Unravelling relationships between fluorescence spectra, molecular weight distribution and hydrophobicity fraction of dissolved organic matter in municipal wastewater.

The characteristics of dissolved organic matter (DOM) in the influent and secondary effluent from 6 municipal wastewater treatment plants (WWTPs) were investigated with a size exclusion chromatogram (SEC) coupled with multiple detectors to simultaneously detect ultraviolet absorbance, fluorescence, dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) as a function of molecular weight (MW). The SEC chromatograms showed that biopolymers (>6 kDa) and humic substances (0.5-6 kDa) comprised the significant fraction in the influent, while humic substances became the abundant proportion in the secondary effluent. Direct linkages between MW distribution and hydrophobicity of DOM in the secondary effluent were further explored via SEC analysis of XAD resin fractions. DON and DOC with different hydrophobicity exhibited significantly distinct MW distribution, indicating that it was improper to consider DOC as a surrogate for DON. Different from DOC, the order of averaged MW in terms of DON was hydrophobic neutral ≈ transphilic neutral > hydrophobic acid > transphilic acid > hydrophilic fraction. Fluorescence spectral properties exhibited a significant semi-quantitative correlation with MW and hydrophobicity of DOC, with Pearson's coefficients of -0.834 and 0.754 (p < 0.01) for biopolymer and humic substances. Meanwhile, regional fluorescence proportion was demonstrated to indicate the MW and hydrophobicity properties of DON at the semi-quantitative level. The fluorescence excitation-emission matrix (EEM) could be explored to provide a rapid estimation of MW distribution and hydrophobic/hydrophilic proportion of DOC and DON in WWTPs.

Release and removal of algal organic matter during prechlorination and coagulation treatment of cyanobacteria-laden water: Are we on track?

A better understanding of the physicochemical properties and fate of algae-derived organic matter (AOM) in water treatments significantly benefits the control of algae-derived disinfection byprodcuts and process parameter optimization. In this study, we conducted a comprehensive investigation of the release and treatability of dissolved organic matter during prechlorination and postcoagulation treatments of cyanobacteria-laden source water via size-exclusion chromatography-tandem diode array detector, fluorescence detector and organic carbon detector. The results revealed that the allochthonous humic substances could protect algal cell membrane from damage during prechlorination at a low level of chlorine dose. Due to the release and oxidation of biopterins during prechlorination of M. aeruginosa cells, the variation of the humic-like fluorescence can be used to indicate the chlorine dose for a sufficient membrane damage of algae cells. The prechlorination of M. aeruginosa cells induced minimal release of large MW biopolymer fractions but much more release of low MW fractions E1 and E2 (i.e., unknown carbonaceous substances and fluorescent nitrogenous biopterins). The physically extracted AOM contained a large proportion of biopolymers and could not well represent those released during prechlorination treatment. During coagulation, the negative effect of humic substances on the coagulant demand to achieve algae removal was more remarkable than AOM released by prechlorination. The high-MW biopolymers and humic substances can be removed over 50% by coagulation. Among the low-MW carbonaceous fractions, E1 released by prechlorination can also be effectively removed via coagulation while fractions C, D (possibly oligopeptides or secondary aromatic metabolites & low MW acids) and nitrogenous biopterins were recalcitrant to coagulation. This study highlights the differences of AOM properties between physical extraction and prechlorination and provides a basis for drinking water treatment plants to give more attention to the recalcitrant low MW fractions in coagulation when treating algae-laden source water.

Developing a restricted chlorine-dosing strategy for UV/chlorine and post-chlorination under different pH and UV irradiation wavelength conditions.

UV/chlorine and chlorination processes have drawn great interests of water treatment utilities for oxidation and disinfection purposes. This work proposed a restricted chlorine-dosing strategy for UV/chlorine and post-chlorination under different pH and UV irradiation conditions by comprehensively assessing the oxidation of natural organic matter (NOM), formation of 9 haloacetic acids (HAA9) and bromate, and alteration of toxicity. During UV/chlorine with restricted chlorine doses, the oxidation of NOM chromophores (i.e., ΔUVA254) showed an apparent dependence on cumulative exposures of free available chlorine (CTFAC); Meanwhile, HAA9 formation was determined by CTFAC values and could be linearly correlated with ΔUVA254 irrespective of pH and UV irradiation wavelength. Irradiated by 254 nm LP-Hg lamp, the faster chlorine photolysis produced relatively higher steady-state concentrations of Cl• and HO• species but resulted in lower CTFAC. Reducing CTFAC values by operation parameters (pH, UV wavelength and irradiation fluence) could mitigate HAA9 formation during UV/chlorine at a specific chlorine dose. Additionally, high bromide concentration and acidic pH promoted more bromo-HAAs formation, and the presence of NOM significantly suppressed bromate formation. Analogous to ozonation, the UV/chlorine pre-oxidation could reduce the HAA9 formation potentials during post-chlorination at mildly alkaline pH. The photobacterium bioassay further demonstrated that although the UV/chlorine treatment might have increased the acute toxicity, the post-chlorination treatment could polish the acute toxicity to the level of chlorination alone. These results suggest that with the restricted chlorine-dosing strategy, the trade-off between oxidation/disinfection efficiency and DBPs formation can be controlled by monitoring CTFAC and ΔUVA254 values during UV/chlorine treatment.