Response of chromophoric dissolved organic matter dynamics to tidal oscillations and anthropogenic disturbances in a large subtropical estuary

Abstract

Estuaries support the livelihood of ~75% of the world's population and maintain high primary production in coastal waters, which are often subjected to strong tides and anthropogenic disturbances. There is a paucity of information on how the optical composition and bioavailability of chromophoric dissolved organic matter (CDOM) are influenced by tidal oscillations in estuaries with highly urbanized surrounding areas. We examined the semi-diurnal Qiantang Bore, one of the Earth's three most predominant tide bores, and found that dissolved organic carbon (DOC), CDOM absorption a(254) and terrestrial humic-like C1, tryptophan-like C2 and C5, fulvic-like C3, and microbial humic-like C4 decreased markedly with increasing salinity. This suggests that physical mixing of riverine freshwater and saltwater can shape the optical composition of CDOM in the estuary. This was supported by the semi-diurnally and hourly observations at Zhijiang (salinity ~0.1‰, upstream of the estuary) that DOC, bioavailable DOC (BDOC), C1-C2, and C4-C5 increased markedly with decreasing tidal level, while DOC and C1-C5 increased notably with increasing salinity. We further found δ¹⁸O was enriched with increasing tidal level, while tryptophan-like C2 and C5, and fulvic-like C3 decreased significantly with increasing tidal level at Zhapu (salinity ~7‰, downstream of the estuary). Furthermore, DOC, BDOC, C1, and C4 decreased, while δ¹⁸O and C3 increased markedly with increasing salinity. Further evidences come from the notably lower mean first principal component (PC1) scores at Zhijiang and Zhapu, both positively associated with anthropogenic tryptophan-like inputs, were observed during ebb than during flood tides, and PC1 at Zhijiang increased notably with increasing salinity. We conclude that anthropogenic inputs contributed primarily to the CDOM pool in the estuary and are mediated by the physical mixing of riverine freshwater and seawater, and ebb tides are often associated with enhanced anthropogenic CDOM with relatively high bioavailability.

Keywords: Chromophoric dissolved organic matter (CDOM); Parallel factor analysis (PARAFAC); Qiantang estuary; Tidal oscillations; Ultrahigh resolution mass spectrometry.