为研究亚硝酸(HONO)在γ-Al_(2)O_(3)(110)表面非均相氧化SO_(2)的机理,基于密度泛函理论(density functional theory,DFT)的第一性原理计算了SO_(2)和HONO在γ-Al_(2)O_(3)(110)表面的吸附机制和氧化机制。结果表明,SO_(2)以分子的形...为研究亚硝酸(HONO)在γ-Al_(2)O_(3)(110)表面非均相氧化SO_(2)的机理,基于密度泛函理论(density functional theory,DFT)的第一性原理计算了SO_(2)和HONO在γ-Al_(2)O_(3)(110)表面的吸附机制和氧化机制。结果表明,SO_(2)以分子的形式吸附在完整或缺陷的γ-Al_(2)O_(3)(110)表面,而HONO仅在完整表面上以分子的形式存在。表面氧缺陷的存在不仅会增强SO_(2)和HONO的吸附强度,而且能诱导HONO在含氧缺陷表面的分解(HONO→NO+·OH)。通过局域态密度(partial density of states,PDOS)和Mulliken电荷布局分析表明,HONO的分解遵循Haber-Weiss机制。当SO_(2)和HONO共同吸附在氧缺陷表面时,HONO分解产生·OH,氧化SO_(2)形成HOSO_(2)团簇分子。该研究不仅有助于理解HONO在矿物氧化物表面氧化SO_(2)的作用,而且为解释大气硫酸盐气溶胶的形成提供了理论依据。展开更多
The Weather Research and Forecasting/Chemistry model （WRF-Chem） was updated by including pho- toexeited nitrogen dioxide （NO2） molecules, heterogeneous reactions on aerosol surfaces, and direct emissions of nitrou...The Weather Research and Forecasting/Chemistry model （WRF-Chem） was updated by including pho- toexeited nitrogen dioxide （NO2） molecules, heterogeneous reactions on aerosol surfaces, and direct emissions of nitrous acid （HONO） in the Carbon-Bond Mechanism Z （CBM-Z）. Five simulations were conducted to assess the effects of each new component and the three additional HONO sources on concentrations of major chemical components. We calculated percentage changes of major aerosol components and concentration ratios of gas NOy （NOyg） to NOy and particulate nitrates （NO3-） to NOy due to the three additional HONO sources in the North China Plain in August of 2007. Our results indicate that when the three additional HONO sources are included, WRF-Chem can reasonably reproduce the HONO observations. Heterogeneous reactions on aerosol surfaces are a key contributor to concentrations of HONO, nitrates （NO3-）, ammonium （NH＋）, and PM2.5 （concentration of particulate matter of ≤2.5 um in the ambient air） across the North China Plain. The three additional HONO sources produced a -5% -20% increase in monthly mean daytime concentration ratios of NO3-/NOy, a -15%- 52% increase in maximum hourly mean concentration ratios of NO3-/NOy, and a -10% -50% increase in monthly mean concentrations of NOx and NH＋ across large areas of the North China Plain. For the Bohai Bay, the largest hourly increases of NO3- exceeded 90%, of NH＋ exceeded 80%, and of PM2.5 exceeded 40%, due to the three additional HONO sources. This implies that the three additional HONO sources can aggravate regional air pollution, further impair visibility, and enhance the incidence of haze in some industrialized regions with high emissions of NOx and particulate matter under favorable meteorological conditions.展开更多
The objective of the present study was to better understand the impacts of the additional sources of nitrous acid （HONO） on visibility, which is an aspect not considered in current air quality models. Simulations of...The objective of the present study was to better understand the impacts of the additional sources of nitrous acid （HONO） on visibility, which is an aspect not considered in current air quality models. Simulations of HONO contributions to visibility over the North China Plain （NCP） during August 2007 using the fully coupled Weather Research and Forecasting/Chemistry （WRF/Chem） model were performed, including three additional HONO sources： （1） the reaction of photo-excited nitrogen dioxide （NO~） with water vapor; （2） the NO2 heterogeneous reaction on aerosol surfaces; and （3） HONO emissions. The model generally reproduced the spatial patterns and diurnal variations of visibility over the NCP well. When the additional HONO sources were included in the simulations, the visibility was occasionally decreased by 20%-30% （3-4 km） in local urban areas of the NCP. Monthly-mean concentrations of NO3, NH＋, SO]- and PM2.5 were increased by 20%-52% （3-11μg m-3）, 10%-38%, 6%-10%, and 6%-11% （9-17 μg m-3）, respectively; and in urban areas, monthly-mean accumulation- mode number concentrations （AMNC） and surface concentrations of aerosols were enhanced by 15%-20% and 10%-20%, respectively. Overall, the results suggest that increases in concentrations of PM2.5, its hydrophilic components, and AMNC, are key factors for visibility degradation. A proposed conceptual model for the impacts of additional HONO sources on visibility also suggests that visibility estimation should consider the heterogeneous reaction on aerosol surfaces and the enhanced atmospheric oxidation capacity due to additional HONO sources, especially in areas with high mass concentrations of NOx and aerosols.展开更多
A laser photolysis/transient absorption technique has been employed to investigate the photolysis kinetics of aqueous CS2-HONO solutions at 355 nm. Spectral analysis shows that CS2OH will react with HONO to form CS2OH...A laser photolysis/transient absorption technique has been employed to investigate the photolysis kinetics of aqueous CS2-HONO solutions at 355 nm. Spectral analysis shows that CS2OH will react with HONO to form CS2OH-HONO. Temperature dependent rate coefficients for the reaction are reported for the first time. The following Arrhenius expressions adequately summarize the kinetic data obtained over the temperature range 273-313 K （units are L·mol^-1·s^-1）： In k = （31.6±0.6）-{（4.1±0.2）×10^3/T}, and the activation energy in unit of kJ.molA is 32.47 with the temperature accuracy 0.2 K.展开更多
文摘为研究亚硝酸(HONO)在γ-Al_(2)O_(3)(110)表面非均相氧化SO_(2)的机理,基于密度泛函理论(density functional theory,DFT)的第一性原理计算了SO_(2)和HONO在γ-Al_(2)O_(3)(110)表面的吸附机制和氧化机制。结果表明,SO_(2)以分子的形式吸附在完整或缺陷的γ-Al_(2)O_(3)(110)表面,而HONO仅在完整表面上以分子的形式存在。表面氧缺陷的存在不仅会增强SO_(2)和HONO的吸附强度,而且能诱导HONO在含氧缺陷表面的分解(HONO→NO+·OH)。通过局域态密度(partial density of states,PDOS)和Mulliken电荷布局分析表明,HONO的分解遵循Haber-Weiss机制。当SO_(2)和HONO共同吸附在氧缺陷表面时,HONO分解产生·OH,氧化SO_(2)形成HOSO_(2)团簇分子。该研究不仅有助于理解HONO在矿物氧化物表面氧化SO_(2)的作用,而且为解释大气硫酸盐气溶胶的形成提供了理论依据。
基金supported by the National Natural Science Foundation of China (Grant Nos. 41175105 and 40905055)the Key Project of Chinese Academy of Sciences (Grant No. kzcx1-yw-06-04)
文摘The Weather Research and Forecasting/Chemistry model （WRF-Chem） was updated by including pho- toexeited nitrogen dioxide （NO2） molecules, heterogeneous reactions on aerosol surfaces, and direct emissions of nitrous acid （HONO） in the Carbon-Bond Mechanism Z （CBM-Z）. Five simulations were conducted to assess the effects of each new component and the three additional HONO sources on concentrations of major chemical components. We calculated percentage changes of major aerosol components and concentration ratios of gas NOy （NOyg） to NOy and particulate nitrates （NO3-） to NOy due to the three additional HONO sources in the North China Plain in August of 2007. Our results indicate that when the three additional HONO sources are included, WRF-Chem can reasonably reproduce the HONO observations. Heterogeneous reactions on aerosol surfaces are a key contributor to concentrations of HONO, nitrates （NO3-）, ammonium （NH＋）, and PM2.5 （concentration of particulate matter of ≤2.5 um in the ambient air） across the North China Plain. The three additional HONO sources produced a -5% -20% increase in monthly mean daytime concentration ratios of NO3-/NOy, a -15%- 52% increase in maximum hourly mean concentration ratios of NO3-/NOy, and a -10% -50% increase in monthly mean concentrations of NOx and NH＋ across large areas of the North China Plain. For the Bohai Bay, the largest hourly increases of NO3- exceeded 90%, of NH＋ exceeded 80%, and of PM2.5 exceeded 40%, due to the three additional HONO sources. This implies that the three additional HONO sources can aggravate regional air pollution, further impair visibility, and enhance the incidence of haze in some industrialized regions with high emissions of NOx and particulate matter under favorable meteorological conditions.
基金supported by the Beijing Natural Science Foundation (Grant No.8144054)the Key Project of the Chinese Academy of Sciences (Grant No.XDB05030301)+1 种基金the National Natural Science Foundation of China (Grant No.41175105)the Carbon and Nitrogen Cycle project of the Institute of Atmospheric Physics, Chinese Academy of Sciences
文摘The objective of the present study was to better understand the impacts of the additional sources of nitrous acid （HONO） on visibility, which is an aspect not considered in current air quality models. Simulations of HONO contributions to visibility over the North China Plain （NCP） during August 2007 using the fully coupled Weather Research and Forecasting/Chemistry （WRF/Chem） model were performed, including three additional HONO sources： （1） the reaction of photo-excited nitrogen dioxide （NO~） with water vapor; （2） the NO2 heterogeneous reaction on aerosol surfaces; and （3） HONO emissions. The model generally reproduced the spatial patterns and diurnal variations of visibility over the NCP well. When the additional HONO sources were included in the simulations, the visibility was occasionally decreased by 20%-30% （3-4 km） in local urban areas of the NCP. Monthly-mean concentrations of NO3, NH＋, SO]- and PM2.5 were increased by 20%-52% （3-11μg m-3）, 10%-38%, 6%-10%, and 6%-11% （9-17 μg m-3）, respectively; and in urban areas, monthly-mean accumulation- mode number concentrations （AMNC） and surface concentrations of aerosols were enhanced by 15%-20% and 10%-20%, respectively. Overall, the results suggest that increases in concentrations of PM2.5, its hydrophilic components, and AMNC, are key factors for visibility degradation. A proposed conceptual model for the impacts of additional HONO sources on visibility also suggests that visibility estimation should consider the heterogeneous reaction on aerosol surfaces and the enhanced atmospheric oxidation capacity due to additional HONO sources, especially in areas with high mass concentrations of NOx and aerosols.
文摘A laser photolysis/transient absorption technique has been employed to investigate the photolysis kinetics of aqueous CS2-HONO solutions at 355 nm. Spectral analysis shows that CS2OH will react with HONO to form CS2OH-HONO. Temperature dependent rate coefficients for the reaction are reported for the first time. The following Arrhenius expressions adequately summarize the kinetic data obtained over the temperature range 273-313 K （units are L·mol^-1·s^-1）： In k = （31.6±0.6）-{（4.1±0.2）×10^3/T}, and the activation energy in unit of kJ.molA is 32.47 with the temperature accuracy 0.2 K.
