title: Kinetics and mechanisms of heterogeneous reaction of gaseous hydrogen peroxide on mineral oxide particles.
abstract: Recent studies have shown that heterogeneous reactions of hydrogen peroxide (H(2)O(2)) on aerosol surfaces may play an important role in tropospheric chemistry. The data concerning the kinetics and mechanisms of these reactions, however, are quite scarce so far. Here, we investigated, for the first time, the heterogeneous reactions of gaseous H(2)O(2) on SiO(2) and α-Al(2)O(3) particles, two major components of mineral dust aerosol, using transmission-Fourier Transform Infrared (T-FTIR) spectroscopy, and high-performance liquid chromatography (HPLC). It is found that H(2)O(2) molecularly adsorbs on SiO(2), and a small amount of molecularly adsorbed H(2)O(2) decomposes due to its thermal instability. For α-Al(2)O(3), catalytic decomposition of H(2)O(2) evidently occurs, but there is also a small amount of H(2)O(2) molecularly adsorbed on the particle surface. The BET uptake coefficients of H(2)O(2) on both particles appear to be independent of gaseous H(2)O(2) concentration (1.27-13.8 ppmv) and particle sample mass (2.8-6.5 mg for SiO(2) and 8.6-18.9 mg for α-Al(2)O(3)), but are strongly dependent on relative humidity with the values ranging from (1.55 ± 0.14) × 10(-8) and (1.21 ± 0.04) × 10(-7) at 2% RH to (0.61 ± 0.06) × 10(-8) and (0.76 ± 0.09) × 10(-7) at 76% RH for SiO(2) and α-Al(2)O(3), respectively. On the basis of the experimental results and literature data, the potential mechanisms for heterogeneous decomposition of H(2)O(2) were proposed, and the atmospheric implications of these reactions were discussed. It is found that heterogeneous reaction of H(2)O(2) on both mineral oxides plays a significant role in processing mineral aerosols, although its role as a sink for ambient H(2)O(2) is probably limited.
authors.affiliation: State Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University , Beijing 100871, China.
authors.forename: Yue
authors.initials: Y
authors.lastname: Zhao
authors.forename: Zhongming
authors.initials: Z
authors.lastname: Chen
authors.forename: Xiaoli
authors.initials: X
authors.lastname: Shen
authors.forename: Xuan
authors.initials: X
authors.lastname: Zhang
mesh_terms: D000336:Aerosols / Q000737:chemistry*; D000393:Air Pollutants / Q000032:analysis / Q000737:chemistry*; D000536:Aluminum Hydroxide / Q000737:chemistry*; D001272:Atmosphere / Q000737:chemistry; D002851:Chromatography, High Pressure Liquid; D004391:Dust / Q000032:analysis; D006861:Hydrogen Peroxide / Q000032:analysis / Q000737:chemistry*; D007700:Kinetics; D010084:Oxidation-Reduction; D012822:Silicon Dioxide / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared; D014867:Water / Q000737:chemistry
chemical_list: D000336:Aerosols; D000393:Air Pollutants; D004391:Dust; D014867:Water; D000536:Aluminum Hydroxide; D012822:Silicon Dioxide; D006861:Hydrogen Peroxide