Fluorescence and absorption properties of chromophoric dissolved organic matter (CDOM) in coastal surface waters of the northwestern Mediterranean Sea, influence of the Rhône River

Abstract

Seawater samples were collected monthly in surface waters (2 and 5 m depths) of the Bay of Marseilles (northwestern Mediterranean Sea; 5°17'30" E, 43°14'30" N) during one year from November 2007 to December 2008 and studied for total organic carbon (TOC) as well as chromophoric dissolved organic matter (CDOM) optical properties (absorbance and fluorescence). The annual mean value of surface CDOM absorption coefficient at 350 nm [a_CDOM (350)] was very low (0.10 ± 0.02 m^-1 ) in comparison to values usually found in coastal waters, and no significant seasonal trend in a_CDOM (350) could be determined. By contrast, the spectral slope of CDOM absorption (S_CDOM ) was significantly higher (0.023 ± 0.003 nm^-1 ) in summer than in fall and winter periods (0.017 ± 0.002 nm^-1 ), reflecting either CDOM photobleaching or production in surface waters during stratified sunny periods. The CDOM fluorescence, assessed through excitation emission matrices (EEMs), was dominated by protein-like component (peak T; 1.30-21.94 QSU) and marine humic-like component (peak M; 0.55-5.82 QSU), while terrestrial humic-like fluorescence (peak C; 0.34-2.99 QSU) remained very low. This reflected a dominance of relatively fresh material from biological origin within the CDOM fluorescent pool. At the end of summer, surface CDOM fluorescence was very low and strongly blue shifted, reinforcing the hypothesis of CDOM photobleaching. Our results suggested that unusual Rhône River plume eastward intrusion events might reach Marseilles Bay within 2-3 days and induce local phytoplankton blooms and subsequent fluorescent CDOM production (peaks M and T) without adding terrestrial fluorescence signatures (peaks C and A). Besides Rhône River plumes, mixing events of the entire water column injected relative aged (peaks C and M) CDOM from the bottom into the surface and thus appeared also as an important source of CDOM in surface waters of the Marseilles Bay. Therefore, the assessment of CDOM optical properties, within the hydrological context, pointed out several biotic (in situ biological production, biological production within Rhône River plumes) and abiotic (photobleaching, mixing) factors controlling CDOM transport, production and removal in this highly urbanized coastal area.

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