Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom.
Environ Sci Technol. 2010 Feb 15;44(4):1360-5. doi: 10.1021/es902916f.
Hydrogen peroxide (H(2)O(2)) is an important atmospheric oxidant that can serve as a sensitive indicator for HO(x) (OH + HO(2)) chemistry. We report the first direct experimental determination of the uptake coefficient for the heterogeneous reaction of gas-phase hydrogen peroxide (H(2)O(2)) with titanium dioxide (TiO(2)), an important component of atmospheric mineral dust aerosol particles. The kinetics of H(2)O(2) uptake on TiO(2) surfaces were investigated using an entrained aerosol flow tube (AFT) coupled with a chemical ionization mass spectrometer (CIMS). Uptake coefficients (gamma(H(2)O(2))) were measured as a function of relative humidity (RH) and ranged from 1.53 x 10(-3) at 15% RH to 5.04 x 10(-4) at 70% RH. The observed negative correlation of RH with gamma(H(2)O(2)) suggests that gaseous water competes with gaseous H(2)O(2) for adsorption sites on the TiO(2) surface. These results imply that water vapor plays a major role in the heterogeneous loss of H(2)O(2) to submicrometer TiO(2) aerosol. The results are compared with related experimental observations and assessed in terms of their potential impact on atmospheric modeling studies of mineral dust and its effect on the heterogeneous chemistry in the atmosphere.
过氧化氢(H2O2)是一种重要的大气氧化剂,可作为 HO(x)(OH + HO2)化学的敏感指示剂。我们首次直接测定了气相过氧化氢(H2O2)与二氧化钛(TiO2)之间非均相反应的吸收系数,二氧化钛是大气矿物气溶胶粒子的重要组成部分。利用载气流溶胶流动管(AFT)与化学电离质谱仪(CIMS)联用,研究了 TiO2 表面上 H2O2 的吸收动力学。吸收系数(γ(H2O2))作为相对湿度(RH)的函数进行了测量,范围从 15% RH 时的 1.53×10-3到 70% RH 时的 5.04×10-4。观察到 RH 与γ(H2O2)之间的负相关表明,气态水与气态 H2O2 竞争 TiO2 表面上的吸附位。这些结果表明,水蒸气在亚微米 TiO2 气溶胶中非均相消耗 H2O2 方面起着主要作用。将结果与相关的实验观察结果进行了比较,并根据它们对矿物尘埃大气模拟研究及其对大气中非均相化学的影响的潜在影响进行了评估。