Journal of Korean Society for Atmospheric Environment (한국대기환경학회지)

Korean Society for Atmospheric Environment (한국대기환경학회)
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Relative Contribution of the Oxidation of VOCs to the Concentrations of Hydroxyl (OH) and Peroxy Radicals in the Air of Seoul Metropolitan Area

서울에서의 VOCs의 히드록실 및 페록시 라디칼 농도에 대한 상대적 기여도 연구

  • Shon, Zang-Ho (Deportment of Environmental Engineering, Dong-Eui University)
  • Published : 2006.12.31
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Abstract

This study examines relative contributions of volatile organic compounds (VOCs) to the formation of hydroxyl (OH) and peroxy radicals such as $HO_2$ and $RO_2$ during the intensive sampling period (Jun. $1{\sim}30$, 2004) in the air of Seoul metropolitan area. As to the contribution of VOCs to $HO_x$ levels, the impact of individual VOC concentration change on $HO_2$ concentration change was more than an order of magnitude higher than that on OH concentration change during the study period. The contribution of change in isoprene concentration to $HO_2$ concentration change was 38 times higher than OH and that in the concentration of alkene compounds to $HO_2$ concentration change was 31 times higher than OH. Moreover, the concentration changes of isoprene and aromatic compounds (AROM) played significant roles in $HO_x$ concentration changes. On the other hands, aldehydes (ALD2) and alkanes (ALKA) showed anti-correlation (negative) in $HO_x$ concentration changes with low contribution ($-4{\times}10^{-3}$ pptv/ppbv (OH) and $-58{\times}10^{-3}$ ($HO_2$) for ALD2; $-1{\times}10^{-3}$ (OH) and $-15{\times}10^{-3}$ ($HO_2$) for ALKA). Unlike other VOCs, $C_2H_6$ and $C_3H_8$ showed positive or negative contribution to peroxy radicals, depending on ambient air conditions. The contribution of VOC concentration changes to changes in $CH_3O_2$ and $RO_2$ concentration showed similar pattern to $HO_x$ contribution.

Keywords

References

  1. 손장호(2006) 2004년 여름 서울에서 발생한 고농도 오존 사례의 광화학적 분석, 한국대기환경학회지, 22(3), 361-371
  2. 이종범, 황경진 (2005) PAMS 자료와 MODEL-3/CMAQ을 이용한 수도권 지역의 VOCs 배출량 평가, 한국대기환경학회 2005년 춘계학술대회논문집, 194-195
  3. 이종현, 조석연 (2004) 수도권지역에서 VOC 증분반응율 및 오존생성기여도 산출에 관한 연구, 한국대기환경학회 2004년 추계학술대회논문집, 252-253
  4. 한진석, 문광주, 김록호, 신선아, 홍유덕, 정일록 (2006) PMF 를 이용한 수도권지역 VOCs의 배출원 추정, 한국대기환경학회지, 22(1), 85-97
  5. Atkinson, R. and S.M. Aschmann (1993) OH radical production from the gas-phase reaction of $O_3 with a series of alkenes under atmospheric conditions, Environmental Science and Technology, 27, 1357-1363 https://doi.org/10.1021/es00044a010
  6. Barletta, B., S. Meinardi, I.J. Simpson, H.A. Khwaja, D.R. Blake, and F.S. Rowland (2002) Mixing ratios of volatile organic compounds (VOCs) in the atmosphere of Karachi, Pakistan, Atmospheric Environment, 36, 3429-3443 https://doi.org/10.1016/S1352-2310(02)00302-3
  7. Carter, W.P.L. and R. Atkinson (1989) A Computer Modeling Study of Incremental Hydrocarbon Reactivity, Environmental Science and Technology, 23, 864-880 https://doi.org/10.1021/es00065a017
  8. Carter, W.P.L. (1994) Development of ozone reactivity scales for volatile organic compounds, Journal of the Air and Waste Management Association, 44, 881-899
  9. Carter, W.P.L. (1995) Computer Modeling of Environmental Chamber Measurements of Maximum Incremental Reactivities of Volatile Organic Compounds, Atmospheric Environment, 29, 2513-2527 https://doi.org/10.1016/1352-2310(95)00150-W
  10. Derwent, R.G. and M.E. Jenkin (1991) Hydrocarbons and the long-range transport of ozone and PAN across Europe, Atmospheric Environment, 25A, 1661-1678
  11. Derwent, R.G., D.R. Middleton, R.A. Field, M.E. Goldstone, J.N. Lester, and R. Perry (1995) Analysis and interpretation of air quality data from an urban roadside location in Central London over the period from July 1991 to July 1992, Atmospheric Environment, 29, 923-946 https://doi.org/10.1016/1352-2310(94)00219-B
  12. Derwent, R.G., M.E. Jenkin, S.M. Saunders, and M.J. Pilling (1998) Photochemical ozone creation potentials for organic compounds in northwest Europe calculated with a master chemical mechanism, Atmospheric Environment, 32, 2429-2441 https://doi.org/10.1016/S1352-2310(98)00053-3
  13. Durana, N., M. Navazo, M.C. Gomez, L. Alonso, J.A. Garcia, J.L. Ilardia, G. Gangoiti, and J. Iza (2006) Long term hourly measurement of 62 non-methane hydrocarbons in an urban area: Main results and contribution of non-traffic sources, Atmospheric Environment, 40, 2860-2872 https://doi.org/10.1016/j.atmosenv.2006.01.005
  14. Edney, E.O., T.E. Kleindienst, M. Jaoui, M. Lewandowski, J.H. Offenberg, W. Wang, and M. Claeys (2005) Formation of 2-methyl tetrols and 2-methylglyceric acid in secondary organic aerosol from laboratory irradiated $isoprene/NO_X/SO_2/air$ mixtures and their detection in ambient PM2.5 samples collected in the eastern United States, Atmospheric Environment, 39, 5281-5289 https://doi.org/10.1016/j.atmosenv.2005.05.031
  15. Grosjean, E., R.A. Rasmussen, and D. Grosjean (1998) Ambient levels of gas phase pollutants in Porto Alegre, Brazil, Atmospheric Environment, 32, 3371-3379 https://doi.org/10.1016/S1352-2310(98)00007-7
  16. Jenkin M.E. and G.D. Hayman (1999) Photochemical Ozone creation potentials for oxygenated organic compounds: sensitivity to variations in kinetic and mechanistic parameters, Atmospheric Environment, 33, 1275-1293 https://doi.org/10.1016/S1352-2310(98)00261-1
  17. Kesselmeier, J. and M. Staudt (1999) Biogenic volatile organic compounds (VOC): An overview on emission, physiology and ecology, Journal of Atmospheric Chemistry, 33, 23-88 https://doi.org/10.1023/A:1006127516791
  18. Lai, C.H., K.S. Chen, Y.T. Ho, and M.S. Chou (2004) Characteristics of C2-C15 hydrocarbons in the air of urban Kaohsiung, Twain, Atmospheric Environment, 38, 1997-2011 https://doi.org/10.1016/j.atmosenv.2003.11.041
  19. Lee, C., Y.J. Choi, J.S. Jung, J.S. Lee, K.H. Kim, and Y.J. Kim (2005) Measurement of atmospheric monoaromatic hydrocarbons using differential optical absorption spectroscopy: Comparison with on-line gas chromatography measurements in urban air, Atmospheric Environment, 32, 2225-2234
  20. Lurmann, F.W., A.C. Lloyd, and R. Atkinson (1986) A chemical mechanism for use in long-range transport /acid deposition computer modeling, Journal of Geophysical Research, 91, 10905-10936 https://doi.org/10.1029/JD091iD10p10905
  21. Odum, J.R., T. Hoffmann, F. Bowman, D. Collins, R.C. Flagan, and J.H. Seinfeld (1996) Gas/particle partitioning and secondary organic aerosol yields, Environmental Science and Technology, 30, 2580-2585 https://doi.org/10.1021/es950943+
  22. Sander, S.P., D.M. Golden, M.J. Kurylo, G.K. Moortgat, A.R. Ravishankara, C.E. Kolb, M.J. Molina, and B. Finlayson-Pitts (2002) Chemical kinetics and photochemical data for use in atmospheric studies, Jet Prop. Lab. Pub. 02-25, Jet Prop. Lab., Pasadena, California
  23. Seinfeld, J.H. and S.N. Pandis (1998): Atmospheric Chemistry and Physics. From Air Pollution to Climate Change. John Wiley and Sons, New York, 1326pp
  24. Shon, Z.-H., K.-H. Kim, K. Bower, G. Lee, and J. Kim (2004) Assessment of the photochemistry of OH and $NO_3$ on Jeju Island during the Asian Dust-Storm Period in the Spring of 2001, Chemosphere, 55, 1127-1142 https://doi.org/10.1016/j.chemosphere.2003.10.003
  25. Shon, Z.-H., G. Lee, M. Lee, J. Han, S.-K. Song, and D. Lee (2006) Characteristics of reactive nitrogen compounds and other relevant trace gases in the atmosphere at urban and rural areas of Korea during May-June, 2004, Chemosphere, submitted
  26. Sin, D.W.M., Y.-C. Wong, and P.K.K. Louie (2001) Trends of ambient carbonyl compounds in the urban environment of Hong Kong, Atmospheric Environment, 35, 5961-5969 https://doi.org/10.1016/S1352-2310(01)00359-4
  27. Thijsse, R.R., R.F. Van Oss., and P. Lenschow (1999) Determination of source contribution to ambient volatile organic compound concentrations in Berlin, Journal of the Air and Waste Management Association, 49, 1394-1404 https://doi.org/10.1080/10473289.1999.10463974
  28. Wang, L., J.B. Millford, and W.P.L. Carter (2000) Reactivity estimates for aromatic compounds. Part 2. Uncertainty in incremental reactivities, Atmospheric Environment, 34, 4349-4360 https://doi.org/10.1016/S1352-2310(00)00206-5