Assessing the spatial and temporal variability of dissolved organic matter in Liverpool Bay using excitation–emission matrix fluorescence and parallel factor analysis

Abstract

The spatial and diurnal tidal variability of dissolved organic carbon (DOC) concentrations and the composition of dissolved organic matter (DOM), as evaluated by high-temperature catalytic oxidation and excitation–emission matrix combined with parallel factor analysis (EEM–PARAFAC), respectively, were determined in Liverpool Bay. EEM–PARAFAC modeling resulted in six fluorescent components characterized as terrestrial humic-like (two), microbial humic-like (two), and protein-like (two). The spatial distributions of DOC and the four humic-like components were negatively correlated with salinity in the high-salinity waters observed in this study (30.41–33.75), suggesting that terrestrial DOM was conservatively distributed. The spatial patterns of protein-like components were largely different from those of DOC, humic-like components, and chlorophyll a, suggesting that these distributions were the combined result of production and degradation in the bay in addition to river inputs. These findings suggest that the DOM dynamics in Liverpool Bay are strongly controlled by river-dominated allochthonous DOM inputs with some less significant contributions of autochthonous DOM within the bay. In addition, the temporal variations of DOM associated with the diurnal tidal cycles were determined at one inshore (31.34–32.24 salinity) and one offshore (33.64–33.75 salinity) station in the bay. Negative linear relationships between salinity and DOM characteristics, i.e., DOC, humic-like, and protein-like components, were observed at the inshore station. In contrast, no relationship was observed at the offshore station, suggesting that the export of DOM through rivers and possibly tidal flats have a noticeable influence on DOM concentration and composition up to a relatively elevated salinity of around 33 in Liverpool Bay.