Microbubble ozonation of the antioxidant butylated hydroxytoluene: Degradation kinetics and toxicity reduction

Butylated hydroxytoluene (BHT) is recognized as a crucial pollutant in aquatic environments, but efforts to achieve its complete removal are without success. The aim of this study was to investigate the degradation efficiency of BHT in water using ozone microbubbles (OMB), coupled with toxicity change assessment at sub-lethal BHT concentrations (0.34, 0.45 and 0.90 μM) based on oxidative stress biomarkers in Daphnia magna. The efficiency of OMB on ozone gas mass transfer was assessed and the contribution of hydroxyl radicals (·OH) in the degradation of BHT was determined using p-chlorobenzoic acid (pCBA) probe compound and a ·OH radical scavenger (sodium carbonate, Na₂CO₃). The ozone gas mass transfer coefficient (k_La = 1.02 × 10⁻² s⁻¹) was much larger than the ozone self-decomposition rate (k_d = 8 × 10⁻⁴ s⁻¹) implying little influence of self-decomposing ozone in the volumetric ozone transfer during OMB generation. Generally, OMB improved ozone gas mass transfer (1.3–19-fold) relative to conventional ozone techniques, while indirect reaction of BHT with ·OH was dominant (82%) over the direct reaction with molecular ozone. Addition of 15, 25 and 35 mM Na₂CO₃ reduced BHT degradation by 30, 50 and 65%, respectively, indicating the significance of ·OH in the degradation of BHT. Increase in initial BHT concentration correspondingly reduced its removal rate by OMB possibly due to increase in metabolites produced during ozonation. Post BHT treatment exposure tests recorded significant (p < 0.05) reductions in oxidative stress (according to enzyme activities changes) in D. magna compared to pretreatment tests, demonstrating the effectiveness of OMB in detoxification of BHT. Overall, the results of the study indicate that OMB is extremely efficient in complete degradation of BHT in water and, consequently, significantly (p < 0.05) reducing its toxicity.