Background: Most particulate organic matter (POM) cannot be directly degraded in the conventional wastewater treatment, which should be transformed into dissolved organic matter (DOM) through a hydrolysis process. However, non-hydrolyzed POM in the biological treatment can limit treated efficiencies for the wastewater treatment plants (WWTPs) facilities. Hence an operational tool is indispensable for insight into removals of DOM and POM factions in the WWTP. In this study, excitation-emission matrix fluorescence spectroscopy (EEM) combined parallel factor analysis (PARAFAC), two-dimensional correlation (2D-COS) and structural equation modeling (SEM) was employed to evaluate removals of DOM and POM in a wastewater treatment plant. Results: Four fluorescence components were identified in DOM and POM substances from the WWTP by EEM combined with PARAFAC, i.e., tyrosine-like (TYLF), tryptophan-like (TRLF), microbial byproduct-like (MBLF), and fulvic acid-like (FALF). In A²/O process, the TYLF and TRLF of DOM were removed to a larger extent than those of MBLF and FALF in anaerobic tank, while TYLF and MBLF of POM were removed to a great extent than those of TRLF and FALF in primary sedimentation and aerobic tanks. By the 2D-COS, a decreasing variation order of DOM fractions in the wastewater treatment process was UV-FALF → MBLF2 → Vis-FALF → TRLF → TYLF, while the decreasing order of POM fractions was Vis-FALF → UV-FALF → MBLF2 → TYLF → MBLF1 → TRLF. SEM revealed that TRLF and TYLF of DOM were degraded by anaerobic microorganism, and TRLF could be transformed partially into FALF. However, TRFL and TYLF of POM were discomposed by aerobic microorganism. Conclusions: The 2D-COS and SEM can be practicable tools as EEM-PARAFAC for monitoring DOM and POM in the WWTP. The study could present a theoretical support to improving the retrofit of WWTP and formulating emission standards for organic pollutants.

A pilot-scale experiment is carried out for treating mixed wastewater containing pharmaceutical wastewater (PW) and domestic wastewater (DW), by a process that is a combination of hydrolysis acidification-ozone-modified anaerobic–anoxic–aerobic-ozone (A²/O) (pre-ozone) or hydrolysis acidification-modified A²/O-ozone (post-ozone). The effects of different mixing ratios of PW and DW and pre-ozone treatment or post-ozone treatment on the removal of nitrogen and phosphorus and chemical oxygen demand (COD) are compared and studied. The optimal ratio of PW in mixing wastewater is 30%, which has the optimal COD removal efficiency and minimum biotoxicity to biological treatment. The pre-ozone treatment shows more advantages in removing nitrogen and phosphate but the post-ozone treatment shows more advantages in COD removal. Analysis of dissolved organic matter (DOM) demonstrates that post-ozone treatment has a more significant effect on the removal of fulvic acid and humic acid than the effect from the pre-ozone treatment, so the COD removal is better. Overall DOM degradation efficiency by post-ozone treatment is 55%, which is much higher than the pre-ozone treatment efficiency of 38%. Microbial community analysis reveals that the genus Thauera and the genus Parasegetibacter take great responsibility for the degradation of phenolics in this process. All the results show that the post-ozone treatment is more efficient for the mixed wastewater treatment in refractory organics removal.

A novel coagulation combined with UV/O₃ process was employed to remove the effluent organic matter (EfOM) from a biotreated pharmaceutical wastewater for harmlessness. The removal behavior of EfOM by UV/O₃ process was characterized by synchronous fluorescence spectroscopy (SFS) integrating two-dimensional correlation (2D-COS) and principal component analysis (PCA) technology. The highest dissolved organic carbon (DOC) and ratio of UV₂₅₄ and DOC (SUVA) removal efficiency reached 55.8% and 68.7% by coagulation-UV/O₃ process after 60 min oxidation, respectively. Five main components of pharmaceutical tail wastewater (PTW) were identified by SFS. Spectral analysis revealed that UV/O₃ was selective for the removal of different fluorescent components, especially fulvic acid-like fluorescent (FLF) component and humus-like fluorescent (HLF) component. Synchronous fluorescence/UV-visible two-dimensional correlation spectra analysis showed that the degradation of organic matter occurred sequentially in the order of HLF, FLF, microbial humus-like fluorescence component (MHLF), tryptophan-like fluorescent component (TRLF), tyrosine-like fluorescent component (TYLF). The UV/O₃ process removed 95.6% of HLF, 80.0% of FLF, 56.0% of TRLF, 50.8% of MHLF and 44.4% of TYLF. Therefore, the coagulation-UV/O₃ process was proven to be an attractive way to reduce the environmental risks of PTW.