Abstract
An intensive field campaign including measurements from the environmental monitoring network and from two super sites took place in the Pearl River Delta region in summer 2006. Using routinely measured O3 and NOx concentrations, the spatial and temporal variation of O3 and of the total oxidant concentrations was characterized. According to the spatial variability of NO2/NO, the two super sites were found to be representative of polluted urban and downwind suburban conditions. In addition, both sites were located in high O3 regions. In-depth diagnostic of photochemical ozone production processes and their key controlling factors are achieved with an observation-based model (OBM) to gain regional perspectives. Budget analysis and sensitivity model runs show that aldehyde and HONO chemistry had significant impacts on local photochemical ozone production rates. The analysis of calculated Relative Incremental Reactivities shows that photochemical ozone production rates are mainly sensitive to anthropogenic hydrocarbons (HCs) in the polluted urban areas. In the suburban areas, sensitivity to nitrogen oxide (NO) concentrations dominated. Key anthropogenic HCs in both areas are alkenes and aromatics. Significant differences of ozone production efficiencies are identified between the urban and suburban regions, consistent with the OBM diagnosed results.
Similar content being viewed by others
References
Haagen-Smit AJ. Chemistry and physiology of Log Angeles smog. Ind Eng Chem Res, 1952, 44(6): 1342
Liu SC. Possible effects on tropospheric O3 and OH due to NO emissions. Geophys Res Lett, 1977, 4(8): 325–328
Chameide W, Walker JCG. Photochemical theory of tropospheric ozone. J Geophys Res, 1973, 78(36): 8751–8760
Hidy GM. Ozone process insights from field experiments Part I: Overview. Atmos Environ, 2000, 34(12–14): 2001–2022
Kleinman LI, Daum PH, Lee YN, Nunnermacker LJ, Springston SR, Weinstein-Lloyd J, Rudolph J. A comparative study of ozone production in five U. S. metropolitan areas. J Geophys Res, 2005, 110(D2): 301–321
Kleinman LI, Daum PH, Imre D, Lee YN, Nunnermacker LJ, Springston SR, Weinstein-Lloyd J, Rudolph J. Ozone production rate and hydrocarbon reactivity in 5 urban areas: a cause of high ozone concentration in Houston. Geophys Res Lett, 2002, 29(10): 1051–1054
Kanaya Y, Fukuda M, Akimoto H, Takegawa N, Komazaki Y, Yokouchi Y, Koike M, Kondo Y. Urban photochemistry in central Tokyo: 2. rates and regimes of oxidant (O3 + NO2) production. J Geophys Res, 2008, 113(D06): 321–335
Zhang YH, Shao KS, Tang XY. Photochemical pollution in Chinese cites. Acta Scientiarum Naturalium Universitatis Pekinensis, 1998, 34(2–3): 392–400
Zhang YH, Hu M, Zhong LJ, Wiedensohler A, Liu SC, Andreae MO, Wang W, Fan SJ. Regional integrated experiments on air quality over Pearl River Delta 2004 (PRIDE-PRD2004): overview. Atmos Environ, 2008, 42(25): 6157–6173
Shao M, Tang XY, Zhang YH, Li W. City clusters in China: air and surface water pollution. Front Ecol Environ, 2006, 4: 353–361
Wang XS, Li JL, Zhang YH, Xie SD, Tang XY. Ozone source apportionment in Beijing areas. Sci China Ser B-Chem, 2009, 39(6): 548–599
Wang T, Ding AJ, Gao J, Wu WS. Strong ozone production in urban plumes from Beijing, China. Geophys Res Lett, 2006, 33(21): 806–811
Zhang YH, Su H, Zhong LJ, Cheng YF, Zeng LM, Wang XS, Xiang YR, Wang JL, Gao DF, Shao M, Fan SJ, Liu SC. Regional ozone pollution and observation-based approach for analyzing ozoneprecursor relationship during the PRIDE-PRD2004 campaign. Atmos Environ, 2008, 42(25): 6203–6218
Zhang J, Wang T, Chameides WL, Cardelino C, Kwok J, Blake DR, Ding A, So KL. Ozone production and hydrocarbon reactivity in Hong Kong, Southern China. Atmos Chem and Phys, 2007, 7: 557–573
Xu J, Zhang YH, Wang W. Numerical study on the impacts of heterogeneous reactions on ozone formation in the Beijing urban area. Adv Atmos Sci, 2006, 23(4): 605–614
Wang XS, Li JL. The contribution of anthropogenic hydrocarbons to ozone formation in Beijing areas. China Environ Sci, 2002, 22(6): 501–505
Tang WY, Zhao CS, Gen FH, Peng L, Zhou GQ, Gao W, Xu JM, Tie X. Research of weekend ozone effect in Shanghai areas. Sci China Ser D, 2009, 39(1): 99–105
Hu JL, Zhang YH. Process analysis of ozone formation in the Yangtze River Delta. Res Environ Sci, 2005, 18(2): 13–18
Zhao CS, Peng L, Sun AD, Qin Y, Liu HL, Li WL, Zhou XJ. Numerical modeling of tropospheric ozone over Yangtze Delta region. Acta Scientiae Circumstance, 2004, 24(3): 525–564
Kleinman LI. Ozone process insights from field experiments-part II: Observation-based analysis for ozone production. Atmos Environ, 2000, 34(12–14): 2023–2033
Wang JL, Wang CH, Lai CH, Chang CC, Liu Y, Zhang YH, Liu S, Shao M. Characterization of ozone precursors in the Pearl River Delta by time series observation of non-methane hydrocarbons. Atmos Environ, 2008, 42(25): 6233–6246
Xie X, Shao M, Liu Y, Lu SH, Chang CC, Chen ZM. Estimate of initial isoprene contribution to ozone formation potential in Beijing, China. Atmos Environ, 2008, 42(24): 6000–6010
Kleffmann J, Heland J, Kurtenbach R, Lorzer J, Wiesen P. A new instrument (LOPAP) for the detection of nitrous acid (HONO). Environ Sci Pollut R, 2002, 48–54
Su H, Cheng YF, Shao M, Gao DF, Yu ZY, Zeng LM, Slanina J, Zhang YH, Wiedensohler A. Nitrous acid (HONO) and its daytime sources at a rural site during the 2004 PRIDE-PRD experiment in China. J Geophys Res, 2008, 113(D14): 312–221
Bohn B, Corlett GK, Gillmann M, Sanghavi S, Stange G, Tensing E, Vrekoussis M, Bloss WJ, Clapp LJ, Kortner M, Dorn HP, Monks PS, Platt U, Plass-Dlmer C, Mihalopoulos N, Heard DE, Clemitshaw KC, Meixner FX, Prevot ASH, Schmitt R. Photolysis frequency measurement techniques: results of a comparison within the ACCENT project. Atmos Chem Phys, 2008, 8(17): 5373–5391
Tang XY, Zhang YH, Shao M. Atmospheric Environmental Chemistry. Beijing: Higher education Press, 2006. 232–242
Cardelino CA, Chameides WL. An observation-based model for analyzing ozone precursor relationships in the urban atmosphere. J Air Waste Manage, 1995, 45(3): 161–180
Gery MW, Whitten GZ, Killus JP, Dodge MC. A photochemical kinetics mechanism for urban and regional scale computer modeling. J Geophys Res, 1989, 94(D10): 12925–12956
Lo JCF, Lau AKH, Fung JCH, Chen F. Investigation of enhanced cross-city transport and trapping of air pollutants by coastal and urban land-sea breeze circulations. J Geophys Res, 2006, 111(D14): 104–117
Zhou W, Wang XS, Zhang YH, Su H, Lu KD. Current status of nitrogen oxides related pollution in China and integrated control strategy. Acta Scientiarum Naturalium Universitatis Pekinensis, 2008, 44(2): 323–330
Shiu CJ, Liu SC, Chang CC, Chen JP, Chou CCK, Lin CY, Young CY. Photochemical production of ozone and control strategy for Southern Taiwan. Atmos Environ, 2007, 41(40): 9324–9340
Atkinson R, Baulch DL, Cox RA, Crowley JN, Hampson RF, Hynes RG, Jenkin ME, Rossi MJ, Troe J. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II-gas phase reactions of organic species. Atmos Chem and Phys, 2006, 6: 3625–4055
Shirley TR, Brune WH, Ren X, Mao J, Lesher R, Cardenas B, Volkamer R, Molina LT, Molina MJ, Lamb B, Velasco E, Jobson T, Alexander M. Atmospheric oxidation in the Mexico City Metropolitan Area (MCMA) during April 2003. Atmos Chem and Phys, 2006, 6: 2753–27
Martinez M, Harder H, Kovacs TA, Simpas JB, Bassis J, Lesher R, Brune WH, Frost GJ, Williams EJ, Stroud CA, Jobson BT, Roberts JM, Hall SR, Shetter RE, Wert B, Fried A, Alicke B, Stutz J, Young VL, White AB, Zamora RJ. OH and HO2 concentrations, sources, and loss rates during the Southern Oxidants Study in Nashville, Tennessee, summer 1999. J Geophys Res, 2003, 108(D19): 81–98
Su H, Cheng YF, Cheng P, Zhang YH, Dong SF, Zeng LM, Wang XS, Slanina J, Shao M, Wiedensohler A. Observation of nighttime nitrous acid (HONO) formation at a non-urban site during PRIDE-PRD2004 in China. Atmos Environ, 2008, 42(25): 6219–6232
Kleffmann J, Gavriloaiei T, Hofzumahaus A, Holland F, Koppmann R, Rupp L, Schlosser E, Siese M, Wahner A. Daytime formation of nitrous acid: a major source of OH radicals in a forest. Geophys Res Lett, 2005, 32(5): 818–822
Alicke B, Geyer A, Hofzumahaus A, Holland F, Konrad S, Patz HW, Schafer J, Stutz J, Volz-Thomas A, Platt U. OH formation by HONO photolysis during the BERLIOZ experiment. J Geophys Res, 2003, 108(D4): 31–48
Ren XR, Harder H, Martinez M, Lesher RL, Oliger A, Simpas JB, Brune W H, Schwab J J, Demerjian K L, He Y, Zhou X L, Gao H G. OH and HO2 chemistry in the urban atmosphere of New York City. Atmos Environ, 2003, 37(26): 3639–3651
Kleffmann J. Daytime sources of nitrous acid (HONO) in the atmospheric boundary layer. Chem phys chem, 2007, 8(8): 1137–1144
Lammel G, Cape JN. Nitrous acid and nitrite in the atmosphere. Chem Soc Rev, 1996, 25(5): 361–382
Sarwar G, Roselle SJ, Mathur R, Appel W, Dennis RL, Vogel B. A comparison of CMAQ HONO predictions with observations from the northeast oxidant and particle study. Atmos Environ, 2008, 42(23): 5760–5770
Liu Y, Shao M, Lu SH, Chang CC, Wang JL, Fu LL. Source apportionment of ambient volatile organic compounds in the Pearl River Delta, China: Part II. Atmos Environ, 2008, 42(25): 6261–6274
Carter WPL, Atkinson R. An experimental-study of incremental hydrocarbon reactivity. Environ Sci Technol, 1987, 21(7): 670–679
Liu SC, Trainer M, Fehsenfeld FC, Parrish DD, Williams EJ, Fahey DW, Hubler G, Murphy PC. Ozone production in the rural troposphere and the implications for regional and global ozone distributions. J Geophys Res, 1987, 92(D4): 4191–4207
Trainer M, Parrish DD, Goldan PD, Roberts J, Fehsenfeld FC. Review of observation-based analysis of the regional factors influencing ozone concentrations. Atmos Environ, 2000, 34(12–14): 2045–2061
Sillman S. The use of NOy, H2O2, and HNO3 as indicators for ozone-NOx-hydrocarbon sensitivity in urban locations. J Geophys Res, 1995, 100(D7): 14175–14188
Chou CCK, Tsai CY, Shiu CJ, Liu SC, Zhu T. Measurement of NOy during campaign of air quality research in Beijing 2006 (CAREBeijing-2006): implications for the ozone production efficiency of NOx. J Geophys Res, 2009: 114–126
Cardelino CA, Chameides WL. The application of data from photochemical assessment monitoring stations to the observation-based model. Atmos Environ, 2000, 34(12–14): 2325–2332
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Lu, K., Zhang, Y., Su, H. et al. Regional ozone pollution and key controlling factors of photochemical ozone production in Pearl River Delta during summer time. Sci. China Chem. 53, 651–663 (2010). https://doi.org/10.1007/s11426-010-0055-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11426-010-0055-6