Dissolved organic matter (DOM) in municipal wastewater was mainly characterized using high-performance liquid chromatography (HPLC) and size exclusion chromatography (HPSEC) with multi-excitation/emission fluorescence scan. Meanwhile, fluorescence excitation-emission-matrix combined with parallel factor analysis (EEM-PARAFAC) was also applied. Compared with chromatography fluorescence fingerprints, the EEM-PARAFAC model could not reflect the variety of DOM species with similar fluorescence but different physicochemical properties. The chromatography results showed that the protein-like species were variable among different municipal wastewater treatment plants, some of which are in combination with humic-like species; while there were two major humic-like species fractionated by hydrophilicity and molecular weight (MW), which are also the major contributors to UV absorbance at 254 nm. It was also identified that the relatively hydrophilic humic fractions were slightly larger than the relatively hydrophobic humic fractions. In all the investigated wastewater treatment plants, the relatively hydrophilic and larger MW humic fraction mainly contributed to the fluorescence intensity of humic-like EEM-PARAFAC components. As well as facilitating interpretations of EEM-PARAFAC components, the HPLC/HPSEC fluorescence fingerprints also contributed to a better understanding of fluorescent DOM species in municipal wastewater.

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