Dissolved organic matter(DOM)is an important element of natural aquatic systems. Due to differences in their hydrophobic/hydrophilic properties and various functional groups, chemical appearances of DOM fractions also vary. In this study, seven natural waters, extending from Xiaheyan to Toudaoguai along the Ning-Meng section of the Yellow river, were sampled in April 2015. Four DOM fractions were obtained by pumping through XAD-4 and XAD-8 resins, i.e., hydrophobic acid (HOA), hydrophobic base (HOB), weak hydrophobic acid (WHOA), and hydrophilic matter (HYI). Based on detection by three-dimensional excitation-emission matrix fluorescence (EEM) and correlation analysis, relationships with five metal ions (Pb, Zn, Cu, Cr, As) were analyzed. Results show that DOC gradually increased along an upstream to downstream continuum in the Ning-Meng section. HYI (small molecular proteins) was the main DOM fraction present, followed by HOA, suggesting enhanced microbial-sourced impact from industrial sewage discharges. The significant peaks of humic-like (A, C) and protein-like compounds (T1) in the EEM chart further highlight the effect of endogenous pollution caused by wastewater. Furthermore, SPSS fitting results indicate that DOM is correlated with all five metal ions, especially with Cu. In terms of the four DOM fractions, HYI showed the strongest correlation with Cu, illustrating the significant relationship between HYI and Cu during the migration and transformation process. Moreover, the fluorescence intensity of protein-like compounds decreased with increasing Cu concentration, possibly due to fluorescence quenching caused by complexation between Cu and proteins in HYI.
Keywords: XAD resin; dissolved organic matter(DOM); fluorescence quenching; heavy metal; hydrophilic matter(HYI).