Hydrogen peroxide enhances the oxidation of oxygenated volatile organic compounds on mineral dust particles: a case study of methacrolein. 2014

Yue Zhao, and Dao Huang, and Liubin Huang, and Zhongming Chen
State Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University , Beijing 100871, People's Republic of China.

Heterogeneous oxidation of oxygenated volatile organic compounds (OVOCs) serves as an important sink of OVOCs as well as a source of secondary organic material. However, the roles of gas phase oxidants in these reactions are poorly understood. In this work, we present the first laboratory study of the heterogeneous reactions of methacrolein (MACR) on various mineral dust particles in the presence of gaseous H2O2. It is found that the presence of gaseous H2O2 significantly promotes both the uptake and oxidation of MACR on kaolinite, α-Al2O3, α-Fe2O3, and TiO2, but not on CaCO3. The oxidation of MACR produces organic acids as its major low-molecular-weight product, whose yields are enhanced by a factor of 2-6 in the presence of H2O2. In addition, organic peroxides such as methyl hydroperoxide, peroxyformic acid, and peroxyacetic acid are only formed in the presence of H2O2, and the formation of methyl hydroperoxide indicates that MACR oxidation on the surface involves reaction with OH radicals. A probe reaction using salicylic acid verifies the production of OH radicals from H2O2 decomposition on kaolinite, α-Al2O3, α-Fe2O3, and TiO2, which rationalizes the enhanced MACR oxidation observed on these particles. The uptake coefficients of MACR on kaolinite, α-Fe2O3, and TiO2 in the presence of H2O2 are on the order of 10(-5)-10(-4). Our results provide new insights into the formation and chemical evolution of organic species in the atmosphere.

UI MeSH Term Description Entries
D007616 Kaolin The most common mineral of a group of hydrated aluminum silicates, approximately H2Al2Si2O8-H2O. It is prepared for pharmaceutical and medicinal purposes by levigating with water to remove sand, etc. (From Merck Index, 11th ed) The name is derived from Kao-ling (Chinese: "high ridge"), the original site. (From Grant & Hackh's Chemical Dictionary, 5th ed) Kaolinite
D010084 Oxidation-Reduction A chemical reaction in which an electron is transferred from one molecule to another. The electron-donating molecule is the reducing agent or reductant; the electron-accepting molecule is the oxidizing agent or oxidant. Reducing and oxidizing agents function as conjugate reductant-oxidant pairs or redox pairs (Lehninger, Principles of Biochemistry, 1982, p471). Redox,Oxidation Reduction
D004391 Dust Earth or other matter in fine, dry particles. (Random House Unabridged Dictionary, 2d ed) House Dust,Housedust,Dust, House
D005290 Ferric Compounds Inorganic or organic compounds containing trivalent iron. Compounds, Ferric
D006861 Hydrogen Peroxide A strong oxidizing agent used in aqueous solution as a ripening agent, bleach, and topical anti-infective. It is relatively unstable and solutions deteriorate over time unless stabilized by the addition of acetanilide or similar organic materials. Hydrogen Peroxide (H2O2),Hydroperoxide,Oxydol,Perhydrol,Superoxol,Peroxide, Hydrogen
D000171 Acrolein Unsaturated three-carbon aldehyde. 2-Propenal,Acraldehyde,Acrylaldehyde,Acrylic Aldehyde,Allyl Aldehyde,Aqualin,Ethylene Aldehyde,2 Propenal,Aldehyde, Acrylic,Aldehyde, Allyl,Aldehyde, Ethylene
D000393 Air Pollutants Any substance in the air which could, if present in high enough concentration, harm humans, animals, vegetation or materials. Substances include GASES; PARTICULATE MATTER; and volatile ORGANIC CHEMICALS. Air Pollutant,Air Pollutants, Environmental,Environmental Air Pollutants,Environmental Pollutants, Air,Air Environmental Pollutants,Pollutant, Air,Pollutants, Air,Pollutants, Air Environmental,Pollutants, Environmental Air
D000537 Aluminum Oxide An oxide of aluminum, occurring in nature as various minerals such as bauxite, corundum, etc. It is used as an adsorbent, desiccating agent, and catalyst, and in the manufacture of dental cements and refractories. Alumina,Alumina Ceramic,Aluminum Oxide (Al130O40),Aluminum Oxide (Al2O),Aluminum Oxide (AlO2),Bauxite,Corundum,Sapphire,Ceramic, Alumina,Oxide, Aluminum
D001272 Atmosphere The gaseous envelope surrounding a planet or similar body. (From Random House Unabridged Dictionary, 2d ed) Atmospheres
D016877 Oxidants Electron-accepting molecules in chemical reactions in which electrons are transferred from one molecule to another (OXIDATION-REDUCTION). Oxidant,Oxidizing Agent,Oxidizing Agents,Agent, Oxidizing,Agents, Oxidizing

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