Are microbubbles magic or just small? a direct comparison of hydroxyl radical generation between microbubble and conventional bubble ozonation under typical operational conditions

The application of microbubbles for water treatment is an emerging technology which has been shown to significantly enhance gas–liquid contacting processes. When applied to ozonation, microbubble technology has been shown to enhance mass transfer and the speed and extent of compound removal compared with conventional bubbling techniques. One explanation as to why microbubble systems outperform conventional systems is that microbubbles shrink, collapse and spontaneously generate hydroxyl radicals which is thought to enhance the speed of compound removal. This study compared microbubble (mean diameter 37 μm) and conventional bubble (mean diameter 5.4 mm) ozonation systems under identical conditions. The experiments were normalised for effective ozone dose to determine whether microbubble ozonation generated significantly more hydroxyl radicals than conventional bubble ozonation. 4-chlorobenzoic was used as the hydroxyl radical probe and the proportion of hydroxyl radicals generated for a given effective ozone dose was quantified. The •OH-exposure to O3-exposure (the Rct) was used to compare the systems. The ratio of the mean RctMicrobubble to mean RctConventional was 0.73, 0.84 and 1.12 at pH 6, 7 and 8 respectively. Statistical assessment of the Rct showed that there was no significant difference between the bubble systems. No evidence was found to support the hypothesis that microbubble systems generate more •OH. Instead, the level of •OH-exposure is linked to the effective dose and pH of the system and future designs should focus on those factors to deliver •OH based benefits.