Distribution and characteristics of molecular size fractions of freshwater-dissolved organic matter in watershed environments: its implication to degradation

Distributions of molecular size and fluorescence properties of dissolved organic matter (DOM) in the Lake Biwa and Lake Baikal watersheds were investigated using the cross-flow ultrafiltration technique and three-dimensional fluorescence measurements. From the fluorescence properties, protein-like substances were usually found in the 0.1 μm-GF/F fraction (the Durapore membrane retentate of the GF/F filtrate) of the lake DOM. The results indicated autochthonous production of protein-like organic-matters in the lake environment. Fulvic acid (FA)-like components were composed of two fractions with respect to fluorescence properties and molecular size. Two FA-like fluorescence peaks, which showed different fluorescence peak positions in the excitation-emission matrix (EEM), were partly fractionated by the molecular size of 5000 daltons (5 kDa). The FA-like fluorescence peak position of the <5-kDa fraction was observed at the shorter wavelength region compared with that of the fraction between 5 kDa and 0.1 μm (5 kDa20.1 μm fraction). A blue shift of the FA-like fluorescence peak position as well as a decrease in the molecular size of the DOM was observed in lake samples. The relative contribution of the <5 kDa fraction to the DOC concentration was high in lake waters (68%–79%) compared with river waters (44%–68%), suggesting characteristic changes in molecular size between riverine and lacustrine DOM. DOM of the 5 kDa–0.1 μm fraction was relatively higher in river waters than in lake waters. These findings coincided with in situ distributions of the fluorescence properties and molecular size of DOM found in both stream and lake environments. These results indicate that FA-like substances from forested watersheds are decomposed qualitatively and quantitatively in the river-lake environment by photochemical and biological processes.