Variations of ground-level O-3 and its precursors in Beijing in summertime between 2005 and 2011

Abstract. Elevated ground-level ozone (O3), reflecting atmospheric oxidative capacity, are of increasing concern. High levels of total oxidants (Ox= O3 + NO2) have been persistently observed as a feature of Beijing's air pollution. Beijing is a well-known megacity requiring the enforcement of stringent air quality controls as rapid economic growth continues. To evaluate the effect of air quality controls in recent years, ground-based on-line measurements at an urban site were conducted in summer and the variations in O3 with simultaneous changes in NOx and volatile organic compounds (VOCs) between 2005 and 2011 were analyzed. Both NOx and total VOCs in Beijing decreased over the study period, 1.4 ppbv yr−1 and 1.6 ppbv yr−1, respectively. However, VOCs reactivity, in terms of OH loss rate, showed an indistinct statistical trend due to unsteady variations from naturally emitted isoprene, though some anthropogenic species showed decreasing trends, such as pentane, benzene and toluene. Meanwhile, daytime average O3 increased rapidly at an annual rate of 2.6 ppbv yr−1, around 5% yr−1 between 2005 and 2011. Considering the influence of NO titration effect and elevated regional ozone background in the North China Plain (NCP), the main reason for such an increase in oxidants was subject to "local" photochemistry. A simplified model was used to evaluate the effect of changes in the levels of ozone precursors on ozone production. We found that between 2001 and 2006, the production rate of total oxidants, P(Ox) increased rapidly due to increased VOC levels and decreasing NO2, while from 2006 to 2011 P(Ox) remained high, though decreased slightly as a consequence of the decrease in both VOC reactivity (−5% yr−1) and NOx (−4% yr−1). Observations have shown that Beijing's efforts to control air pollution were somehow effective in cutting ozone precursors, but still left higher ground-level ozone. We surmised that it resulted from potential contributions from OVOCs and regional transport near Beijing. Therefore, Beijing needs deeper cooperation with adjacent provinces to control ozone pollution together. To impel this kind of joint prevention and control program, ground-level ozone should become a mandatory index for air quality management, and a faster reduction of VOCs, especially reactive VOCs, in urban areas, should coordinate with national NOx emission control programs.

[1]  Chang-Chuan Chan,et al.  Validation of a laboratory-constructed automated gas chromatograph for the measurement of ozone precursors through comparison with a commercial analogy. , 2004, Journal of chromatography. A.

[2]  Yuhui Yang,et al.  Decreasing trend of sunshine hours and related driving forces in North China , 2009 .

[3]  M. Riese,et al.  Tropospheric ozone trend over Beijing from 2002–2010: ozonesonde measurements and modeling analysis , 2012 .

[4]  Binyu Wang,et al.  Air quality during the 2008 Beijing Olympic Games , 2007 .

[5]  David D. Nelson,et al.  Evaluation of nitrogen dioxide chemiluminescence monitors in a polluted urban environment , 2007 .

[6]  Leiming Zhang,et al.  Response to referee , 2010 .

[7]  Tong Zhu,et al.  Use of a mobile laboratory to evaluate changes in on-road air pollutants during the Beijing 2008 Summer Olympics , 2009 .

[8]  Fankun Wu,et al.  Characterization of volatile organic compounds in the urban area of Beijing from 2000 to 2007. , 2012, Journal of environmental sciences.

[9]  M. Shao,et al.  Variation of ambient non-methane hydrocarbons in Beijing city in summer 2008 , 2010 .

[10]  J. Murphy,et al.  Long term changes in nitrogen oxides and volatile organic compounds in Toronto and the challenges facing local ozone control , 2009 .

[11]  S. Liu,et al.  Photochemical production of ozone and control strategy for Southern Taiwan , 2007 .

[12]  Jiming Hao,et al.  Understanding of regional air pollution over China using CMAQ, part II. Process analysis and sensitivity of ozone and particulate matter to precursor emissions , 2010 .

[13]  J. Tao,et al.  The Impact of aerosol hygroscopicity on the single-scattering albedo and the NO2 photolysis rate coefficient in the North China Plain , 2013 .

[14]  Bin Wang,et al.  Source profiles of volatile organic compounds associated with solvent use in Beijing, China , 2010 .

[15]  Ken Yamashita,et al.  Evaluation of Premature Mortality Caused by Exposure to PM2.5 and Ozone in East Asia: 2000, 2005, 2020 , 2012, Water, Air, & Soil Pollution.

[16]  Z. Ouyang,et al.  Ambient air quality trends and driving factor analysis in Beijing, 1983-2007. , 2011, Journal of environmental sciences.

[17]  Min Shao,et al.  Volatile organic compounds measured in summer in Beijing and their role in ground‐level ozone formation , 2009 .

[18]  Michael B. McElroy,et al.  Detection from space of a reduction in anthropogenic emissions of nitrogen oxides during the Chinese economic downturn , 2011 .

[19]  Chein-Jung Shiu,et al.  The trend of surface ozone in Taipei, Taiwan, and its causes: Implications for ozone control strategies , 2006 .

[20]  P. Zhao,et al.  Long-term visibility trends and characteristics in the region of Beijing, Tianjin, and Hebei, China , 2011 .

[21]  J. Mao,et al.  Relationships between submicrometer particulate air pollution and air mass history in Beijing, China, 2004-2006 , 2008 .

[22]  R. Martin,et al.  Growth in NO x emissions from power plants in China: bottom-up estimates and satellite observations , 2012 .

[23]  Yu Zhou,et al.  Trends in vehicular emissions in China's mega cities from 1995 to 2005. , 2010, Environmental pollution.

[24]  Yuhang Wang,et al.  Summertime photochemistry during CAREBeijing-2007: ROx budgets and O3 formation , 2012 .

[25]  D. Blake,et al.  Impact of organic nitrates on urban ozone production , 2010 .

[26]  William J. Collins,et al.  Multimodel estimates of intercontinental source-receptor relationships for ozone pollution , 2008 .

[27]  M. Shao,et al.  Increase of ambient formaldehyde in Beijing and its implication for VOC reactivity , 2012 .

[28]  X. Tie,et al.  Characteristics and source apportionment of VOCs measured in Shanghai, China , 2010 .

[29]  Yuesi Wang,et al.  Surface ozone trend details and interpretations in Beijing, 2001–2006 , 2009 .

[30]  S. Oltmans,et al.  Characterizing changes in surface ozone levels in metropolitan and rural areas in the United States for 1980–2008 and 1994–2008 , 2010 .

[31]  Roger Atkinson,et al.  Atmospheric degradation of volatile organic compounds. , 2003, Chemical reviews.

[32]  Min Shao,et al.  Source profiles of volatile organic compounds (VOCs) measured in China. Part I , 2008 .

[33]  M. Shao,et al.  Measurements of C1–C4 alkyl nitrates and their relationships with carbonyl compounds and O3 in Chinese cities , 2013 .

[34]  Shaodong Xie,et al.  Ozone source attribution during a severe photochemical smog episode in Beijing,China , 2009 .

[35]  Yuhang Wang,et al.  Evidence of reactive aromatics as a major source of peroxy acetyl nitrate over China. , 2010, Environmental science & technology.

[36]  A. Goldstein,et al.  Observations of the temperature dependent response of ozone to NO x reductions in the Sacramento, CA urban plume , 2011 .

[37]  M. Luo,et al.  Seasonal and spatial variability of surface ozone over China: contributions from background and domestic pollution , 2010 .

[38]  H. Akimoto,et al.  Premature mortality in Japan due to ozone , 2013 .

[39]  Chih-Chung Chang,et al.  Estimate of initial isoprene contribution to ozone formation potential in Beijing, China , 2008 .

[40]  Jiming Hao,et al.  Quantifying the air pollutants emission reduction during the 2008 Olympic games in Beijing. , 2010, Environmental science & technology.

[41]  Xingying Zhang,et al.  The trend, seasonal cycle, and sources of tropospheric NO2 over China during 1997–2006 based on satellite measurement , 2007 .

[42]  Yuhang Wang,et al.  East China plains: a "basin" of ozone pollution. , 2009, Environmental science & technology.

[43]  Akimoto Hajime,et al.  Hemispheric transport of air pollution 2010: Part A - Tropospheric ozone and particulate matter , 2011 .

[44]  Simone Meinardi,et al.  Volatile organic compounds in 43 Chinese cities , 2005 .

[45]  Xiaobin Xu,et al.  Long-term trend of surface ozone at a regional background station in eastern China 1991–2006 : enhanced variability , 2008 .

[46]  Jun Yu Li,et al.  Fast increasing of surface ozone concentrations in Pearl River Delta characterized by a regional air quality monitoring network during 2006-2011. , 2014, Journal of environmental sciences.

[47]  Harihara M. Mehendale,et al.  Volatile Organic Compounds , 2014 .

[48]  Xiaobin Xu,et al.  Characteristics of trace gaseous pollutants at a regional background station in Northern China , 2008 .

[49]  S. Liu,et al.  Effects of reactive hydrocarbons on ozone formation in southern Taiwan , 2005 .

[50]  J. Staehelin,et al.  Long-term changes in lower tropospheric baseline ozone concentrations at northern mid-latitudes , 2012 .

[51]  Aijun Ding,et al.  Increasing surface ozone concentrations in the background atmosphere of Southern China, 1994–2007 , 2009 .

[52]  Tong Zhu,et al.  Correction to “Oxidant (O3+NO2) production processes and formation regimes in Beijing” , 2010 .

[53]  S. Madronich Photodissociation in the atmosphere: 1. Actinic flux and the effects of ground reflections and clouds , 1987 .

[54]  K. He,et al.  On-road vehicle emission control in Beijing: past, present, and future. , 2011, Environmental science & technology.

[55]  Trissevgeni Stavrakou,et al.  Trend detection in satellite observations of formaldehyde tropospheric columns , 2010 .

[56]  Chih-Chung Chang,et al.  Volatile Organic Compound (VOC) measurements in the Pearl River Delta (PRD) region, China , 2007 .

[57]  Tong Zhu,et al.  The impact of circulation patterns on regional transport pathways and air quality over Beijing and its surroundings , 2011 .

[58]  Jingchun Duan,et al.  Concentration, sources and ozone formation potential of volatile organic compounds (VOCs) during ozone episode in Beijing , 2008 .

[59]  James F. Meagher,et al.  Nonmethane hydrocarbon and oxy hydrocarbon measurements during the 2002 New England Air Quality Study , 2004 .

[60]  M. Monge,et al.  Photoenhanced NO2 loss on simulated urban grime. , 2010, Chemphyschem : a European journal of chemical physics and physical chemistry.

[61]  Xingying Zhang,et al.  The trend, seasonal cycle, and sources of tropospheric NO 2 over China during 1997―2006 based on satellite measurement , 2007 .

[62]  Tao Wang,et al.  Strong ozone production in urban plumes from Beijing, China , 2006 .

[63]  Xiaobin Xu,et al.  Measurements of ozone and its precursors in Beijing during summertime: impact of urban plumes on ozone pollution in downwind rural areas , 2011 .

[64]  P. Lin,et al.  Photochemical production of ozone in Beijing during the 2008 Olympic Games , 2011 .

[65]  Ming-Ho Yu,et al.  Volatile Organic Compounds , 2016 .

[66]  Tao Wang,et al.  Tropospheric ozone climatology over Beijing: analysis of aircraft data from the MOZAIC program , 2007 .

[67]  Min Shao,et al.  City clusters in China: air and surface water pollution , 2006 .

[68]  D. Blake,et al.  Air quality during the 2008 Beijing Olympics: secondary pollutants and regional impact , 2010 .

[69]  J. Burrows,et al.  Increase in tropospheric nitrogen dioxide over China observed from space , 2005, Nature.

[70]  Min Shao,et al.  Source apportionment of ambient volatile organic compounds in Beijing. , 2007, Environmental science & technology.

[71]  James M. Roberts,et al.  Trends in ozone, its precursors, and related secondary oxidation products in Los Angeles, California: A synthesis of measurements from 1960 to 2010 , 2013 .

[72]  Hajime Akimoto,et al.  HEMISPHERIC TRANSPORT OF AIR POLLUTION 2010 PART A : OZONE AND PARTICULATE MATTER AIR POLLUTION STUDIES No . 17 , 2011 .