The formation of carcinogenic bromate ions is a constraint when ozone is used for the remediation of water containing brominated organic materials. With its strong oxidizing ability, ozone rapidly transforms bromide in aqueous media to bromate, through a series of reactions involving hydroxyl radicals. Several strategies, such as limiting the ozone concentration, maintaining pH < 6, or the use of ammonia or hydrogen peroxide were explored to minimize bromate generation. However, most of the above strategies had a negative effect on the ozonation efficiency. The advanced oxidation processes, using catalysts together with ozone, have proven to be a promising technology for the degradation of pollutants in wastewater, but very few studies have been conducted to find ways to minimize bromate formation during this approach. The proposed article, therefore, presents a comprehensive review on recent advances in bromate reduction in water by catalytic ozonation and proposes reaction mechanisms associated with the catalytic process. The main aim is to highlight any gaps in the reported studies, thus creating a platform for future research and a quest to find environment friendly and efficacious catalysts for minimizing bromate formation in aqueous media during ozonation of brominated organic compounds.

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The ozone-initiated oxidation of 2-chloroethanol was followed by monitoring the consumption of the halogenated organic substrate. Gas chromatographic analysis of the ozonated products showed an increase in conversion from about 1 % after 3 h of ozone treatment to about 22 % after 12 h. The yields of major ozonated products identified and quantified namely acetaldehyde, acetic acid, and chloride ion increased proportionately as a function of ozone treatment time. The percent conversion of 2-chloroethanol in the presence of acetic acid or ethyl acetate were found to be higher than those under solvent-free conditions with similar products obtained. The use of activated charcoal during the ozonolyis of 2-chloroethanol showed a significant increase in the percent conversion of the substrate compared to solvent free ozonation. Based on the experimental findings, the overall mechanism for the reaction between 2-chloroethanol and ozone is described.

Background 2,4-dichlorophenoxyacetic acid (2,4-DCPA acid) is a toxic herbicide. Earlier studies to remove 2,4-DCPA acid from water used expensive and/or toxic reagents, resulting in the formation of toxic organic by-products (Org-BPs). This study evaluates the removal of 2,4-DCPA acid from aqueous media using uncatalysed and catalytic ozonation with Fe doped with Ni and Co respectively. Methods Mixed metal oxides of Ni and Co loaded on Fe respectively, prepared by co-precipitation and physical mixing were used as catalyst for ozone facilitated oxidation degradation of 2,4-DCPA acid. Their surface properties were determined by employing SEM, BET and NH 3 -TPD. HPLC, IC and TOC data were used for quantifying substrate and oxidation products. Results Conversion of 2,4-DCPA acid increased from 38% in acidic water to 73% in basic water, however, only 26% of the total carbon was removed and 9.5% in the form of Org-BPs. With 7:3 Fe:Ni (Co-ppt) catalyst (surface area 253 m 2 g −1 ; particle size 236 nm), 97% of pollutant was converted. Most importantly, 92% of carbon was removed and Org-BP formation was minimized to 1.5%. With 7:3 Fe:Ni (Mixed) catalyst (surface area 12 m 2 g −1 ; particle size 1274 nm), 68% of 2,4-DCPA acid was converted, while 23% of TOC was removed, however, 66% of Org-BP's still remained. Conclusion In uncatalysed ozonation degradation of 2,4-DCPA acid improved with the increase in hydroxide ion concentration. Ozonation in presence of 7:3 Fe:Ni (Co-ppt) catalyst resulted in highest activity for dechlorination, TOC removal and Org-BP minimization, thus improving the quality of contaminated water.

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