气团来源对沿海城市PM_(2.5)中二次水溶性无机离子形成特征的影响研究
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摘要
大气细颗粒物(PM_(2.5))与雾霾天气密切相关,PM_(2.5)吸附的有毒有害物质,可能给人体健康带来危害。二次水溶性无机离子(SNA,包括SO_4~(2-)、NO_3~-和NH_4~+)是PM_(2.5)的重要组分,研究PM_(2.5)中SNA污染特征及形成和演化的影响因素,对认识雾霾污染的生消机制,提升人们的生活质量具有重要意义。利用在线气体及气溶胶成分监测系统(MARGA)观测了宁波市滨海地区春季、夏季和秋季大气PM_(2.5)中的SNA和气态污染物的变化趋势,并利用后向轨迹分析研究了不同气团影响下污染物的日变化规律。结果表明,观测期间,SNA在PM_(2.5)中的平均占比约为70.7%,NO_3~-是导致PM_(2.5)污染加重的主导离子。NO_3~-和SO_4~(2-)受气团传输影响较大,来自陆地气团的质量浓度普遍高于海洋气团,来自西北内陆方向的污染物输送是导致宁波空气质量下降的主要原因。宁波大气中的硫氧化率(SOR)较高,SO_4~(2-)主要由SO_2发生二次氧化反应生成;SO_4~(2-)的形成与相对湿度(RH)密切相关,SOR随着RH的增加而显著增大,当RH>85%时,大气中的硫氧化物绝大部分以SO_4~(2-)形式存在,SOR接近1;而温度变化对SOR无明显影响;来自西南与东部受海洋显著影响的气团SOR高于来自陆地气团的相应值。夏季RH普遍较高,西南方向气团影响下高浓度的气态污染物(NO_2、O_3、NH_3)可明显促进SO_4~(2-)的生成,一定程度上控制人为气态污染物的排放能有效减少SO_4~(2-)生成。与SOR比较而言,氮氧化率(NOR)和NO_3~-与温度、RH、气态污染物浓度等环境因素的关系比较复杂,暗示多种反应机理共同作用影响氮氧化物的转化。
Severe haze weather is closely related to atmospheric fine particulate matter(PM_(2.5)), which could adsorb toxic and harmful substances, pose a severe danger to human health. Secondary water-soluble inorganic ions(SNA, including SO_4~(2-), NO_3~-and NH_4~+) are important components in PM_(2.5). In order to control haze pollutant and improve people's quality of life, it is of great significance to study the characteristics of SNA and the influencing factors of its formation and evolution in PM_(2.5). A monitor for aerosols and gases in ambient Air(MARGA) was used to continuously measure SO_4~(2-), NO_3~-and NH_4~+ and trace gases at a coastal site in Ningbo. Based on the clusters analysis of back trajectory, the daily variations of SNA associated with different air mass originations were analyzed. It showed that 70.7% of PM_(2.5) was SO_4~(2-), NO_3~- and NH_4~+ during the study period, and the elevated NO_3~- was the dominant ion during the polluted periods. The transmission of NO_3~- and SO_4~(2-)ions was greatly influenced by air masses.The SNA concentrations associated with the land air masses were significantly higher than that from the ocean air masses. The air mass from the northwest land was the main reason for the decline of air quality in Ningbo. The sulfur oxidation rate(SOR) was relatively high in Ningbo and SO_4~(2-) was mainly formed by secondary reaction activity. The formation of SO_4~(2-)was closely related to relative humidity(RH), SOR increased significantly with the increase of RH, when RH>85%, SO_4~(2-)became the dominant form of atmospheric sulfur oxides, and SOR was close to 1. However, temperature had no obvious effect on SOR. The SOR associated with air masses from southwest and east, which were significantly affected by oceans, were higher than the corresponding values from terrestrial air masses. In summer, the high RH and the high concentration of gaseous pollutants(NO_2, O_3, NH_3) associated southwest air mass, would obviously promote the formation of SO_4~(2-). Thus, we only can effectively reduce the formation of SO_4~(2-) through controlling the emission of anthropogenic gaseous pollutants to a certain extent. The relationships between nitrogen oxidation rate(NOR), NO_3~- and environmental factors such as temperature, RH and gaseous pollution are more complicated comparing with SOR,which imply that there are several combination of reaction mechanisms affecting the transformation of nitrogen oxides.
Severe haze weather is closely related to atmospheric fine particulate matter(PM_(2.5)), which could adsorb toxic and harmful substances, pose a severe danger to human health. Secondary water-soluble inorganic ions(SNA, including SO_4~(2-), NO_3~-and NH_4~+) are important components in PM_(2.5). In order to control haze pollutant and improve people's quality of life, it is of great significance to study the characteristics of SNA and the influencing factors of its formation and evolution in PM_(2.5). A monitor for aerosols and gases in ambient Air(MARGA) was used to continuously measure SO_4~(2-), NO_3~-and NH_4~+ and trace gases at a coastal site in Ningbo. Based on the clusters analysis of back trajectory, the daily variations of SNA associated with different air mass originations were analyzed. It showed that 70.7% of PM_(2.5) was SO_4~(2-), NO_3~- and NH_4~+ during the study period, and the elevated NO_3~- was the dominant ion during the polluted periods. The transmission of NO_3~- and SO_4~(2-)ions was greatly influenced by air masses.The SNA concentrations associated with the land air masses were significantly higher than that from the ocean air masses. The air mass from the northwest land was the main reason for the decline of air quality in Ningbo. The sulfur oxidation rate(SOR) was relatively high in Ningbo and SO_4~(2-) was mainly formed by secondary reaction activity. The formation of SO_4~(2-)was closely related to relative humidity(RH), SOR increased significantly with the increase of RH, when RH>85%, SO_4~(2-)became the dominant form of atmospheric sulfur oxides, and SOR was close to 1. However, temperature had no obvious effect on SOR. The SOR associated with air masses from southwest and east, which were significantly affected by oceans, were higher than the corresponding values from terrestrial air masses. In summer, the high RH and the high concentration of gaseous pollutants(NO_2, O_3, NH_3) associated southwest air mass, would obviously promote the formation of SO_4~(2-). Thus, we only can effectively reduce the formation of SO_4~(2-) through controlling the emission of anthropogenic gaseous pollutants to a certain extent. The relationships between nitrogen oxidation rate(NOR), NO_3~- and environmental factors such as temperature, RH and gaseous pollution are more complicated comparing with SOR,which imply that there are several combination of reaction mechanisms affecting the transformation of nitrogen oxides.
引文
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AN J L,CAO Q M,ZOU J A,et al.,2018.Seasonal Variation in water-soluble ions in airborne particulate deposition in the suburban Nanjing area,Yangtze River delta,China,during haze days and normal days[J].Archives of Environmental Contamination and Toxicology,74(1):1-15.
CHENG Y F,ZHENG G J,WEI C,et al.,2016.Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China[J].Science Advances,2(12):e1601530.
CHENG Y,HE K B,DU Z Y,et al.,2015.Humidity plays an important role in the PM2.5 pollution in Beijing[J].Environmental Pollution,197:68-75.
GAO J,PENG X,CHEN G,et al.,2016.Insights into the chemical characterization and sources of PM2.5 in Beijing at a 1-h time resolution[J].Science of the Total Environment,542(Part A):162-171.
GE B Z,SUN Y L,LIU Y,et al.,2013.Nitrogen dioxide measurement by cavity attenuated phase shift spectroscopy(CAPS)and implications in ozone production efficiency and nitrate formation in Beijing,China[J].Journal of Geophysical Research:Atmospheres,118(16):9499-9509.
LI G H,BEI N F,CAO J J,et al.,2016.A Possible pathway for rapid growth of sulfate during haze days in China[J].Atmospheric Chemistry and Physics Discussions,17(5):3301-3316.
LI K W,CHEN L H,YING F,et al.,2017.Meteorological and chemical impacts on ozone formation:A case study in Hangzhou,China[J].Atmospheric Research,196:40-52.
MA J,CHU B,LIU J,et al.,2018.NOx promotion of SO2 conversion to sulfate:An important mechanism for the occurrence of heavy haze during winter in Beijing[J].Environmental Pollution,233:662-669.
PAN Y P,WANG Y S,ZHANG J K,et al.,2016.Redefining the importance of nitrate during haze pollution to help optimize an emission control strategy[J].Atmospheric Environment,141:197-202.
PATHAK R K,WU W S,WANG T,2009.Summertime PM2.5 ionic species in four major cities of China:nitrate formation in an ammonia-deficient atmosphere[J].Atmospheric Chemistry and Physics,9(5):1711-1722.
PIERSON W R,BRACHACZEK W W,MCKEE D E,1979.Sulfate emissions from catalyst equipped automobiles on the highway[J].Journal of Air Pollution Control Association,29(3):255-257
QIAO B Q,CHEN Y,TIAN M W,et al.,2019.Characterization of water soluble inorganic ions and their evolution processes during PM2.5pollution episodes in a small city in southwest China[J].Science of the Total Environment,650:2605-2613.
SHON Z H,GHOSH S,KIM K H,et al.,2013.Analysis of water-soluble ions and their precursor gases over diurnal cycle[J].Atmospheric research,132-133:309-321.
TRUEX T J,PIERSON W R,MCKEE D E,1980.Sulfate in diesel exhaust[J].Environmental Science&Technology,14(9):1118-1121.
WANG G,ZHANG R,GOMEZ M E,et al.,2016.Persistent sulfate formation from London Fog to Chinese haze[J].Proceedings of the National Academy of Sciences,113(48):13630-13635.
XUE J,GRIFFITH S M,YU X,et al.,2014b.Effect of nitrate and sulfate relative abundance in PM2.5 on liquid water content explored through half-hourly observations of inorganic soluble aerosols at a polluted receptor site[J].Atmospheric environment,99:24-31.
XUE J,YUAN Z,LAU A K H,et al.,2014a.Insights into factors affecting nitrate in PM2.5 in a polluted high NOx environment through hourly observations and size distribution measurements[J].Journal of Geophysical Research:Atmospheres,119(8):4888-4902.
YANG H,ZHEN C,WANG S X,et al.,2015.Characteristics and source apportionment of PM2.5 during a fall heavy haze episode in the Yangtze River Delta of China[J].Atmospheric Environment,123(Part B):380-391.
ZHANG R J,JING J S,TAO J,et al.,2013.Chemical characterization and source apportionment of PM2.5 in Beijing:seasonal perspective[J].Atmospheric Chemistry and Physics,13(14):7053-7074.
ZHANG R,SUN X,SHI A,et al.,2018.Secondary inorganic aerosols formation during haze episodes at an urban site in Beijing,China[J].Atmospheric Environment,177:275-282.
ZHANG T,CAO J J,TIE X X,et al.,2011.Water-soluble ions in atmospheric aerosols measured in Xi'an,China:seasonal variations and sources[J].Atmospheric Research,102(1-2):110-119.
安静宇,2015.长三角地区冬季大气细颗粒物来源追踪模拟研究[D].上海:东华大学.AN J Y,2015.Source apportionment of fine particles in the Yang River delta region in winter season based on air quality simulation[D].Shanghai:Donghua University.
邓君俊,2011.长三角地区霾天气形成机理和预报方法研究[D].南京:南京大学.DENG J J,2011.Study on the formation mechanism and forecasting methodology on haze weather in Yangtze River delta[D].Nanjing:NanjingUniversity.
高韩钰,魏静,王跃思,2017.北京南郊区PM2.5中水溶性无机盐季节变化及来源分析[J].环境科学,39(5):1988-1993.GAO H Y,WEI J,WANG Y S,2017.Seasonal variation and source analysis of water-soluble inorganic salts in PM2.5 in the southern suburbs of Beijing[J].Environmental Science,39(5):1988-1993.
耿彦红,刘卫,单健,等,2010.上海市大气颗粒物中水溶性无机离子的粒径分布特征[J].中国环境科学,30(12):1585-1589.GENG Y H,LIU W,SHAN J,et al.,2010.Characterization of major water-soluble ions in size-fractionated particulate matters in Shanghai[J].China Environmental Science,30(12):1585-1589.
李莉,蔡鋆琳,周敏,2015.2013年12月中国中东部地区严重灰霾期间上海市颗粒物的输送途径及潜在源贡献分析[J].环境科学,36(7):2327-2336.LI L,CAI Y L,ZHOU M,2015.Potential source contribution analysis of the particulate matters in Shanghai during the heavy haze episode in eastern and middle China in December,2013[J].Environmental Science,36(7):2327-2336.
刘寿东,张莉,张园园,等,2018.温湿度对南京北郊PM2.5中二次无机离子生成演化的影响[J].生态环境学报,27(4):714-721.LIU S D,ZHANG L,ZHANG Y Y,et al.,2018.Influencesof temperature and humidity on formation and evolution of secondary aerosol inorganic ions of PM2.5 at Northern Suburban Nanjing[J].Ecology and Environmental Sciences,27(4):714-721.
齐梦溪,赵文慧,孙爽,等,2019.2014-2016年北京市PM2.5污染时空分布特征[J].生态环境学报,28(1):97-105.QI M X,ZHAO W H,SUN S,et al.,2019.Temporal and spatial distribution characteristics of PM2.5 pollution in Beijing from 2014 to2016[J].Ecology and Environmental Sciences,28(1):97-105.
施洋,2014.上海市大气亚微米级颗粒物PM1污染特征与霾污染形成机制[D].上海:复旦大学.SHI Y,2014.Airborne Submicron Particulate(PM1)Polluton in Shanghai:chemical variability,source apportionments and the impacts on haze formation[D].Shanghai:Fudan University.
魏玉香,杨卫芬,银燕,等,2009.霾天气南京市大气PM2.5中水溶性无机离子污染特征[J].环境科学与技术,32(11):66-71.WEI Y X,YANG W F,YIN Y,et al.,2009.Pollution characteristics of Nanjing water-soluble ions in air fine particles under haze days[J].Environmental Science&Technology,32(11):66-71.
赵倩彪,胡鸣,张懿华,2014.利用后向轨迹模式研究上海市PM2.5来源分布及传输特征[J].环境监测管理与技术,26(4):22-26.ZHAO Q B,HU M,ZHANG Y H,2014.Study of source distribution and transportation characteristics of PM2.5 in Shanghai using backward trajectory model[J].The Administration and Technique of Environmental Monitoring,26(4):22-26.
朱书慧,周敏,乔利平,等,2016.2015年12月气流轨迹对长三角区域细颗粒物浓度和分布的影响[J].环境科学学报,36(12):4285-4294.ZHU S H,ZHOU M,QIAO L P,et al.,2016.Impact of the air mass trajectories on PM2.5 concentrations and distribution in the Yangtze River Delta in December 2015[J].Acta Scientiae Circumstantiae,36(12):4285-4294.
张园园,2017.南京北郊PM2.5中水溶性离子特征在线监测研究[D].南京:南京信息工程大学.ZHANG Y Y,2017.Characteristic of Water-Soluble Ions in PM2.5 in the Northern Suburb of Nanjing Based on On-Line Monitoring[D].Nanjing:Nanjing University of Information Science&Technology.
AN J L,CAO Q M,ZOU J A,et al.,2018.Seasonal Variation in water-soluble ions in airborne particulate deposition in the suburban Nanjing area,Yangtze River delta,China,during haze days and normal days[J].Archives of Environmental Contamination and Toxicology,74(1):1-15.
CHENG Y F,ZHENG G J,WEI C,et al.,2016.Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China[J].Science Advances,2(12):e1601530.
CHENG Y,HE K B,DU Z Y,et al.,2015.Humidity plays an important role in the PM2.5 pollution in Beijing[J].Environmental Pollution,197:68-75.
GAO J,PENG X,CHEN G,et al.,2016.Insights into the chemical characterization and sources of PM2.5 in Beijing at a 1-h time resolution[J].Science of the Total Environment,542(Part A):162-171.
GE B Z,SUN Y L,LIU Y,et al.,2013.Nitrogen dioxide measurement by cavity attenuated phase shift spectroscopy(CAPS)and implications in ozone production efficiency and nitrate formation in Beijing,China[J].Journal of Geophysical Research:Atmospheres,118(16):9499-9509.
LI G H,BEI N F,CAO J J,et al.,2016.A Possible pathway for rapid growth of sulfate during haze days in China[J].Atmospheric Chemistry and Physics Discussions,17(5):3301-3316.
LI K W,CHEN L H,YING F,et al.,2017.Meteorological and chemical impacts on ozone formation:A case study in Hangzhou,China[J].Atmospheric Research,196:40-52.
MA J,CHU B,LIU J,et al.,2018.NOx promotion of SO2 conversion to sulfate:An important mechanism for the occurrence of heavy haze during winter in Beijing[J].Environmental Pollution,233:662-669.
PAN Y P,WANG Y S,ZHANG J K,et al.,2016.Redefining the importance of nitrate during haze pollution to help optimize an emission control strategy[J].Atmospheric Environment,141:197-202.
PATHAK R K,WU W S,WANG T,2009.Summertime PM2.5 ionic species in four major cities of China:nitrate formation in an ammonia-deficient atmosphere[J].Atmospheric Chemistry and Physics,9(5):1711-1722.
PIERSON W R,BRACHACZEK W W,MCKEE D E,1979.Sulfate emissions from catalyst equipped automobiles on the highway[J].Journal of Air Pollution Control Association,29(3):255-257
QIAO B Q,CHEN Y,TIAN M W,et al.,2019.Characterization of water soluble inorganic ions and their evolution processes during PM2.5pollution episodes in a small city in southwest China[J].Science of the Total Environment,650:2605-2613.
SHON Z H,GHOSH S,KIM K H,et al.,2013.Analysis of water-soluble ions and their precursor gases over diurnal cycle[J].Atmospheric research,132-133:309-321.
TRUEX T J,PIERSON W R,MCKEE D E,1980.Sulfate in diesel exhaust[J].Environmental Science&Technology,14(9):1118-1121.
WANG G,ZHANG R,GOMEZ M E,et al.,2016.Persistent sulfate formation from London Fog to Chinese haze[J].Proceedings of the National Academy of Sciences,113(48):13630-13635.
XUE J,GRIFFITH S M,YU X,et al.,2014b.Effect of nitrate and sulfate relative abundance in PM2.5 on liquid water content explored through half-hourly observations of inorganic soluble aerosols at a polluted receptor site[J].Atmospheric environment,99:24-31.
XUE J,YUAN Z,LAU A K H,et al.,2014a.Insights into factors affecting nitrate in PM2.5 in a polluted high NOx environment through hourly observations and size distribution measurements[J].Journal of Geophysical Research:Atmospheres,119(8):4888-4902.
YANG H,ZHEN C,WANG S X,et al.,2015.Characteristics and source apportionment of PM2.5 during a fall heavy haze episode in the Yangtze River Delta of China[J].Atmospheric Environment,123(Part B):380-391.
ZHANG R J,JING J S,TAO J,et al.,2013.Chemical characterization and source apportionment of PM2.5 in Beijing:seasonal perspective[J].Atmospheric Chemistry and Physics,13(14):7053-7074.
ZHANG R,SUN X,SHI A,et al.,2018.Secondary inorganic aerosols formation during haze episodes at an urban site in Beijing,China[J].Atmospheric Environment,177:275-282.
ZHANG T,CAO J J,TIE X X,et al.,2011.Water-soluble ions in atmospheric aerosols measured in Xi'an,China:seasonal variations and sources[J].Atmospheric Research,102(1-2):110-119.
安静宇,2015.长三角地区冬季大气细颗粒物来源追踪模拟研究[D].上海:东华大学.AN J Y,2015.Source apportionment of fine particles in the Yang River delta region in winter season based on air quality simulation[D].Shanghai:Donghua University.
邓君俊,2011.长三角地区霾天气形成机理和预报方法研究[D].南京:南京大学.DENG J J,2011.Study on the formation mechanism and forecasting methodology on haze weather in Yangtze River delta[D].Nanjing:NanjingUniversity.
高韩钰,魏静,王跃思,2017.北京南郊区PM2.5中水溶性无机盐季节变化及来源分析[J].环境科学,39(5):1988-1993.GAO H Y,WEI J,WANG Y S,2017.Seasonal variation and source analysis of water-soluble inorganic salts in PM2.5 in the southern suburbs of Beijing[J].Environmental Science,39(5):1988-1993.
耿彦红,刘卫,单健,等,2010.上海市大气颗粒物中水溶性无机离子的粒径分布特征[J].中国环境科学,30(12):1585-1589.GENG Y H,LIU W,SHAN J,et al.,2010.Characterization of major water-soluble ions in size-fractionated particulate matters in Shanghai[J].China Environmental Science,30(12):1585-1589.
李莉,蔡鋆琳,周敏,2015.2013年12月中国中东部地区严重灰霾期间上海市颗粒物的输送途径及潜在源贡献分析[J].环境科学,36(7):2327-2336.LI L,CAI Y L,ZHOU M,2015.Potential source contribution analysis of the particulate matters in Shanghai during the heavy haze episode in eastern and middle China in December,2013[J].Environmental Science,36(7):2327-2336.
刘寿东,张莉,张园园,等,2018.温湿度对南京北郊PM2.5中二次无机离子生成演化的影响[J].生态环境学报,27(4):714-721.LIU S D,ZHANG L,ZHANG Y Y,et al.,2018.Influencesof temperature and humidity on formation and evolution of secondary aerosol inorganic ions of PM2.5 at Northern Suburban Nanjing[J].Ecology and Environmental Sciences,27(4):714-721.
齐梦溪,赵文慧,孙爽,等,2019.2014-2016年北京市PM2.5污染时空分布特征[J].生态环境学报,28(1):97-105.QI M X,ZHAO W H,SUN S,et al.,2019.Temporal and spatial distribution characteristics of PM2.5 pollution in Beijing from 2014 to2016[J].Ecology and Environmental Sciences,28(1):97-105.
施洋,2014.上海市大气亚微米级颗粒物PM1污染特征与霾污染形成机制[D].上海:复旦大学.SHI Y,2014.Airborne Submicron Particulate(PM1)Polluton in Shanghai:chemical variability,source apportionments and the impacts on haze formation[D].Shanghai:Fudan University.
魏玉香,杨卫芬,银燕,等,2009.霾天气南京市大气PM2.5中水溶性无机离子污染特征[J].环境科学与技术,32(11):66-71.WEI Y X,YANG W F,YIN Y,et al.,2009.Pollution characteristics of Nanjing water-soluble ions in air fine particles under haze days[J].Environmental Science&Technology,32(11):66-71.
赵倩彪,胡鸣,张懿华,2014.利用后向轨迹模式研究上海市PM2.5来源分布及传输特征[J].环境监测管理与技术,26(4):22-26.ZHAO Q B,HU M,ZHANG Y H,2014.Study of source distribution and transportation characteristics of PM2.5 in Shanghai using backward trajectory model[J].The Administration and Technique of Environmental Monitoring,26(4):22-26.
朱书慧,周敏,乔利平,等,2016.2015年12月气流轨迹对长三角区域细颗粒物浓度和分布的影响[J].环境科学学报,36(12):4285-4294.ZHU S H,ZHOU M,QIAO L P,et al.,2016.Impact of the air mass trajectories on PM2.5 concentrations and distribution in the Yangtze River Delta in December 2015[J].Acta Scientiae Circumstantiae,36(12):4285-4294.
张园园,2017.南京北郊PM2.5中水溶性离子特征在线监测研究[D].南京:南京信息工程大学.ZHANG Y Y,2017.Characteristic of Water-Soluble Ions in PM2.5 in the Northern Suburb of Nanjing Based on On-Line Monitoring[D].Nanjing:Nanjing University of Information Science&Technology.
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