Changes in dissolved organic matter (DOM) characteristics were investigated during a storm event in the Kyungan River using UV-visible, fluorescence spectroscopy, resin fractionation, and size exclusion chromatography (SEC). Water samples were collected at nine sampling times to reflect a variation of the river water level. A dramatic increase was observed for chemical oxygen demand (COD) versus biochemical oxygen demand, suggesting that non-biodegradable organic components may be more contained in the organic matters driven by the storm. Specific UV absorbance values increased from 2.15 to 3.16 L/mgC-m, reaching the maximum level at the highest water level. The storm runoff resulted in the reduction of protein-like fluorescence (PLF), the increase of fulvic-like and humic-like fluorescence for the synchronous fluorescence spectra of DOM. Weight-average molecular weight (MW w ) values increased from 1,100 to 1,510 Da due to the increment of high MW fractions in the SEC chromatograms. Overall changes in DOM composition may be explained by the inflow of soil-derived DOM from the upstream basins brought by the storm. The humification index (HIX) exhibited a positive correlation with MW w values, suggesting that HIX may be suggested to a prediction descriptor for DOM MW during the storm event. PLF presented a negative correlation with DOM MW, suggesting that protein-like fluorescent compounds are associated with low MW components in the river. More input of humic substances by the storm runoff appears to shift DOM into a higher MW value as revealed by a positive correlation between MW w and hydrophobic fraction.

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Different land uses of upstream catchments may affect the quantity and the quality of dissolved organic matter (DOM) in watersheds, but the influence may differ by season. In this study, we examined concentrations and selected spectroscopic properties of DOM and the propensity to form trihalomethanes (THMs) for 19 different middle-sized watersheds across the Han River basin in Korea. Sampling was conducted for non-storm events during pre-monsoon (May) and monsoon seasons (July). The anthropogenic land uses including agricultural and residential areas occupied 2.3 to 49.4% of the upstream catchments of the watersheds. Non-aromatic, labile, and less condensed DOM structures were more abundant in the monsoon season. Parallel factor analysis (PARAFAC) modeling with fluorescence data demonstrated that a combination of three different fluorescence components could explain the seasonal and the spatial distributions of DOM characteristics. Terrestrial humic-like fluorescence was the most abundant component for all the DOM samples, while protein-like fluorescence became more pronounced for the monsoon season. THM concentrations did not differ between the two seasons. Observed seasonal differences in the concentrations and the characteristics of DOM suggested a greater contribution of groundwater to the streams in watersheds in the monsoon versus the pre-monsoon season. Significant correlations among anthropogenic land use, microbial humic-like fluorescence, and the propensity to form THMs were found only for the pre-monsoon season. Principal component analysis (PCA) demonstrated that, regardless of the season, anthropogenic land uses increased the concentrations of DOM and nutrients but that their effects on the DOM properties were not evident for the monsoon season.

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