VOC emissions, evolutions and contributions to SOA formation at a receptor site in eastern China

Abstract. Volatile organic compounds (VOCs) were measured by two online instruments (GC-FID/MS and PTR-MS) at a receptor site on Changdao Island (37.99° N, 120.70° E) in eastern China. Reaction with OH radical dominated chemical losses of most VOC species during the Changdao campaign. A photochemical-age-based parameterization method is used to calculate VOC emission ratios and to quantify the evolution of ambient VOCs. The calculated emission ratios of most hydrocarbons agree well with those obtained from emission inventory data, but determined emission ratios of oxygenated VOCs (OVOCs) are significantly higher than those from emission inventory data. The photochemical-age-based parameterization method is also used to investigate primary emissions and secondary formation of organic aerosol. The primary emission ratio of organic aerosol (OA) to CO is determined to be 14.9 μg m−3 ppm−1, and secondary organic aeorosols (SOA) are produced at an enhancement ratio of 18.8 μg m−3 ppm−1 to CO after 50 h of photochemical processing in the atmosphere. SOA formation is significantly higher than the level determined from VOC oxidation under both high-NOx (2.0 μg m−3 ppm−1 CO) and low-NOx conditions (6.5 μg m−3 ppm−1 CO). Polycyclic aromatic hydrocarbons (PAHs) and higher alkanes (> C10) account for as high as 17.4% of SOA formation, which suggests semi-volatile organic compounds (SVOCs) may be a large contributor to SOA formation during the Changdao campaign. The SOA formation potential of primary VOC emissions determined from field campaigns in Beijing and Pearl River Delta (PRD) is lower than the measured SOA levels reported in the two regions, indicating SOA formation is also beyond explainable by VOC oxidation in the two city clusters.

[1]  Junji Cao,et al.  Regional modeling of organic aerosols over China in summertime , 2008 .

[2]  Yu Song,et al.  Volatile organic compounds (VOCs) in urban air: How chemistry affects the interpretation of positive matrix factorization (PMF) analysis , 2012 .

[3]  D. Koch Transport and direct radiative forcing of carbonaceous and sulfate aerosols in the GISS GCM , 2001 .

[4]  J. Jimenez,et al.  Insights on organic aerosol aging and the influence of coal combustion at a regional receptor site of central eastern China , 2013 .

[5]  Barry J. Huebert,et al.  A large organic aerosol source in the free troposphere missing from current models , 2005 .

[6]  Andrew J. Kean,et al.  Carbonyl and nitrogen dioxide emissions from gasoline- and diesel-powered motor vehicles. , 2008, Environmental science & technology.

[7]  Y. H. Zhang,et al.  The characteristics and origins of carbonaceous aerosol at a rural site of PRD in summer of 2006 , 2012 .

[8]  G R Cass,et al.  Measurement of emissions from air pollution sources. 3. C1-C29 organic compounds from fireplace combustion of wood. , 2001, Environmental science & technology.

[9]  S. Tao,et al.  Emission of Polycyclic Aromatic Hydrocarbons from Indoor Straw Burning and Emission Inventory Updating in China , 2008, Annals of the New York Academy of Sciences.

[10]  J. A. de Gouw,et al.  Determination of urban volatile organic compound emission ratios and comparison with an emissions database , 2007 .

[11]  H. Akimoto,et al.  Measurements of volatile organic compounds in the middle of Central East China during Mount Tai Experiment 2006 (MTX2006): observation of regional background and impact of biomass burning , 2009 .

[12]  A. Robinson,et al.  Secondary organic aerosol formation from high-NO(x) photo-oxidation of low volatility precursors: n-alkanes. , 2010, Environmental science & technology.

[13]  J. Hamilton,et al.  Secondary organic aerosol from biogenic VOCs over West Africa during AMMA , 2008 .

[14]  R. Griffin,et al.  Secondary organic aerosol from photooxidation of polycyclic aromatic hydrocarbons. , 2010, Environmental science & technology.

[15]  Y. H. Zhang,et al.  Highly time-resolved chemical characterization of atmospheric submicron particles during 2008 Beijing Olympic Games using an Aerodyne High-Resolution Aerosol Mass Spectrometer , 2010 .

[16]  S. K. Akagi,et al.  Emission factors for open and domestic biomass burning for use in atmospheric models , 2010 .

[17]  Franz Rohrer,et al.  Dependence of the OH concentration on solar UV , 2000 .

[18]  John H. Seinfeld,et al.  Global modeling of secondary organic aerosol formation from aromatic hydrocarbons: high- vs. low-yield pathways , 2007 .

[19]  Wang Bin,et al.  Effects of Beijing Olympics control measures on reducing reactive hydrocarbon species. , 2011, Environmental science & technology.

[20]  Scott C. Herndon,et al.  Measurements of volatile organic compounds at a suburban ground site (T1) in Mexico City during the MILAGRO 2006 campaign: measurement comparison, emission ratios, and source attribution , 2010 .

[21]  Pierre Tulet,et al.  Evaluation of recently-proposed secondary organic aerosol models for a case study in Mexico City , 2009 .

[22]  James M. Roberts,et al.  Validation of proton transfer reaction-mass spectrometry (PTR-MS) measurements of gas-phase organic compounds in the atmosphere during the New England Air Quality Study (NEAQS) in 2002 , 2003 .

[23]  S. Madronich,et al.  Chemical evolution of volatile organic compounds in the outflow of the Mexico City Metropolitan area , 2009, Atmospheric Chemistry and Physics.

[24]  Wei Li,et al.  Emissions of PAHs from indoor crop residue burning in a typical rural stove: emission factors, size distributions, and gas-particle partitioning. , 2011, Environmental science & technology.

[25]  Y. H. Zhang,et al.  Characterization of submicron aerosols at a rural site in Pearl River Delta of China using an Aerodyne High-Resolution Aerosol Mass Spectrometer , 2010 .

[26]  R. Derwent,et al.  Atmospheric Chemistry and Physics Protocol for the Development of the Master Chemical Mechanism, Mcm V3 (part B): Tropospheric Degradation of Aromatic Volatile Organic Compounds , 2022 .

[27]  Qiang Liu,et al.  Regional modeling of secondary organic aerosol over China using WRF/Chem , 2012 .

[28]  Zifa Wang,et al.  Influence of Beijing outflow on Volatile Organic Compounds (VOC) observed at a mountain site in North China Plain , 2012 .

[29]  M. Brauer,et al.  Global Estimates of Ambient Fine Particulate Matter Concentrations from Satellite-Based Aerosol Optical Depth: Development and Application , 2010, Environmental health perspectives.

[30]  K. Boersma,et al.  Trends, seasonal variability and dominant NOx source derived from a ten year record of NO2 measured from space , 2008 .

[31]  S. Tao,et al.  Emission factors and particulate matter size distribution of polycyclic aromatic hydrocarbons from residential coal combustions in rural Northern China. , 2010, Atmospheric environment.

[32]  A. Goldstein,et al.  Known and Unexplored Organic Constituents in the Earth's Atmosphere , 2007 .

[33]  A. Goldstein,et al.  In situ measurements of gas/particle-phase transitions for atmospheric semivolatile organic compounds , 2010, Proceedings of the National Academy of Sciences.

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

[35]  S. Tao,et al.  Emission of polycyclic aromatic hydrocarbons in China. , 2006, Environmental science & technology.

[36]  Michael J. Kleeman,et al.  MEASUREMENT OF EMISSIONS FROM AIR POLLUTION SOURCES. 2. C1 THROUGH C30 ORGANIC COMPOUNDS FROM MEDIUM DUTY DIESEL TRUCKS , 1999 .

[37]  James M. Roberts,et al.  Budget of organic carbon in a polluted atmosphere: Results from the New England Air Quality Study in 2002 , 2005 .

[38]  G. Carmichael,et al.  Asian emissions in 2006 for the NASA INTEX-B mission , 2009 .

[39]  D. Salcedo,et al.  A missing sink for gas‐phase glyoxal in Mexico City: Formation of secondary organic aerosol , 2007 .

[40]  R. Draxler HYSPLIT (HYbrid Single-Particle Lagrangian Integrated Trajectory) Model access via NOAA ARL READY Website , 2010 .

[41]  D. Blake,et al.  Emission and chemistry of organic carbon in the gas and aerosol phase at a sub-urban site near Mexico City in March 2006 during the MILAGRO study , 2008 .

[42]  John H. Seinfeld,et al.  Secondary organic aerosol formation from m-xylene, toluene, and benzene , 2007 .

[43]  D. Blake,et al.  The glyoxal budget and its contribution to organic aerosol for Los Angeles, California, during CalNex 2010 , 2011 .

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

[45]  C. N. Hewitt,et al.  Fluxes and concentrations of volatile organic compounds above central London, UK , 2009 .

[46]  Dirk Richter,et al.  Organic aerosol formation in urban and industrial plumes near Houston and Dallas, Texas , 2009 .

[47]  J. Schauer,et al.  Seasonal trends in PM2.5 source contributions in Beijing, China , 2005 .

[48]  D. Blake,et al.  Evolution of submicron organic aerosol in polluted air exported from Tokyo , 2006 .

[49]  S. M. Aschmann,et al.  Kinetics of the gas‐phase reactions of OH radicals with a series of α,β‐unsaturated carbonyls at 299 ± 2 K , 1983 .

[50]  A. Goldstein,et al.  Biogenic carbon and anthropogenic pollutants combine to form a cooling haze over the southeastern United States , 2009, Proceedings of the National Academy of Sciences.

[51]  A. R. Ravishankara,et al.  Organic Aerosol Formation Downwind from the Deepwater Horizon Oil Spill , 2011, Science.

[52]  Dui Wu,et al.  Characteristics and diurnal variations of NMHCs at urban, suburban, and rural sites in the Pearl River Delta and a remote site in South China , 2007 .

[53]  J. D. de Gouw,et al.  Organic aerosols in the Earth's atmosphere. , 2009, Environmental science & technology.

[54]  Y. Yokouchi,et al.  Secondary organic aerosol formation in urban air: Temporal variations and possible contributions from unidentified hydrocarbons , 2009 .

[55]  N. Takegawa,et al.  Emissions of black carbon in East Asia estimated from observations at a remote site in the East China Sea , 2011 .

[56]  Yong Bin Lim,et al.  Products and mechanism of secondary organic aerosol formation from reactions of n-alkanes with OH radicals in the presence of NOx. , 2005, Environmental science & technology.

[57]  W. B. Knighton,et al.  Measurements of Volatile Organic Compounds Using Proton Transfer Reaction - Mass Spectrometry during the MILAGRO 2006 Campaign , 2008 .

[58]  Min Shao,et al.  Comparison of air pollutant emissions among mega-cities , 2009 .

[59]  John P. Burrows,et al.  Global budgets of atmospheric glyoxal and methylglyoxal, and implications for formation of secondary organic aerosols , 2007 .

[60]  Allen L Robinson,et al.  Rethinking Organic Aerosols: Semivolatile Emissions and Photochemical Aging , 2007, Science.

[61]  E. Monedero,et al.  Night-time atmospheric fate of acrolein and crotonaldehyde. , 2008, Environmental science & technology.

[62]  P. Ziemann,et al.  Effects of molecular structure on aerosol yields from OH radical-initiated reactions of linear, branched, and cyclic alkanes in the presence of NOx. , 2009, Environmental science & technology.

[63]  J. A. de Gouw,et al.  summer: 1. Direct emissions and secondary formation of organic matter in urban plumes , 2008 .

[64]  C. N. Hewitt,et al.  Mixing ratios and eddy covariance flux measurements of volatile organic compounds from an urban canopy (Manchester, UK) , 2008 .

[65]  P. Wiesen,et al.  The contribution of traffic and solvent use to the total NMVOC emission in a German city derived from measurements and CMB modelling , 2007 .

[66]  A. R. Ravishankara,et al.  Comparison of daytime and nighttime oxidation of biogenic and anthropogenic VOCs along the New England coast in summer during New England Air Quality Study 2002 , 2004 .

[67]  Xiaoye Zhang,et al.  Carbonaceous aerosol composition over various regions of China during 2006 , 2008 .

[68]  J. A. de Gouw,et al.  Effects of mixing on evolution of hydrocarbon ratios in the troposphere , 2005 .

[69]  D. Blake,et al.  Seasonal variations of atmospheric C2–C7 nonmethane hydrocarbons in Tokyo , 2007 .

[70]  B. Sive,et al.  Calibration and intercomparison of acetic acid measurements using proton-transfer-reaction mass spectrometry (PTR-MS) , 2012 .

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

[72]  Dingli Yue,et al.  Measurements of gaseous H 2 SO 4 by AP-ID-CIMS during CAREBeijing 2008 Campaign , 2011 .

[73]  John H. Seinfeld,et al.  Secondary organic aerosol formation from photooxidation of naphthalene and alkylnaphthalenes: implications for oxidation of intermediate volatility organic compounds (IVOCs) , 2009 .

[74]  M. Molina,et al.  Secondary organic aerosol formation from anthropogenic air pollution: Rapid and higher than expected , 2006 .

[75]  Rainer Volkamer,et al.  Secondary Organic Aerosol Formation from Acetylene (C 2 H 2 ): seed effect on SOA yields due to organic photochemistry in the aerosol aqueous phase , 2008 .

[76]  B. Lamb,et al.  Flux measurements of volatile organic compounds from an urban landscape , 2005 .

[77]  J. Seinfeld,et al.  Gas/Particle Partitioning and Secondary Organic Aerosol Yields , 1996 .

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

[79]  Renjian Zhang,et al.  Carbonaceous aerosols in China: top-down constraints on primary sources and estimation of secondary contribution , 2012 .

[80]  A. Goldstein,et al.  Volatile Organic Compound Measurements at Trinidad Head, California, during Itct 2k2: Analysis of Sources, Atmospheric Composition, and Aerosol Residence Times , 2004 .