Unraveling the over-oxidation inhibition mechanism during the hybrid ozonation-coagulation process: Immediate entrapment and complexation between intermediate organic matter and coagulants.

Pre-ozonation coagulation process had a very low and narrow range of ozone dosages for enhancing the dissolved organic matter (DOC) removal efficiency, in which over-oxidation may occur if the ozone dosage was not strictly controlled. In contrast, the proposed hybrid ozonation-coagulation (HOC) process with higher oxidation ability notably inhibited over-oxidation in this study, and exhibited improved DOC removal efficiency compared with coagulation at a much wider range of ozone dosages at different initial pH for the treatment of WWTP effluent. The HOC process also had a higher DOC removal efficiency than pre-ozonation coagulation. According to zeta potential analysis, a rising trend indicated that complexation between organic matter and metal coagulants persisted throughout the HOC process. However, the zeta potential remained almost unchanged during subsequent coagulation after pre-ozonation at high ozone dosages. Synchronous fluorescence spectroscopy analysis revealed that immediate entrapment and complexation between hydrolysed coagulants and oxidized intermediate organic matter occurred in the HOC process. Furthermore, FT-IR analysis showed that more oxygen-containing functional groups were generated, which were effectively trapped by metal coagulants and readily flocculated. To further prove the immediate entrapment and complexation during the HOC process, UPLC-Q-TOF-MS was applied to analyze the intermediate organic matter in the supernatant and flocs. The results implied that C21- organic matter was oxidized and decomposed into C11-C20, and C11-C20 intermediate organic matter was trapped and complexed by metal coagulants once formed, which led to the increase of C11-C20 in the flocs. Nevertheless, the catalytic ozonation process (γ-Al2O3/O3) with the same oxidation ability as the HOC process decomposed the organic matter into C1-C10. XPS analysis further confirmed the immediate entrapment and removal of aliphatic/aromatic carbon and oxygen-containing functional groups during the HOC process. Therefore, over-oxidation can be effectively inhibited, and wide range of ozone dosages was obtained during the HOC process, which facilitate the application of the HOC process.

Assessing the performance of coral reef-like floc towards the removal of low molecular weight organic contaminant.

The removal of low molecular weight (MW) organics by coagulation is always a challenge in water treatment. In this study, we proposed a novel coagulation strategy: continuous dosing coagulation (CDC). The metallic coagulant and alkali were continuously dosed into water that was pre-acidized, rather than adding all the coagulant and alkali at once as in conventional coagulation (CC). The CDC process promoted the removal of different low MW organics, performing 15% better than the CC process. The best performance occurred at initial pH 6 and the coagulant dosing rate was 2 mg/(L·min). Under optimal conditions, the continuously dosed coagulant formed medium polymer Al in the early stages, which bound low MW organics to form complexes. Then, the subsequently dosed coagulant could adhere to the primary complexes and form coral reef-like surfaces with higher zeta potential and specific surface area. Each freshly formed surface bound contaminants and covered the previous surface. As a result, more dissolved low MW organic contaminants were included in the interior of flocs. However, in the CC process, all the coagulant was dosed at once, resulting in the rapid formation of aluminum hydroxide clusters, which had cotton-like surfaces with fewer binding sites. To achieve similar organic removal in treating secondary effluent, the CDC dosage was half of the CC dosage, indicating the potential economic benefits. The CDC process is a promising technology and the application in various water treatments should be further investigated.

Behaviour of ozone in the hybrid ozonation-coagulation (HOC) process for ibuprofen removal: Reaction selectivity and effects on coagulant hydrolysis.

Simultaneous ozonation and coagulation can be realized in one unit in the developed hybrid ozonation-coagulation (HOC) process. To reveal the reaction sequence within the HOC process, the ibuprofen (IBP) removal efficiency of the ozonation only, HOC and HOC-PO43- (inhibition of the reactions between ozone and metal coagulant) processes at pH 5 and different ozone dosages were investigated. The removal efficiency is almost the same for the three processes at a low ozone dosage (4.8 mg/L), and higher removal performance can be achieved by the HOC process with increasing ozone dosage. It can be implied that ozone preferentially reacts with OH- to generate OH which react with IBP in the HOC process, and subsequently reacts with the surface hydroxyl groups of hydrolysed Al species to enhance OH generation. Moreover, based on the kinetics, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR) analyses, the synergistic reactions between ozone and the metal coagulants (SOC) started to take effect from ozone dosage of 9.6 mg/L, which further verified that ozone will be involved in the IBP ozonation prior to the SOC reactions. The subsequent SOC reactions also resulted in the increased generation of polymeric Al species and more abundant intermediates in the HOC process.