Size fractionation and optical properties of colloids in an organic-rich estuary (Thurso, UK)

The optical characteristics of a black water river estuary from the north coast of Scotland were examined in the filtered (0.4 µm), ultrafiltered (5 kDa) and colloid-enriched fractions of estuarine samples. The samples were collected over the full salinity range during a period when the pH was relatively constant (8.2–8.5) throughout the estuary, allowing the influence of salinity on estuarine colloidal processes to be distinguished. The properties examined in the bulk, the low molecular weight (LMW) and the colloidal fraction (HMW) were UV–visible absorption, 3-D fluorescence excitation–emission matrix (EEM) spectrum, inorganic and organic carbon, mean size (by dynamic light scattering), and size distribution by flow field-flow fractionation analysis (FlFFF). The combined results of these analyses support the view that river-borne, humic-rich colloids underwent two types of transformation upon mixing with the seawater end member. The first one resulted in an apparent increase in the abundance of LMW constituents and may be explained by coiling of the individual humic macromolecules. The second one resulted in an increase in the mean size measured in both the lower and higher colloidal size ranges, and may be explained by aggregation of colloids to form entities that were still mostly colloidal i.e., smaller than 0.4 µm. The LMW contribution to the bulk optical properties increased with increasing salinity. Very similar findings were obtained from simulated mixing experiments using a Nordic Reference NOM extract as a source of freshwater colloids. This indicates that changes in the molecular architecture and molar mass of river-borne colloids—not changes in their chemical nature—were responsible for the observed variations in the spectral characteristics of CDOM in this estuary.