Relating dissolved organic matter fluorescence to functional properties

The fluorescence excitation emission matrix properties of dissolved organic matter from three rivers and one lake in NW England are analysed. Sites are sampled in duplicate and for some sites seasonally to cover variations in dissolved organic matter composition, river flow, and carbon isotopic (13C, 14C) variability. Results are compared to the functional properties of the dissolved organic matter, the functional assays provide quantitative information on light absorption, fluorescence, photochemical fading, pH buffering, copper binding, benzo[a]pyrene binding, hydrophilicity and adsorption to alumina. Fluorescence characterization of the dissolved organic matter samples demonstrates that peak C fluorescence emission wavelength, the ratio of peak T to peak C fluorescence intensity, and the fluorescence : absorbance ratio best differentiate different dissolved organic matter samples. These parameters correspond to dissolved organic matter aromaticity, the ratio of labile to recalcitrant organic matter, and dissolved organic matter molecular weight. Peak C fluorescence emission wavelength, the ratio of peak T to peak C fluorescence intensity, and the fluorescence : absorbance ratio fluorescence parameters also have strong correlations with several of the functional assays, in particular the extinction coefficients, benzo(a)pyrene binding and alumina adsorption, and buffering capacity. In many cases, regression equations with a correlation coefficient >0.9 are obtained, suggesting that dissolved organic matter functional character can be predicted from DOM fluorescence properties. For one site, the relationship between dissolved organic matter source, fluorescence, function and carbon isotopic composition is discussed.