Absorption and fluorescence properties of chromophoric dissolved organic matter of the eastern Bering Sea in the summer with special reference to the influence of a cold pool

Abstract. The absorption and fluorescence properties of chromophoric dissolved organic matter (CDOM) are reported for the inner shelf, slope waters and outer shelf regions of the eastern Bering Sea during the summer of 2008, when a warm, thermally stratified surface mixed layer lay over a cold pool (< 2 °C) that occupied the entire middle shelf. CDOM absorption at 355 nm (a_g355) and its spectral slope (S) in conjunction with excitation–emission matrix (EEM) fluorescence and parallel factor analysis (PARAFAC) revealed large variability in the characteristics of CDOM in different regions of the Bering Sea. PARAFAC analysis aided in the identification of three humic-like (components one, two and five) and two protein-like (a tyrosine-like component three, and a tryptophan-like component four) components. In the extensive shelf region, average absorption coefficients at 355 nm (a_g355, m⁻¹) and DOC concentrations (μM) were highest in the inner shelf (0.342 ± 0.11 m⁻¹, 92.67 ± 14.60 μM) and lower in the middle (0.226 ± 0.05 m⁻¹, 78.38 ± 10.64 μM) and outer (0.185 ± 0.05 m⁻¹, 79.24 ± 18.01 μM) shelves, respectively. DOC concentrations, however were not significantly different, suggesting CDOM sources and sinks to be uncoupled from DOC. Mean spectral slopes S were elevated in the middle shelf (24.38 ± 2.25 μm⁻¹) especially in the surface waters (26.87 ± 2.39 μm⁻¹) indicating high rates of photodegradation in the highly stratified surface mixed layer, which intensified northwards in the northern middle shelf likely contributing to greater light penetration and to phytoplankton blooms at deeper depths. The fluorescent humic-like components one, two, and five were most elevated in the inner shelf most likely from riverine inputs. Along the productive "green belt" in the outer shelf/slope region, absorption and fluorescence properties indicated the presence of fresh and degraded autochthonous DOM. Near the Unimak Pass region of the Aleutian Islands, low DOC and a_g355 (mean 66.99 ± 7.94 μM; 0.182 ± 0.05 m⁻¹) and a high S (mean 25.95 ± 1.58 μm⁻¹) suggested substantial photobleaching of the Alaska Coastal Water, but high intensities of humic-like and protein-like fluorescence suggested sources of fluorescent DOM from coastal runoff and glacier meltwaters during the summer. The spectral slope S vs. a_g355 relationship revealed terrestrial and oceanic end members along with intermediate water masses that were modeled using nonlinear regression equations that could allow water mass differentiation based on CDOM optical properties. Spectral slope S was negatively correlated (r² = 0.79) with apparent oxygen utilization (AOU) for waters extending from the middle shelf into the deep Bering Sea indicating increasing microbial alteration of CDOM with depth. Although our data show that the CDOM photochemical environment of the Bering Sea is complex, our current information on its optical properties will aid in better understanding of the biogeochemical role of CDOM in carbon budgets in relation to the annual sea ice and phytoplankton dynamics, and to improved algorithms of ocean color remote sensing for this region.