As a key precursor of hydroxyl(OH) radicals, the budget of nitrous acid(HONO) at different altitudes has received extensive attention. In this study, vertically resolved observations of HONO, NO_(2), O_(3), and HCHO w...As a key precursor of hydroxyl(OH) radicals, the budget of nitrous acid(HONO) at different altitudes has received extensive attention. In this study, vertically resolved observations of HONO, NO_(2), O_(3), and HCHO were conducted during an autumn field campaign in Beijing in 2019. The significant correlation between HONO and NO2, along with variations in their ratios across different altitudes, underscores the importance of aerosol surface chemistry in HONO formation and its altitude-dependent behavior. To enhance the model performance, the heterogeneous conversion of NO_(2) and its photochemical enhancement are incorporated into the 1D model. The simulations reveal that the nocturnal HONO production is dominated by the heterogeneous conversion of NO_(2) both at the surface and aloft. During the daytime, groundsurface sources of HONO are mainly driven by nitrate photolysis and light-enhanced heterogeneous conversion of NO_(2).Meanwhile, a large portion of the HONO generated at the surface is transported upwards through vertical mixing. In the higher atmosphere, HONO originates from vertical transport and in situ processes. As precursors of OH radicals, the observed concentrations of HONO, O_(3), and HCHO exhibit distinct diurnal variations and vertical distribution patterns.HONO contributes to OH radical production predominantly during the early morning across all layers and it even becomes the main contributor throughout the daytime in the lowest layer near the ground, while O_(3) and HCHO become more prominent towards midday, especially in the higher layers. These results will be beneficial for a deeper understanding of the atmospheric oxidation process within the urban boundary layer.展开更多
HONO is a critical precursor of•OH,but its sources are controversial due to its complex formation mechanism.This study conducted comprehensive observations in Zhengzhou from April 26 to May 11,2022.Low NO_(x)concentra...HONO is a critical precursor of•OH,but its sources are controversial due to its complex formation mechanism.This study conducted comprehensive observations in Zhengzhou from April 26 to May 11,2022.Low NO_(x)concentrations were observed during the Covid epidemic period(EP)(10.4±3.0 ppb),compared to the pre-epidemic period(PEP)(12.5±3.8 ppb).The mean HONO concentration during EP(0.53±0.34 ppb)was 0.09 ppb lower than that during PEP(0.62±0.53 ppb).The decrease in HONO concentration during EP came mainly at night due to the reduction in the direct emission(P_(emi))(0.03 ppb/hr),the homogeneous reaction between•OHandNO(P_(OH+NO))(0.02 ppb/hr),and the heterogeneous conversion of NO_(2)on the ground(0.01 ppb/hr).Notably,there was no significant change in daytime HONO concentration.The daytime HONO budget indicated that the primary HONO sources during PEP were the nitrate photolysis(P_(nitrate)),followed by the P_(OH+NO),Pemi,the photo-enhanced reaction of NO_(2)on the ground(P_(ground+hv))and aerosol surface(Paerosol+hv).The primary HONO sources were Pnitrate,POH+NO,P_(emi),and_(Paerosol+hv)during EP,respectively.The missing source has a high correlation with solar radiation,there might be other photo-related HONO sources or the contributions of photosensitized reactions were underestimated.In the extremely underestimated cases,HONO production rates fromthe P_(nitrate),P_(ground+hv),and Paerosol+hv increased by 0.17,0.10,and 0.10 ppb/hr during PEP,0.23,0.13,and 0.16 ppb/hr during EP,and P_(nitrate)was still the primary source during both PEP and EP.展开更多
The authors regret that in 1.2.Instruments section of the article,when describing the principle of TiH300,the original content of“Briefly,ambient HONO was first absorbed by deionized water in a two-channel stripping ...The authors regret that in 1.2.Instruments section of the article,when describing the principle of TiH300,the original content of“Briefly,ambient HONO was first absorbed by deionized water in a two-channel stripping coil.The absorbed liquid nitrite was mixed with sulfanilamide,N-(1-naphthyl)-ethylenediamine dihydrochloride,and hydrogen chloride solution to form the azo dye derivative.”展开更多
Gaseous nitrous acid(HONO)is a critical contributor to daytime hydroxyl radical in the troposphere.Livestock farming has been recognized as an overlooked HONO source,but the lack of detailed flux measurements from liv...Gaseous nitrous acid(HONO)is a critical contributor to daytime hydroxyl radical in the troposphere.Livestock farming has been recognized as an overlooked HONO source,but the lack of detailed flux measurements from livestock and poultry wastes would cause uncertainties in modeling its environmental impacts.Here,based on field flux measurements and laboratory experiments,we observed substantial HONO emissions from the composting of swine feces and chicken manure in the warm season,which might be mainly attributed to nitrification process in livestock and poultry wastes.The HONO emission from chicken manure was found to bemuch higher than that from swine feces,and the higher NH3 emission but lower N2O and NO emissions fromchicken manurewere also observed.Considering that the interaction among these nitrogen species during nitrification process,the obviously lower HONO emission from swine feces was likely to be explained by the lack of the total ammonia nitrogen and H+donors in swine feces.Temperature is also a key factor that influences the HONO emission from livestock wastes.In addition,the total HONO emission from swine feces in Chinawas estimated to be approximately 107.7 Gg-N/yr according to the national swine amounts,which is comparable to the national soil HONO emissions,underscoring its non-negligible contribution to regional air quality.Therefore,effective emission control of HONO fromlivestock and poultry wastes should be carried out to further improve air quality in China.展开更多
在2007-08-14-2007-08-24期间,利用差分光学吸收光谱（DOAS）技术,对北京市大气中HONO、NO2和O3等污染物进行了连续监测,分析了HONO和NO2的日变化特征,讨论了夜间直接排放对HONO来源的贡献,进行了24 h和夜间13 h HONO非均相反应形成与...在2007-08-14-2007-08-24期间,利用差分光学吸收光谱（DOAS）技术,对北京市大气中HONO、NO2和O3等污染物进行了连续监测,分析了HONO和NO2的日变化特征,讨论了夜间直接排放对HONO来源的贡献,进行了24 h和夜间13 h HONO非均相反应形成与黑碳气溶胶（BC）和相对湿度（RH）等要素的相关分析.结果表明,HONO和NO2均在01：00左右达到峰值,HONO的另一峰值浓度出现在06：00,比NO2第2个峰值出现时间07：00早1 h;夜间（19：00-次日07：00）直接排放对HONO的贡献最大达到31.3%,出现在20：00,平均贡献为15%;夜间HONOcorr/NO2比率与BC和RH具有非常明显的相关性,说明HONO的非均相生成速率与NO2的浓度以及反应介质BC表面的吸附水的浓度即RH成正比,得到夜间HONO平均转化率（HONO/NO2）为0.8%·h^-1;而且RH的增加对HONO的非均相形成有利,但是当RH〉80%对反应也将产生抑制作用,通过对监测期间的个例分析也证实了这一假设.展开更多
基金supported by the National Natural Science Foundation of China (Grant Nos.42075097,42177081 and 22176037)。
文摘As a key precursor of hydroxyl(OH) radicals, the budget of nitrous acid(HONO) at different altitudes has received extensive attention. In this study, vertically resolved observations of HONO, NO_(2), O_(3), and HCHO were conducted during an autumn field campaign in Beijing in 2019. The significant correlation between HONO and NO2, along with variations in their ratios across different altitudes, underscores the importance of aerosol surface chemistry in HONO formation and its altitude-dependent behavior. To enhance the model performance, the heterogeneous conversion of NO_(2) and its photochemical enhancement are incorporated into the 1D model. The simulations reveal that the nocturnal HONO production is dominated by the heterogeneous conversion of NO_(2) both at the surface and aloft. During the daytime, groundsurface sources of HONO are mainly driven by nitrate photolysis and light-enhanced heterogeneous conversion of NO_(2).Meanwhile, a large portion of the HONO generated at the surface is transported upwards through vertical mixing. In the higher atmosphere, HONO originates from vertical transport and in situ processes. As precursors of OH radicals, the observed concentrations of HONO, O_(3), and HCHO exhibit distinct diurnal variations and vertical distribution patterns.HONO contributes to OH radical production predominantly during the early morning across all layers and it even becomes the main contributor throughout the daytime in the lowest layer near the ground, while O_(3) and HCHO become more prominent towards midday, especially in the higher layers. These results will be beneficial for a deeper understanding of the atmospheric oxidation process within the urban boundary layer.
基金supported by China Postdoctoral Science Foundation(2023M733220)Zhengzhou PM_(2.5)and O_(3)Collaborative Control and Monitoring Project(20220347A)the National Key Research and Development Program of China(No.2017YFC0212403).
文摘HONO is a critical precursor of•OH,but its sources are controversial due to its complex formation mechanism.This study conducted comprehensive observations in Zhengzhou from April 26 to May 11,2022.Low NO_(x)concentrations were observed during the Covid epidemic period(EP)(10.4±3.0 ppb),compared to the pre-epidemic period(PEP)(12.5±3.8 ppb).The mean HONO concentration during EP(0.53±0.34 ppb)was 0.09 ppb lower than that during PEP(0.62±0.53 ppb).The decrease in HONO concentration during EP came mainly at night due to the reduction in the direct emission(P_(emi))(0.03 ppb/hr),the homogeneous reaction between•OHandNO(P_(OH+NO))(0.02 ppb/hr),and the heterogeneous conversion of NO_(2)on the ground(0.01 ppb/hr).Notably,there was no significant change in daytime HONO concentration.The daytime HONO budget indicated that the primary HONO sources during PEP were the nitrate photolysis(P_(nitrate)),followed by the P_(OH+NO),Pemi,the photo-enhanced reaction of NO_(2)on the ground(P_(ground+hv))and aerosol surface(Paerosol+hv).The primary HONO sources were Pnitrate,POH+NO,P_(emi),and_(Paerosol+hv)during EP,respectively.The missing source has a high correlation with solar radiation,there might be other photo-related HONO sources or the contributions of photosensitized reactions were underestimated.In the extremely underestimated cases,HONO production rates fromthe P_(nitrate),P_(ground+hv),and Paerosol+hv increased by 0.17,0.10,and 0.10 ppb/hr during PEP,0.23,0.13,and 0.16 ppb/hr during EP,and P_(nitrate)was still the primary source during both PEP and EP.
文摘The authors regret that in 1.2.Instruments section of the article,when describing the principle of TiH300,the original content of“Briefly,ambient HONO was first absorbed by deionized water in a two-channel stripping coil.The absorbed liquid nitrite was mixed with sulfanilamide,N-(1-naphthyl)-ethylenediamine dihydrochloride,and hydrogen chloride solution to form the azo dye derivative.”
基金supported by the National Key Research and Development Program(No.2022YFC3701102)the National Natural Science Foundation of China(Nos.41905109,42405114,and 42105105).
文摘Gaseous nitrous acid(HONO)is a critical contributor to daytime hydroxyl radical in the troposphere.Livestock farming has been recognized as an overlooked HONO source,but the lack of detailed flux measurements from livestock and poultry wastes would cause uncertainties in modeling its environmental impacts.Here,based on field flux measurements and laboratory experiments,we observed substantial HONO emissions from the composting of swine feces and chicken manure in the warm season,which might be mainly attributed to nitrification process in livestock and poultry wastes.The HONO emission from chicken manure was found to bemuch higher than that from swine feces,and the higher NH3 emission but lower N2O and NO emissions fromchicken manurewere also observed.Considering that the interaction among these nitrogen species during nitrification process,the obviously lower HONO emission from swine feces was likely to be explained by the lack of the total ammonia nitrogen and H+donors in swine feces.Temperature is also a key factor that influences the HONO emission from livestock wastes.In addition,the total HONO emission from swine feces in Chinawas estimated to be approximately 107.7 Gg-N/yr according to the national swine amounts,which is comparable to the national soil HONO emissions,underscoring its non-negligible contribution to regional air quality.Therefore,effective emission control of HONO fromlivestock and poultry wastes should be carried out to further improve air quality in China.
文摘在2007-08-14-2007-08-24期间,利用差分光学吸收光谱（DOAS）技术,对北京市大气中HONO、NO2和O3等污染物进行了连续监测,分析了HONO和NO2的日变化特征,讨论了夜间直接排放对HONO来源的贡献,进行了24 h和夜间13 h HONO非均相反应形成与黑碳气溶胶（BC）和相对湿度（RH）等要素的相关分析.结果表明,HONO和NO2均在01：00左右达到峰值,HONO的另一峰值浓度出现在06：00,比NO2第2个峰值出现时间07：00早1 h;夜间（19：00-次日07：00）直接排放对HONO的贡献最大达到31.3%,出现在20：00,平均贡献为15%;夜间HONOcorr/NO2比率与BC和RH具有非常明显的相关性,说明HONO的非均相生成速率与NO2的浓度以及反应介质BC表面的吸附水的浓度即RH成正比,得到夜间HONO平均转化率（HONO/NO2）为0.8%·h^-1;而且RH的增加对HONO的非均相形成有利,但是当RH〉80%对反应也将产生抑制作用,通过对监测期间的个例分析也证实了这一假设.
