典型华北农村地区冬季HONO的浓度水平及来源分析
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摘要
气态亚硝酸(HONO)容易光解,是对流层大气羟基自由基(·OH)的重要来源之一,对区域二次污染的形成具有重要作用.我国在大气HONO观测研究方面主要集中在一些城市区域,而在我国北方农村区域的研究还鲜见报道.为此,本文利用亚硝酸在线分析仪(long path absorption photo meter,LOPAP)于2017年11月在中国科学院农村环境研究站(河北省望都县东白陀村)开展了为期一个月的HONO外场观测,并分析了HONO的浓度水平、变化特征及收支情况.大气HONO的浓度在观测期间呈现夜间高、白天低的日变化特征,夜间最高浓度(体积分数,下同)可达约3. 70×10-9,中午最低浓度也维持在0. 10×10-9以上,表明农村区域存在比较强的HONO来源.采暖前后CO浓度显著提高,而HONO浓度无显著变化,说明供暖燃烧对HONO的贡献较小;夜间机动车直接排放在污染天气和清洁天气条件下对HONO的贡献分别为23. 20%和31. 20%,说明在污染天气条件下存在着某些较强的HONO源;夜间·OH与NO的均相反应HONO平均生成速率可高达0. 40×10-9h-1,比NO2的非均相反应HONO生成速率(0. 24×10-9h-1)高0. 67倍,是HONO的主要来源; HONO在白天存在着很强的未知源,其强度可达1. 37×10-9h-1,对于HONO的贡献达到50%左右.
Nitrous acid( HONO) is easily photolyzed with the production of ·OH,which plays an important role in the formation of regional secondary pollution. In China,research of HONO observation is concentrated mainly in urban areas and is rarely reported in rural areas. In our study,a one-month HONO field observation was conducted at the Station of Rural Environment,Chinese Academy of Sciences( Dongbaituo Village,Wangdu County,Hebei Province) in November 2017 using the long path absorption photo meter( LOPAP). The concentration,variety characteristics,and budget of HONO was studied. During the observation period,HONO exhibited pronounced diurnal variation with low concentrations in the day and high concentration in the evening. The highest concentration at night was about 3. 70 × 10-9,and the lowest concentration at noon was about 0. 10 × 10-9,indicating the presence of a strong source of HONO in rural areas. The CO concentration increased significantly before and after heating,whereas the HONO concentration did not change significantly,indicating that heating combustion contributed less to HONO,Direct emission of motor vehicles at night contributed 23. 20% and 31. 20% to HONO in polluted and clean weather conditions,respectively,indicating the presence of strong sources of HONO in polluted weather conditions. The average formation rate of HONO at night from homogeneous reaction of·OH and NO could reach 0. 40 × 10-9 h-1,which is 0. 67 times higher than that of heterogeneous reaction of NO2( 0. 24 ×10-9 h-1),indicating that the homogeneous reaction of ·OH and NO is the main source of HONO at night. HONO has a strong unknown source in the daytime with an intensity reaching 1. 37 × 10-9 h-1,which contributes about 50% to HONO.
Nitrous acid( HONO) is easily photolyzed with the production of ·OH,which plays an important role in the formation of regional secondary pollution. In China,research of HONO observation is concentrated mainly in urban areas and is rarely reported in rural areas. In our study,a one-month HONO field observation was conducted at the Station of Rural Environment,Chinese Academy of Sciences( Dongbaituo Village,Wangdu County,Hebei Province) in November 2017 using the long path absorption photo meter( LOPAP). The concentration,variety characteristics,and budget of HONO was studied. During the observation period,HONO exhibited pronounced diurnal variation with low concentrations in the day and high concentration in the evening. The highest concentration at night was about 3. 70 × 10-9,and the lowest concentration at noon was about 0. 10 × 10-9,indicating the presence of a strong source of HONO in rural areas. The CO concentration increased significantly before and after heating,whereas the HONO concentration did not change significantly,indicating that heating combustion contributed less to HONO,Direct emission of motor vehicles at night contributed 23. 20% and 31. 20% to HONO in polluted and clean weather conditions,respectively,indicating the presence of strong sources of HONO in polluted weather conditions. The average formation rate of HONO at night from homogeneous reaction of·OH and NO could reach 0. 40 × 10-9 h-1,which is 0. 67 times higher than that of heterogeneous reaction of NO2( 0. 24 ×10-9 h-1),indicating that the homogeneous reaction of ·OH and NO is the main source of HONO at night. HONO has a strong unknown source in the daytime with an intensity reaching 1. 37 × 10-9 h-1,which contributes about 50% to HONO.
引文
[1] Perner D,Platt U. Detection of nitrous acid in the atmosphere by differential optical absorption[J]. Geophysical Research Letters,1979,6(12):917-920.
[2] Kurtenbach R,Becker K H,Gomes J A G,et al. Investigations of emissions and heterogeneous formation of HONO in a road traffic tunnel[J]. Atmospheric Environment,2001,35(20):3385-3394.
[3]秦敏,刘文清,谢品华,等.大气中HONO来源的研究进展[J].中国环境监测,2005,21(3):82-88.Qin M,Liu W Q,Xie P H,et al. Study progress on the source of atmospheric HONO[J]. Environmental Monitoring in China,2005,21(3):82-88.
[4] Su H,Cheng Y F,Oswald R,et al. Soil nitrite as a source of atmospheric HONO and OH radicals[J]. Science,2011,333(6049):1616-1618.
[5]程鹏.大气亚硝酸(HONO)的测量和土壤来源研究[D].北京:北京大学,2013.
[6] Li X,Brauers T,Hseler R,et al. Exploring the atmospheric chemistry of nitrous acid(HONO)at a rural site in Southern China[J]. Atmospheric Chemistry and Physics,2012,12(3):1497-1513.
[7] Finlayson-Pitts B J,Wingen L M,Sumner A L,et al. The heterogeneous hydrolysis of NO2in laboratory systems and in outdoor and indoor atmospheres:an integrated mechanism[J].Physical Chemistry Chemical Physics,2003,5(2):223-242.
[8] Ndour M,D'Anna B,George C,et al. Photoenhanced uptake of NO2on mineral dust:laboratory experiments and model simulations[J]. Geophysical Research Letters,2008,35(5):L05812.
[9]安俊岭,李颖,汤宇佳,等. HONO来源及其对空气质量影响研究进展[J].中国环境科学,2014,34(2):273-281.An J L,Li Y,Tang Y J,et al. Advances in HONO sources,HONO simulations,and the impacts of the HONO sources on regional or global air quality[J]. China Environmental Science,2014,34(2):273-281.
[10] Zhou X L,He Y,Huang G,et al. Photochemical production of nitrous acid on glass sample manifold surface[J]. Geophysical Research Letters,2002,29(14):1681.
[11] Bejan I,El Aal Y,Barnes I,et al. The photolysis of orthonitrophenols:a new gas phase source of HONO[J]. Physical Chemistry Chemical Physics,2006,8(17):2028-2035.
[12] Li S P,Matthews J,Sinha A. Atmospheric hydroxyl radical production from electronically excited NO2and H2O[J].Science,2008,319(5870):1657-1660.
[13] Qin M,Xie P H,Su H,et al. An observational study of the HONO-NO2coupling at an urban site in Guangzhou City,South China[J]. Atmospheric Environment,2009,43(36):5731-5742.
[14]朱燕舞,刘文清,谢品华,等.北京夏季大气HONO的监测研究[J].环境科学,2009,30(6):1567-1573.Zhu Y W,Liu W Q,Xie P H,et al. Observational study of atmospheric HONO in summer of Beijing[J]. Environmental Science,2009,30(6):1567-1573.
[15]安俊岭,汤宇佳,王峰,等.白天气态亚硝酸(HONO)未知源对我国东部沿海地区HONO和OH自由基收支的影响[J].海峡科技与产业,2015,(11):55-59.
[16] Hou S Q,Tong S R,Ge M F,et al. Comparison of atmospheric nitrous acid during severe haze and clean periods in Beijing,China[J]. Atmospheric Environment,2016,124:199-206.
[17] Liu P F,Zhang C L,Xue C Y,et al. The contribution of residential coal combustion to atmospheric PM2. 5in northern China during winter[J]. Atmospheric Chemistry and Physics,2017,17(18):11503-11520.
[18]汪午,王省良,李黎,等.天然源二次有机气溶胶的研究进展[J].地球化学,2008,37(1):77-86.Wang W, Wang S L, Li L, et al. Advances in biogenic secondary organic aerosols[J]. Geochimica,2008,37(1):77-86.
[19] GB 3095-2012,环境空气质量标准[S].
[20]田智林,杨闻达,虞小芳,等.广州秋季HONO污染特征及夜间来源分析[J].环境科学,2018,39(5):2000-2009.Tian Z L, Yang W D, Yu X F, et al. HONO pollution characteristics and nighttime sources during autumn in Guangzhou,China[J]. Environmental Science,2018,39(5):2000-2009.
[21]裴淑玮,张圆圆,刘俊锋,等.华北平原玉米-小麦轮作农田N2O交换通量的研究[J].环境科学,2012,33(10):3641-3646.Pei S W,Zhang Y Y,Liu J F,et al. N2O exchange fluxes from wheat-maize crop rotation system in the North China Plain[J].Environmental Science,2012,33(10):3641-3646.
[22]裴淑玮,张圆圆,刘俊锋,等.施肥及秸秆还田处理下玉米季温室气体的排放[J].环境化学,2012,31(4):407-414.Pei S W,Zhang Y Y,Liu J F,et al. Greenhouse gas emission under the treatments of fertilization and wheat straw returning during the maize growing seasons[J]. Environmental Chemistry,2012,31(4):407-414.
[23]闫严,周丽娜,常雪羽,等.保定不同土地利用类型土壤性状的灰色综合评估[J].天津师范大学学报(自然科学版),2018,38(2):68-72.Yan Y,Zhou L N,Chang X Y,et al. Grey comprehensive evaluation for physicochemical properties of soil under different land utilization types in Baoding[J]. Journal of Tianjin Normal University(Natural Science Edition),2018,38(2):68-72.
[24] Su H,Cheng Y F,Peng C,et al. Observation of nighttime nitrous acid(HONO)formation at a non-urban site during PRIDE-PRD2004 in China[J]. Atmospheric Environment,2008,42(25):6219-6232.
[25] Su H,Cheng Y F,Shao M,et al. Nitrous acid(HONO)and its daytime sources at a rural site during the 2004 PRIDE-PRD experiment in China[J]. Journal of Geophysical Research:Atmospheres,2008,113(D14):D14312.
[26] Hao N,Zhou B,Chen D,et al. Observations of nitrous acid and its relative humidity dependence in Shanghai[J]. Journal of Environmental Sciences,2006,18(5):910-915.
[27] Cheng M T,Chen S P,Lin Y C,et al. Concentrations and formation rates of ambient nitrous acid in Taichung City,Taiwan[J]. Environmental Engineering Science,2008,25(8):1149-1158.
[28] Wang L W,Wen L,Xu C H,et al. HONO and its potential source particulate nitrite at an urban site in North China during the cold season[J]. Science of the Total Environment,2015,538:93-101.
[29] Zhang W Q,Tong S R,Ge M F,et al. Variations and sources of nitrous acid(HONO)during a severe pollution episode in Beijing in winter 2016[J]. Science of The Total Environment,2019,648:253-262.
[30] Alicke B,Platt U,Stutz J. Impact of nitrous acid photolysis on the total hydroxyl radical budget during the Limitation of Oxidant Production/Pianura Padana Produzione di Ozono study in Milan[J]. Journal of Geophysical Research:Atmospheres,2002,107(D22):8196.
[31] Kleffmann J,Kurtenbach R,Lrzer J,et al. Measured and simulated vertical profiles of nitrous acid—Part I:field measurements[J]. Atmospheric Environment,2003,37(21):2949-2955.
[32] Tan Z F,Rohrer F,Lu K D,et al. Wintertime photochemistry in Beijing:observations of ROXradical concentrations in the North China Plain during the BEST-ONE campaign[J]. Atmospheric Chemistry and Physics,2018,18(16):12391-12411.
[33] Gutzwiller L,Arens F,Baltensperger U,et al. Significance of semivolatile diesel exhaust organics for secondary HONO formation[J]. Environmental Science&Technology,2002,36(4):677-682.
[34] Ammann M,Rssler E,Strekowski R,et al. Nitrogen dioxide multiphase chemistry:uptake kinetics on aqueous solutions containing phenolic compounds[J]. Physical Chemistry Chemical Physics,2005,7(12):2513-2518.
[35] Zhang B Q,Tao F M. Direct homogeneous nucleation of NO2,H2O,and NH3for the production of ammonium nitrate particles and HONO gas[J]. Chemical Physics Letters,2010,489(4-6):143-147.
[36] Wang S S,Zhou R,Zhao H,et al. Long-term observation of atmospheric nitrous acid(HONO)and its implication to local NO2levels in Shanghai,China[J]. Atmospheric Environment,2013,77:718-724.
[37] Wang J Q,Zhang X S,Guo J,et al. Observation of nitrous acid(HONO)in Beijing, China:Seasonal variation, nocturnal formation and daytime budget[J]. Science of The Total Environment,2017,587-588:350-359.
[38] Huang R J,Yang L,Cao J J,et al. Concentration and sources of atmospheric nitrous acid(HONO)at an urban site in Western China[J]. Science of the Total Environment,2017,593-594:165-172.
[39] Harrison R M,Peak J D,Collins G M. Tropospheric cycle of nitrous acid[J]. Journal of Geophysical Research:Atmospheres,1996,101(D9):14429-14439.
[40] Li Y,An J L,Min M,et al. Impacts of HONO sources on the air quality in Beijing,Tianjin and Hebei Province of China[J].Atmospheric Environment,2011,45(27):4735-4744.
[41] Yang Q,Su H,Li X,et al. Daytime HONO formation in the suburban area of the megacity Beijing,China[J]. Science China Chemistry,2014,57(7):1032-1042.
[42]杨闻达,程鹏,田智林,等.广州市夏秋季HONO污染特征及白天未知源分析[J].中国环境科学,2017,37(6):2029-2039.Yang W D,Cheng P,Tian Z L,et al. Study on HONO pollution characteristics and daytime unknown sources during summer and autumn in Guangzhou,China[J]. China Environmental Science,2017,37(6):2029-2039.
[2] Kurtenbach R,Becker K H,Gomes J A G,et al. Investigations of emissions and heterogeneous formation of HONO in a road traffic tunnel[J]. Atmospheric Environment,2001,35(20):3385-3394.
[3]秦敏,刘文清,谢品华,等.大气中HONO来源的研究进展[J].中国环境监测,2005,21(3):82-88.Qin M,Liu W Q,Xie P H,et al. Study progress on the source of atmospheric HONO[J]. Environmental Monitoring in China,2005,21(3):82-88.
[4] Su H,Cheng Y F,Oswald R,et al. Soil nitrite as a source of atmospheric HONO and OH radicals[J]. Science,2011,333(6049):1616-1618.
[5]程鹏.大气亚硝酸(HONO)的测量和土壤来源研究[D].北京:北京大学,2013.
[6] Li X,Brauers T,Hseler R,et al. Exploring the atmospheric chemistry of nitrous acid(HONO)at a rural site in Southern China[J]. Atmospheric Chemistry and Physics,2012,12(3):1497-1513.
[7] Finlayson-Pitts B J,Wingen L M,Sumner A L,et al. The heterogeneous hydrolysis of NO2in laboratory systems and in outdoor and indoor atmospheres:an integrated mechanism[J].Physical Chemistry Chemical Physics,2003,5(2):223-242.
[8] Ndour M,D'Anna B,George C,et al. Photoenhanced uptake of NO2on mineral dust:laboratory experiments and model simulations[J]. Geophysical Research Letters,2008,35(5):L05812.
[9]安俊岭,李颖,汤宇佳,等. HONO来源及其对空气质量影响研究进展[J].中国环境科学,2014,34(2):273-281.An J L,Li Y,Tang Y J,et al. Advances in HONO sources,HONO simulations,and the impacts of the HONO sources on regional or global air quality[J]. China Environmental Science,2014,34(2):273-281.
[10] Zhou X L,He Y,Huang G,et al. Photochemical production of nitrous acid on glass sample manifold surface[J]. Geophysical Research Letters,2002,29(14):1681.
[11] Bejan I,El Aal Y,Barnes I,et al. The photolysis of orthonitrophenols:a new gas phase source of HONO[J]. Physical Chemistry Chemical Physics,2006,8(17):2028-2035.
[12] Li S P,Matthews J,Sinha A. Atmospheric hydroxyl radical production from electronically excited NO2and H2O[J].Science,2008,319(5870):1657-1660.
[13] Qin M,Xie P H,Su H,et al. An observational study of the HONO-NO2coupling at an urban site in Guangzhou City,South China[J]. Atmospheric Environment,2009,43(36):5731-5742.
[14]朱燕舞,刘文清,谢品华,等.北京夏季大气HONO的监测研究[J].环境科学,2009,30(6):1567-1573.Zhu Y W,Liu W Q,Xie P H,et al. Observational study of atmospheric HONO in summer of Beijing[J]. Environmental Science,2009,30(6):1567-1573.
[15]安俊岭,汤宇佳,王峰,等.白天气态亚硝酸(HONO)未知源对我国东部沿海地区HONO和OH自由基收支的影响[J].海峡科技与产业,2015,(11):55-59.
[16] Hou S Q,Tong S R,Ge M F,et al. Comparison of atmospheric nitrous acid during severe haze and clean periods in Beijing,China[J]. Atmospheric Environment,2016,124:199-206.
[17] Liu P F,Zhang C L,Xue C Y,et al. The contribution of residential coal combustion to atmospheric PM2. 5in northern China during winter[J]. Atmospheric Chemistry and Physics,2017,17(18):11503-11520.
[18]汪午,王省良,李黎,等.天然源二次有机气溶胶的研究进展[J].地球化学,2008,37(1):77-86.Wang W, Wang S L, Li L, et al. Advances in biogenic secondary organic aerosols[J]. Geochimica,2008,37(1):77-86.
[19] GB 3095-2012,环境空气质量标准[S].
[20]田智林,杨闻达,虞小芳,等.广州秋季HONO污染特征及夜间来源分析[J].环境科学,2018,39(5):2000-2009.Tian Z L, Yang W D, Yu X F, et al. HONO pollution characteristics and nighttime sources during autumn in Guangzhou,China[J]. Environmental Science,2018,39(5):2000-2009.
[21]裴淑玮,张圆圆,刘俊锋,等.华北平原玉米-小麦轮作农田N2O交换通量的研究[J].环境科学,2012,33(10):3641-3646.Pei S W,Zhang Y Y,Liu J F,et al. N2O exchange fluxes from wheat-maize crop rotation system in the North China Plain[J].Environmental Science,2012,33(10):3641-3646.
[22]裴淑玮,张圆圆,刘俊锋,等.施肥及秸秆还田处理下玉米季温室气体的排放[J].环境化学,2012,31(4):407-414.Pei S W,Zhang Y Y,Liu J F,et al. Greenhouse gas emission under the treatments of fertilization and wheat straw returning during the maize growing seasons[J]. Environmental Chemistry,2012,31(4):407-414.
[23]闫严,周丽娜,常雪羽,等.保定不同土地利用类型土壤性状的灰色综合评估[J].天津师范大学学报(自然科学版),2018,38(2):68-72.Yan Y,Zhou L N,Chang X Y,et al. Grey comprehensive evaluation for physicochemical properties of soil under different land utilization types in Baoding[J]. Journal of Tianjin Normal University(Natural Science Edition),2018,38(2):68-72.
[24] Su H,Cheng Y F,Peng C,et al. Observation of nighttime nitrous acid(HONO)formation at a non-urban site during PRIDE-PRD2004 in China[J]. Atmospheric Environment,2008,42(25):6219-6232.
[25] Su H,Cheng Y F,Shao M,et al. Nitrous acid(HONO)and its daytime sources at a rural site during the 2004 PRIDE-PRD experiment in China[J]. Journal of Geophysical Research:Atmospheres,2008,113(D14):D14312.
[26] Hao N,Zhou B,Chen D,et al. Observations of nitrous acid and its relative humidity dependence in Shanghai[J]. Journal of Environmental Sciences,2006,18(5):910-915.
[27] Cheng M T,Chen S P,Lin Y C,et al. Concentrations and formation rates of ambient nitrous acid in Taichung City,Taiwan[J]. Environmental Engineering Science,2008,25(8):1149-1158.
[28] Wang L W,Wen L,Xu C H,et al. HONO and its potential source particulate nitrite at an urban site in North China during the cold season[J]. Science of the Total Environment,2015,538:93-101.
[29] Zhang W Q,Tong S R,Ge M F,et al. Variations and sources of nitrous acid(HONO)during a severe pollution episode in Beijing in winter 2016[J]. Science of The Total Environment,2019,648:253-262.
[30] Alicke B,Platt U,Stutz J. Impact of nitrous acid photolysis on the total hydroxyl radical budget during the Limitation of Oxidant Production/Pianura Padana Produzione di Ozono study in Milan[J]. Journal of Geophysical Research:Atmospheres,2002,107(D22):8196.
[31] Kleffmann J,Kurtenbach R,Lrzer J,et al. Measured and simulated vertical profiles of nitrous acid—Part I:field measurements[J]. Atmospheric Environment,2003,37(21):2949-2955.
[32] Tan Z F,Rohrer F,Lu K D,et al. Wintertime photochemistry in Beijing:observations of ROXradical concentrations in the North China Plain during the BEST-ONE campaign[J]. Atmospheric Chemistry and Physics,2018,18(16):12391-12411.
[33] Gutzwiller L,Arens F,Baltensperger U,et al. Significance of semivolatile diesel exhaust organics for secondary HONO formation[J]. Environmental Science&Technology,2002,36(4):677-682.
[34] Ammann M,Rssler E,Strekowski R,et al. Nitrogen dioxide multiphase chemistry:uptake kinetics on aqueous solutions containing phenolic compounds[J]. Physical Chemistry Chemical Physics,2005,7(12):2513-2518.
[35] Zhang B Q,Tao F M. Direct homogeneous nucleation of NO2,H2O,and NH3for the production of ammonium nitrate particles and HONO gas[J]. Chemical Physics Letters,2010,489(4-6):143-147.
[36] Wang S S,Zhou R,Zhao H,et al. Long-term observation of atmospheric nitrous acid(HONO)and its implication to local NO2levels in Shanghai,China[J]. Atmospheric Environment,2013,77:718-724.
[37] Wang J Q,Zhang X S,Guo J,et al. Observation of nitrous acid(HONO)in Beijing, China:Seasonal variation, nocturnal formation and daytime budget[J]. Science of The Total Environment,2017,587-588:350-359.
[38] Huang R J,Yang L,Cao J J,et al. Concentration and sources of atmospheric nitrous acid(HONO)at an urban site in Western China[J]. Science of the Total Environment,2017,593-594:165-172.
[39] Harrison R M,Peak J D,Collins G M. Tropospheric cycle of nitrous acid[J]. Journal of Geophysical Research:Atmospheres,1996,101(D9):14429-14439.
[40] Li Y,An J L,Min M,et al. Impacts of HONO sources on the air quality in Beijing,Tianjin and Hebei Province of China[J].Atmospheric Environment,2011,45(27):4735-4744.
[41] Yang Q,Su H,Li X,et al. Daytime HONO formation in the suburban area of the megacity Beijing,China[J]. Science China Chemistry,2014,57(7):1032-1042.
[42]杨闻达,程鹏,田智林,等.广州市夏秋季HONO污染特征及白天未知源分析[J].中国环境科学,2017,37(6):2029-2039.Yang W D,Cheng P,Tian Z L,et al. Study on HONO pollution characteristics and daytime unknown sources during summer and autumn in Guangzhou,China[J]. China Environmental Science,2017,37(6):2029-2039.
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