coefficients could serve as indicators of DOC in August and January. Freshwater endmembers in all seasons mainly contained fresh, protein-rich DOM of microbial origin, a large part of it likely being pollution-derived. Protein-like materials were preferentially consumed in the head region but the dominance of the protein signature was maintained throughout the estuary. Exports of DOC and CDOM (in terms of the absorption coefficient at 330 nm) into the South China Sea were estimated as 195×109 g and 266×109 m2 for the PRE and 362×109 g and 493×109 m2 for the entire Pearl River Delta. The PRE presents the lowest concentrations and export fluxes of DOC and CDOM among the world's major estuaries. DOM delivered from the PRE is, however, protein-rich and thus may enhance heterotrophs in the adjacent coastal waters. Overall, the PRE manifests lower abundance and smaller spatiotemporal variability of DOM than expected for a sizable estuary with a marked seasonality of river runoff due supposedly to the poorly forested watershed of the Pearl River, the rapid degradation of the pollution-derived DOM in the upper reach, and the short residence time of freshwater.

Water samples collected from various depths of the offshore South China and Philippine Seas were exposed to solar‐simulated radiation. Photomineralization of dissolved organic carbon (DOC) and photobleaching of chromophoric dissolved organic matter (CDOM) and its humic‐like fluorescent constituent (FDOM) were observed in all samples. Protein‐like FDOM was, however, either photo‐decomposed or photo‐produced, depending on the sample's depth. The photobleaching of CDOM and humic‐like FDOM was much faster in deep than in shallow water samples while photomineralization displayed a weaker vertical zonation. Prior‐irradiated deep water inoculated with surface‐water bacteria showed enhanced microbial DOC removal but CDOM production. Results from this study suggest that deep‐ocean CDOM and FDOM can barely survive photobleaching during one ocean mixing cycle, but photochemical turnover of the bio‐refractory deep DOC is considerably longer than its average radiocarbon age. Coupled photochemical‐microbial processes can not only remove part of the bio‐refractory deep DOM but also regenerate part of it during ocean overturning circulation.

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