Elsevier, Applied Catalysis B: Environmental, (168-169), p. 183-194, 2015
DOI: 10.1016/j.apcatb.2014.11.048
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This study investigates the photocatalytic oxidation of limonene, used as a model terpenoid, close to indoor air conditions. Beside the characterization of limonene removal kinetic on the ppb range, special attention has been paid to reaction intermediates and by-products: (i) in the gas phase, (ii) in the adsorbed phase and (iii) in the particulate phase. All along the oxidation reaction organic reaction intermediates have been monitored. Despite a high conversion rate of limonene after 10 hours of treatment, 20 primary and secondary reaction intermediates were detected and quantified in the gas phase. The most abundant ones are acetone and acetaldehyde. The characterization of limonene adsorbed TiO2 surface under UV illumination using DRIFTS pointed out the fact that the photocatalyst surface acts as a pool of heavy reaction intermediates, close to terpenoid structure, which may be responsible for the release of some secondary reaction intermediates. The mineralization of limonene has been assessed during the whole oxidation process through CO and CO2 monitoring. CO2 formation is observed more than 12 hours beyond limonene complete removal, confirming the long term oxidation of the adsorbed phase. The photocatalytic heterogeneous formation of secondary organic aerosol is reported for the first time. A massive production of SOA since the first steps of limonene photocatalytic oxidation is evidenced. Based on the quantitative analyses performed, carbon mass balances have been calculated along the oxidation reaction advancement. The highest contributions of organic reaction intermediates and SOA in the carbon balance are respectively 12% and 1.6%. When limonene is removed from the gas phase, more than 60% of the carbon balance remains unidentified but this contribution can be mainly attributed to the adsorbed organic species. After 24 hours of treatment, almost 75% of the organics are mineralized into CO2.