基于高分辨率MARGA分析桂林市PM_(2.5)水溶性离子特征
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摘要
利用高时间分辨率MARGA于2017年2月17日～3月24日在桂林市开展PM_(2.5)组分监测,结合同一点位环境和气象监测数据,分析桂林市大气PM_(2.5)水溶性无机离子组分特征及气溶胶酸性.结果表明:MARGA监测的PM_(2.5)中8种水溶性离子与PM_(2.5)变化趋势一致.8种水溶性离子总浓度均值29.27μg/m~3, 3种二次水溶性离子SO_4~(2-)、NO_3~-和NH_4~+浓度均值26.91μg/m~3,占水溶性离子总浓度的93.50%,是桂林市大气PM_(2.5)的主要组分.二次水溶性离子SO_4~(2-)、NH_4~+和NO_3~-两两之间存在显著正相关性(相关系数均>0.80),提示二次离子产生的机制及在大气中的演化、沉积具有一定的相似性.无论有无降雨,能见度(Vis)均随着水溶性离子,尤其是二次水溶性离子浓度的增加呈幂函数规律递减.24h累计降雨量≥10.0mm时,湿清除作用明显.晴天及降雨量不大的天气下,需注意管控机动车尾气、生物质燃烧和扬尘污染.SOR、NOR分别为0.35、0.12,SO_2同时通过均相和非均相氧化反应转化为SO_4~(2-), NO_x主要是通过白天光化学反应转化为NO_3~-.大多数离子和气态前体物均存在明显的日变化规律,这与物质的来源、形成机制和气象条件不同有关.CE/AE摩尔浓度均值为1.5,桂林市PM_(2.5)总体偏碱性.PM_(2.5)中SO_4~(2-)、NO_3~-、Cl~-主要以(NH_4)_2SO_4、NH_4NO_3和NH_4Cl形式存在.PM_(2.5)中NH_4~+可能与监测点位交通源排放有关,桂林市应加强交通污染物排放管控.
The composition of PM_(2.5) was serially on-line monitored by using Monitor for Aerosols and Gases in Ambient Air(MARGA ADI 2080) at atmosphere monitoring sites of Guilin in a time span of February 17 to March 24, 2017 continuously. Composition characteristics of water-soluble inorganic matter, secondary conversion mechanism and aerosol acidity were analyzed combining with environmental monitoring data and meteorological monitoring data. The results shown that variability of 8 water-soluble ions concentration was in consistent with the trend of PM_(2.5) varieties in Guilin. The average mass concentration of the total water-soluble ions was 29.27μg/m~3, and the average mass concentration of three secondary water soluble ions SO_4~(2-), NH_4~+ and NO_3~- was 26.91μg/m~3, accounting for 93.50% of PM_(2.5), indicating that secondary water-soluble ions were the major components of PM_(2.5) in Guilin. There was a significant positive correlation between secondary water-soluble ions, namely SO_4~(2-), NH_4~+ and NO_3~-(all the correlation coefficients were over 0.80),indicating that the mechanism of evolution and deposition of secondary water-soluble ions in the atmosphere are similar to each other.Visibility declined in terms of power function with the increase of the water-soluble ions, especially secondary water-soluble ions despite if there was rain fell or not. When the rain fell significantly(accumulated rainfall of 24 hours≥310 mm), the effect of wet removal was obvious.In sunny days and days of light rainy, the focal point should be the control of vehicle exhaust, biomass burning and dust pollution. SOR and NOR were 0.35 and 0.12, respectively. SO_2 was converted to SO_4~(2-) by homogeneous and heterogeneous oxidation reactions at the same time. NO_x was mainly converted to NO_3~-by photochemical reactions during the day. A pronounced diurnal cycle was found for most ions and gaseous precursors which could be attributed to their respective sources, formation mechanisms and meteorological conditions.The mean value of CE/AE was 1.5, indicating that most aerosols in Guilin were relatively alkaline. In PM_(2.5), SO_4~(2-), NO_3~- and Cl~- mainly exist in the forms of(NH_4)_2SO_4, NH_4NO_3 and NH_4Cl, respectively. NH_4~+ in PM_(2.5) was related to local vehicle emissions. Regulatory actions in minimizing traffic emissions may represent the critical step in mitigating haze in Guilin.
The composition of PM_(2.5) was serially on-line monitored by using Monitor for Aerosols and Gases in Ambient Air(MARGA ADI 2080) at atmosphere monitoring sites of Guilin in a time span of February 17 to March 24, 2017 continuously. Composition characteristics of water-soluble inorganic matter, secondary conversion mechanism and aerosol acidity were analyzed combining with environmental monitoring data and meteorological monitoring data. The results shown that variability of 8 water-soluble ions concentration was in consistent with the trend of PM_(2.5) varieties in Guilin. The average mass concentration of the total water-soluble ions was 29.27μg/m~3, and the average mass concentration of three secondary water soluble ions SO_4~(2-), NH_4~+ and NO_3~- was 26.91μg/m~3, accounting for 93.50% of PM_(2.5), indicating that secondary water-soluble ions were the major components of PM_(2.5) in Guilin. There was a significant positive correlation between secondary water-soluble ions, namely SO_4~(2-), NH_4~+ and NO_3~-(all the correlation coefficients were over 0.80),indicating that the mechanism of evolution and deposition of secondary water-soluble ions in the atmosphere are similar to each other.Visibility declined in terms of power function with the increase of the water-soluble ions, especially secondary water-soluble ions despite if there was rain fell or not. When the rain fell significantly(accumulated rainfall of 24 hours≥310 mm), the effect of wet removal was obvious.In sunny days and days of light rainy, the focal point should be the control of vehicle exhaust, biomass burning and dust pollution. SOR and NOR were 0.35 and 0.12, respectively. SO_2 was converted to SO_4~(2-) by homogeneous and heterogeneous oxidation reactions at the same time. NO_x was mainly converted to NO_3~-by photochemical reactions during the day. A pronounced diurnal cycle was found for most ions and gaseous precursors which could be attributed to their respective sources, formation mechanisms and meteorological conditions.The mean value of CE/AE was 1.5, indicating that most aerosols in Guilin were relatively alkaline. In PM_(2.5), SO_4~(2-), NO_3~- and Cl~- mainly exist in the forms of(NH_4)_2SO_4, NH_4NO_3 and NH_4Cl, respectively. NH_4~+ in PM_(2.5) was related to local vehicle emissions. Regulatory actions in minimizing traffic emissions may represent the critical step in mitigating haze in Guilin.
引文
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[12]Hu G Y,Zhang Y M,Sun J Y,et al.Variability,formation and acidity of water-soluble ions in Beijing based on the semi-continuous observations[J].Atmospheric Research,2014,145-146(2014):1-11.
[13]杜娟,宋韶华,张志朋,等.桂林市细颗粒物典型排放源单颗粒质谱特征研究[J].环境科学学报,2015,35(5):1556-1562.Du J,Song S H,Zhang Z P,et al.Single particle characteristics of fine particulate matter emitted from typical sources of Guilin[J].Acta Scientiae Circumstantiae,2015,35(5):1556-1562.
[14]张志朋,杜娟,宋韶华,等.夏季桂林市大气PM2.5化学组成和成分分布的质谱研究[J].环境监测管理与技术,2015,27(6):22-26.Zhang Z P,Du J,Song S H,Study on chemical constitution and component distribution of airborne PM2.5 in summer of Guilin by mass spectrometer[J].The Administration and Technique of Environmental Monitoring,2015,27(6):22-26.
[15]张志朋.基于环境库兹涅茨曲线特征的桂林市大气环境状况研究[J].环境监测管理与技术,2014,26(1):14-18.Zhang Z P,Song Y X,Zou Z Y.Study on the atmospheric environmental conditions in Guilin city based on environmental Kuznets Curve[J].The Administration and Technique of Environmental Monitoring,2014,26(1):14-18.
[16]Millero F J.Chemical oceanography[M].Boca Raton:CRC Press,1996.
[17]Kerminen V M,Hillamo R,Teinila K,et al.Ion balances of sizeresolved tropospheric aerosol samples:implications for the acidity and atmospheric processing of aerosol[J].Atmospheric Environment,2001,(35):5255-5265.
[18]Schwab J J,Felton H D,Demerjian K L.Aerosol chemical composition in New York state from integrated filter samples:urban rural and seasonal contrasts[J].Journal of Ggeophysical Researchatmospheres,2004,109,D16S05.
[19]Stevens R K,Dzubay T G,Shaw R W,et al.Characterization of the aerosol in the Great Smoky Mountains.Environmental Science&Technology,1980,14:1491-1498.
[20]姚青,孙玫玲,张长春,等.潮州沿海大气气溶胶无机离子浓度分布与气象要素的相关分析[J].气象与环境学报,2007,23(4):39-42.Yao Q,Sun M L,Zhang C C,et al.Relationship between inorganic ion concentration distribution of atmospheric aerosol and meteorological element at Chaozhou coastland[J].Journal of Meteorology and Environment,2007,23(4):39-42.
[21]何俊杰,吴耕晨,张国华,等.广州雾霾期间气溶胶水溶性离子的日变化特征及形成机制[J].中国环境科学,2014,34(5):1107-1112.He J J,Wu G C,Zhang G H,et al.Diurnal variations and formation mechanisms of water-soluble inorganic ions in aerosols during a haze-fog period in Guangzhou[J].China Environmental Science,2014,34(5):1107-1112.
[22]Wang Y,Zhuang G S,Zhang X Y,et al.An.The ion chemistry,seasonal cycle,and sources of PM2.5 and TSP aerosol in Shanghai[J].Atmospheric Environment,2006,40(16):2935-2952.
[23]袁超.香港PM2.5水溶性离子的在线监测仪器评估及理化特征分析[D].济南:山东大学,2012.Yuan C.Evaluation of ambient PM2.5 real-time monitoring instruments and online measurement of inorganic water soluble ions in Hong Kong[D].Jinan:Shandong University,2012.
[24]Wang G H,Zhang F,Peng J F,et al.Particle acidity and sulfate production during severe haze events in China cannot be reliably inferred by assuming a mixture of inorganic salts[J].Atmospheric Chemistry and Physics,2018,18:10123-10132.
[25]Wang G H,Zhang R Y,Gomez M E,et al.Persistent sulfate formation from London Fog to Chinese haze[J].Proceedings of the National Academy of Sciences of the United States of America,2016,113(48):13630-13635.
[26]Cheng Y F,Zheng G J,Wei C,et al.Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China[J].Science Advances,2016,2(12):e1601530.
[27]Liu X J,Ying Z,Han W X,et al.Enhanced nitrogen deposition over China[J].Nature,2013,494(7438):459-462.
[28]Pan Y P,Tian S L,Liu D W,et al.Fossil fuel combustion-related emissions dominate atmospheric ammonia sources during severe haze episodes:evidence from 15N-stable isotope in size-resolved aerosol ammonium[J].Environmental Science&Technology,2016,50(15):8049-8056.
[2]程真.长三角城市群灰霾污染与颗粒物理化性质的关系[D].北京:清华大学,2013.Cheng Z.Relationship between haze pollution and aerosol properties in the Yangtze River Delta of China[D].Beijing:Tsinghua University,2013.
[3]程玉婷,王格慧,孙涛,等.西安冬季非灰霾天与灰霾天PM2.5中水溶性有机氮污染特征比较[J].环境科学,2014,35(7):2468-2476.Cheng Y T,Wang G H,Sun T,et al.Characteristics of water-soluble organic nitrogen of PM2.5 in Xi’an during winter time non-haze and haze periods[J].Environmental Science,2014,35(7):2468-2476.
[4]丛晓光,程玲珑,王莉莉,等.北京城区灰霾期间大气PM2.5中水溶性离子污染特征及来源研究[J].首都师范大学学报(自然科学版),2017,38(1):49-57.Cong X G,Cheng L L,Wang L L,et al.The mass concentration levels,diurnal variation and source apportionment of water-soluble inorganic ions in PM2.5during haze days in Beijing urban area[J].Journal of Capital Normal University(Natural Science Edition),2017,38(1):49-57.
[5]吴烈善,孔德超,孙康,等.香河夏季PM2.5水溶性无机离子组分特征[J].中国环境科学,2015,35(10):2925-2933.Wu L S,Kong D C,Sun K,et al.Characteristics of water-soluble inorganic ions of PM2.5 in summer at Xianghe[J].China Environmental Science,2015,35(10):2925-2933
[6]廖碧婷,吴兑,常越,等.广州地区SO42-、NO3-、NH4+与相关气体污染特征研究[J].环境科学学报,2013,34(6):1551-1559.Liao B T,Wu D,Chang Y,et al.Characteristics of particulate SO42-,NO3-,NH4+and related gaseous pollutants in Guangzhou[J].Acta Scientiae Circumstantiae,2013,34(6):1551-1559.
[7]陈静,杨鹏,韩军彩,等.基于高分辨率MARGA数据分析石家庄PM2.5成分谱特征[J].中国环境科学,2015,35(9):2594-2604.Chen J,Yang P,Han J C,et al.Analysis of PM2.5 spectrum characteristics in Shijiazhuang based on high resolution MARGA data[J].China Environmental Science,2015,35(9):2594-2604.
[8]李永麒,张国斌.太原市春季大气PM2.5中水溶性离子在线观测分析[J].环境化学,2017,36(8):1777-1784.Li Y Q,Zhang G B.Continuous online observation analysis of watersoluble ions in PM2.5 from the atmosphere in spring in Taiyuan,Environmental Chemistry[J].2017,36(8):1777-1784.
[9]高嵩,范美益,曹芳,等.基于高分辨率在线气溶胶监测仪数据分析南京北郊冬季PM2.5中水溶性离子污染特性[J].科学技术与工程,2018,18(11):337-342.Gao S,Fan M Y,Cao F,et al.Characteristics and source of water soluble inorganic ions in PM2.5 based on high resolution MARGA data in Nanjing[J].Science Technology and Engineering,2018,18(11):337-342.
[10]陈慧忠.基于高时间分辨率MARGA数据分析珠三角地区气溶胶的特征[D].北京:中国气象科学研究院,2013.Chen H Z.Analyses of the characteristics of aerosols in Pearl River Delta based on the MARGA data[D].Beijing:Chinese Academy of Meteorological Sciences,2013.
[11]乔利平.利用在线高分辨观测手段研究烟花爆竹燃放的大气污染物理化特征[J].环境科学学报,2014,34(9):2398-2406.Qiao L P.Chemical and physical characterization of atmospheric pollutants during the firework episodes based on the high timeresolution observation methods[J].Acta Scientiae Circumstantiae,2014,34(9):2398-2406.
[12]Hu G Y,Zhang Y M,Sun J Y,et al.Variability,formation and acidity of water-soluble ions in Beijing based on the semi-continuous observations[J].Atmospheric Research,2014,145-146(2014):1-11.
[13]杜娟,宋韶华,张志朋,等.桂林市细颗粒物典型排放源单颗粒质谱特征研究[J].环境科学学报,2015,35(5):1556-1562.Du J,Song S H,Zhang Z P,et al.Single particle characteristics of fine particulate matter emitted from typical sources of Guilin[J].Acta Scientiae Circumstantiae,2015,35(5):1556-1562.
[14]张志朋,杜娟,宋韶华,等.夏季桂林市大气PM2.5化学组成和成分分布的质谱研究[J].环境监测管理与技术,2015,27(6):22-26.Zhang Z P,Du J,Song S H,Study on chemical constitution and component distribution of airborne PM2.5 in summer of Guilin by mass spectrometer[J].The Administration and Technique of Environmental Monitoring,2015,27(6):22-26.
[15]张志朋.基于环境库兹涅茨曲线特征的桂林市大气环境状况研究[J].环境监测管理与技术,2014,26(1):14-18.Zhang Z P,Song Y X,Zou Z Y.Study on the atmospheric environmental conditions in Guilin city based on environmental Kuznets Curve[J].The Administration and Technique of Environmental Monitoring,2014,26(1):14-18.
[16]Millero F J.Chemical oceanography[M].Boca Raton:CRC Press,1996.
[17]Kerminen V M,Hillamo R,Teinila K,et al.Ion balances of sizeresolved tropospheric aerosol samples:implications for the acidity and atmospheric processing of aerosol[J].Atmospheric Environment,2001,(35):5255-5265.
[18]Schwab J J,Felton H D,Demerjian K L.Aerosol chemical composition in New York state from integrated filter samples:urban rural and seasonal contrasts[J].Journal of Ggeophysical Researchatmospheres,2004,109,D16S05.
[19]Stevens R K,Dzubay T G,Shaw R W,et al.Characterization of the aerosol in the Great Smoky Mountains.Environmental Science&Technology,1980,14:1491-1498.
[20]姚青,孙玫玲,张长春,等.潮州沿海大气气溶胶无机离子浓度分布与气象要素的相关分析[J].气象与环境学报,2007,23(4):39-42.Yao Q,Sun M L,Zhang C C,et al.Relationship between inorganic ion concentration distribution of atmospheric aerosol and meteorological element at Chaozhou coastland[J].Journal of Meteorology and Environment,2007,23(4):39-42.
[21]何俊杰,吴耕晨,张国华,等.广州雾霾期间气溶胶水溶性离子的日变化特征及形成机制[J].中国环境科学,2014,34(5):1107-1112.He J J,Wu G C,Zhang G H,et al.Diurnal variations and formation mechanisms of water-soluble inorganic ions in aerosols during a haze-fog period in Guangzhou[J].China Environmental Science,2014,34(5):1107-1112.
[22]Wang Y,Zhuang G S,Zhang X Y,et al.An.The ion chemistry,seasonal cycle,and sources of PM2.5 and TSP aerosol in Shanghai[J].Atmospheric Environment,2006,40(16):2935-2952.
[23]袁超.香港PM2.5水溶性离子的在线监测仪器评估及理化特征分析[D].济南:山东大学,2012.Yuan C.Evaluation of ambient PM2.5 real-time monitoring instruments and online measurement of inorganic water soluble ions in Hong Kong[D].Jinan:Shandong University,2012.
[24]Wang G H,Zhang F,Peng J F,et al.Particle acidity and sulfate production during severe haze events in China cannot be reliably inferred by assuming a mixture of inorganic salts[J].Atmospheric Chemistry and Physics,2018,18:10123-10132.
[25]Wang G H,Zhang R Y,Gomez M E,et al.Persistent sulfate formation from London Fog to Chinese haze[J].Proceedings of the National Academy of Sciences of the United States of America,2016,113(48):13630-13635.
[26]Cheng Y F,Zheng G J,Wei C,et al.Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China[J].Science Advances,2016,2(12):e1601530.
[27]Liu X J,Ying Z,Han W X,et al.Enhanced nitrogen deposition over China[J].Nature,2013,494(7438):459-462.
[28]Pan Y P,Tian S L,Liu D W,et al.Fossil fuel combustion-related emissions dominate atmospheric ammonia sources during severe haze episodes:evidence from 15N-stable isotope in size-resolved aerosol ammonium[J].Environmental Science&Technology,2016,50(15):8049-8056.
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