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测量 HO2 非均相损耗到亚微米无机盐气溶胶的吸收系数。

Measurements of uptake coefficients for heterogeneous loss of HO2 onto submicron inorganic salt aerosols.

机构信息

School of Chemistry, University of Leeds, Leeds, UK.

出版信息

Phys Chem Chem Phys. 2013 Aug 21;15(31):12829-45. doi: 10.1039/c3cp51831k.

Abstract

Laboratory studies were conducted to investigate the kinetics of HO2 radical uptake onto submicron inorganic salt aerosols. HO2 reactive uptake coefficients were measured at room temperature using an aerosol flow tube and the Fluorescence Assay by Gas Expansion (FAGE) technique that allowed for measurements to be conducted under atmospherically relevant HO2 concentrations ([HO2] = 10(8) to 10(9) molecule cm(-3)). The uptake coefficient for HO2 uptake onto dry inorganic salt aerosols was consistently below the detection limit (γ(HO2) < 0.004). The mass accommodation coefficient of HO2 radicals onto Cu(II)-doped (NH4)2SO4 aerosols was measured to be α(HO2) = 0.4 ± 0.3 representing the kinetic upper limit to γ. For aqueous (NH4)2SO4, NaCl and NH4NO3 aerosols not containing traces of transition metal ions, a range of γ(HO2) = 0.003-0.02 was measured. These values were much lower than γ values previously measured on aqueous (NH4)2SO4 and NaCl aerosols and also those typically used in atmospheric models (γ(HO2) = 0.1-1.0). Evidence is presented showing that the HO2 uptake coefficients onto aqueous salt aerosol particles are dependent both on the exposure time to the aerosol and on the HO2 concentration used.

摘要

实验室研究了 HO2 自由基在亚微米无机盐气溶胶上的吸收动力学。在室温下,使用气溶胶流动管和荧光分析气相扩展(FAGE)技术测量了 HO2 反应性吸收系数,该技术允许在与大气相关的 HO2 浓度([HO2]=10^8 至 10^9 分子 cm^-3)下进行测量。HO2 对干燥无机盐气溶胶的吸收系数始终低于检测限(γ(HO2)<0.004)。HO2 自由基在 Cu(II)掺杂(NH4)2SO4 气溶胶上的质量容纳系数α(HO2)测量为 0.4±0.3,代表 γ 的动力学上限。对于不含痕量过渡金属离子的水合(NH4)2SO4、NaCl 和 NH4NO3 气溶胶,测量得到的 HO2 吸收系数范围为 0.003-0.02。这些值远低于以前在水合(NH4)2SO4 和 NaCl 气溶胶上测量的γ值,也低于大气模型中通常使用的值(γ(HO2)=0.1-1.0)。研究结果表明,HO2 对水合盐气溶胶颗粒的吸收系数既取决于对气溶胶的暴露时间,也取决于使用的 HO2 浓度。

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