Oxidative degradation of alternative gasoline oxygenates in aqueous solution by ultrasonic irradiation: Mechanistic study

Widespread pollution has been associated with gasoline oxygenates of branched ethers methyl tert-butyl ether (MTBE), di-isopropyl ether (DIPE), ethyl tert-butyl ether (ETBE), and tert-amyl ether (TAME) which enter groundwater. The contaminated plume develops rapidly and treatment for the removal/destruction of these ethers is difficult when using conventional methods. Degradation of MTBE, with biological methods and advanced oxidation processes, are rather well known; however, fewer studies have been reported for degradation of alternative oxygenates. Degradation of alternative gasoline oxygenates (DIPE, ETBE, and TAME) by ultrasonic irradiation in aqueous oxygen saturation was investigated to elucidate degradation pathways. Detailed degradation mechanisms are proposed for each gasoline oxygenate. The common major degradation pathways are proposed to involve abstraction of α-hydrogen atoms by hydroxyl radicals generated during ultrasound cavitation and low temperature pyrolytic degradation of ETBE and TAME. Even some of the products from β-H abstraction overlap with those from high temperature pyrolysis, the effect of β-H abstraction was not shown clearly from product study because of possible 1,5 H-transfer inside cavitating bubbles. Formation of hydrogen peroxide and organic peroxides was also determined during sonolysis. These data provide a better understanding of the degradation pathways of gasoline oxygenates by sonolysis in aqueous solutions. The approach may also serve as a model for others interested in the details of sonolysis.

► Gasoline oxygenates (ETBE, TAME, DIPE) were completely degraded after 6 hours under ultrasonic irradiation in O2 saturation.
► The major degradation pathways were proposed to involve abstraction of α-hydrogen atoms by hydroxyl radicals and low temperature pyrolytic degradation.
► The effect of β-H abstraction was not observed possibly because of 1,5 H-transfer inside cavitating bubbles.
► Formation mechanisms of hydrogen peroxide and organic peroxides were also discussed.