International Journal of Earth & Environmental Sciences Volume 2 (2017), Article ID 2:IJEES-130, 10 pages
Research Article
Global Budget and Distribution of Peroxyacetyl Nitrate (PAN) for Present and Preindustrial Scenarios

M. Anwar H. Khan1, Michael C. Cooke1,a, Steven R. Utembe1,b, Alexander T. Archibald1,c, Richard G. Derwent2, Michael E. Jenkin1,3, Kimberley E. Leather4, Carl J. Percival4 and Dudley E. Shallcross1*

1Atmospheric Chemistry Research Group, School of Chemistry, University of Bristol, Cantock’s Close, Bristol BS8 1TS, UK
2rdscientific, Newbury, Berkshire, UK
3Atmospheric Chemistry Services, Okehampton, Devon, EX20 4QB, UK
4The Centre for Atmospheric Science, The School of Earth, Atmospheric and Environmental Science, The University of Manchester, Brunswick Street, Manchester, M13 9PL, UK
aNow at the Met Office, FitzRoy Road, Exeter, Devon, EX1 3PB, UK
bNow at the School of Earth Sciences, University of Melbourne, Parkville VIC 3010, Australia
cNow at the NCAS- Climate and the Centre for Atmospheric Science, University of Cambridge, Cambridge, UK
Dr. Dudley E. Shallcross, Atmospheric Chemistry Research Group, School of Chemistry, University of Bristol, Cantock’s Close, Bristol BS8 1TS, United Kingdom; E-mail:
14 November 2016; 28 February 2017; 03 March 2017
Khan MAH, Cooke MC, Utembe SR, Archibald AT, Derwent RG, et al. (2017) Global Budget and Distribution of Peroxyacetyl Nitrate (PAN) for Present and Preindustrial Scenarios. Int J Earth Environ Sci 2: 130. doi:


  1. Finlayson-Pitts BJ, Pitts Jr JN (1986) Atmospheric Chemistry: Fundamental and Experimental Techniques. Wiley and Sons, New York.
  2. Seinfeld JH (1986) Atmospheric Chemistry and Physics of Air Pollution. Wiley and Sons, New York.
  3. Stephens ER, Darley EF, Taylor OC, Scott WE (1961) Photochemical reaction products in air pollution. Int J Air Water Pollut 4: 79-100.
  4. Sun EJ, Huang MH (1995) Detection of peroxyacetyl nitrate at phytotoxic levels and its effects on vegetation in Taiwan. Atmos Environ 29: 2899- 2904. View
  5. Altshuller AP (1978) Assessment of the contribution of chemical species to the eye irritation potential of photochemical smog. J Air Pollut Contr Assoc 28: 594-598. View
  6. Wayne RP (2000) Chemistry of the atmospheres. 3rd Edn. Oxford Science publications. Clarendon Press, Oxford, UK, 337 pp.
  7. Crutzen PJ (1979) The role of NO and NO2 in the chemistry of the troposphere and stratosphere. Annu Rev Earth Planet Sci 7: 443-472. View
  8. Singh HB, Hanst PL (1981) Peroxyacetyl nitrate (PAN) in the unpolluted atmosphere: An important reservoir for nitrogen oxides. Geophys Res Lett 8: 941-944. View
  9. Singh HB (1987) Reactive nitrogen in the troposphere: Chemistry and transport of PAN. Environ Sci Technol 21: 320-327. View
  10. Ridley BA, Shetter JD, Walega JG, Madronich S, Elsworth CM, et al. (1990) The behavior of some organic nitrates at Boulder and Niwot Ridge, Colorado. J Geophys Res 95: 13949-13961. View
  11. Roberts JM, Tanner RL, Newman L, Bowersox VC, Bottenheim JW, et al. (1995) Relationships between PAN and ozone at sites in eastern North America. J Geophys Res 100: 22821-22830. View
  12. Moxim WJ, Levy II H, Kasibhatla PS (1996) Simulated global tropospheric PAN: its transport and impact on NOx. J Geophys Res 101: 12621-12638. View
  13. Suppan P, Fabian P, Vyras L, Gryning SE (1998) The behaviour of ozone and peroxyacetyl nitrate concentrations for different wind regimes during the MEDCAPHOT-TRACE campaign in the greater area of Athens, Greece. Atmos Environ 32: 2089-2102. View
  14. Hudman RC, Jacob DJ, Cooper OR, Evans MJ, Heald CL, et al. (2004) Ozone production in transpacific Asian pollution plumes and implications for ozone air quality in California. J Geophys Res 109: D23S10. View
  15. Fischer EV, Jaffe DA, Reidmiller DR, Jaeglé L (2010) Meteorological controls on observed peroxyacetyl nitrate at Mount Bachelor during the spring of 2008. J Geophys Res 115: D03302. View
  16. Roberts JM, Bertman SB (1992) The thermal decomposition of peroxyacetic nitric anhydride (PAN) and peroxymethacrylic nitric anhydride (MPAN). Int J Chem Kin 24: 297-307. View
  17. Bridier I, Caralp F, Loirat H, Lesclaux R, Veyret B, et al. (1991) Kinetic and theoretical studies of the reactions of acetylperoxy+nitrogen dioxide + M acetyl peroxynitrate + M between 248 and 393 K and between 30 and 760 torr. J Phys Chem 95: 3594-3600. View
  18. Orlando JJ, Tyndall GS, Calvert JG (1992) Thermal decomposition pathways for peroxyacetyl nitrate (PAN): Implications for atmospheric methyl nitrate levels. Atmos Environ 26: 3111-3118. View
  19. Cox RA, Roffey MJ (1977) Thermal decomposition of peroxyacetyl nitrate in the presence of nitric oxide. Environ Sci Technol 11: 900-906. View
  20. Talukdar RK, Burkholder JB, Schmoltner AM, Roberts JM, Wilson RR, et al. (1995) Investigation of the loss processes for peroxyacetyl nitrate in the atmosphere: UV photolysis and reaction with OH. J Geophys Res Atmos 100: 14163-14173. View
  21. Tsalkani N, Mellouki A, POulet G, Toupance G, LeBras G (1988) Rate constant measurements for the reactions of OH and Cl with peroxyacetyl nitrate at 298 K. J Atmos Chem 7: 409-419. View
  22. Kames J, Schweighoefer S, Schurath U (1991) Henry’s law constant and hydrolysis of peroxyacetyl nitrate (PAN). J Atmos Chem 12: 169-180. View
  23. Kames J, Schurath U (1995) Henry’s law and hydrolysis rate constants for peroxyacyl nitrates (PANs) using a homogeneous gas-phase source. J Atmos Chem 21: 151-164. View
  24. Peake E, Maclean MA, Lester PF, Sandhu HS (1988) Peroxyacetylnitrate (PAN) in the atmosphere of Edmonton, Alberta, Canada. Atmos Environ 22: 973-981. View
  25. Gallagher MS, Carsey TP, Farmer ML (1990) Peroxyacetyl nitrate in the North Atlantic marine boundary layer. Global Biogeochem Cycles 4: 297- 308. View
  26. Muller KP, Rudolph J (1992) Measurements of peroxyacetylnitrate in the marine boundary layer over the Atlantic. J Atmos Chem 15: 361-367. View
  27. Singh HB, Condon E, Vedder J, O’Hara D, Ridley BA, et al. (1990) Peroxyacetyl nitrate measurements during CITE 2: Atmospheric distribution and precursor relationships. J Geophys Res 95: 10163-10178. View
  28. Singh HB, O’Hara D, Herlth D, Bradshaw JD, Sandholm ST, et al. (1992) Atmospheric measurements of peroxyacetyl nitrate and other organic nitrate at high latitudes: Possible sources and sinks. J Geophys Res 97: 16511-16522. View
  29. Walega JG, Ridley BA, Madronich S, Grahek FE, Shetter JD, et al. (1992) Observations of peroxyacetyl nitrate, peroxypropionyl nitrate, methyl nitrate and ozone during the Mauna Loa Observatory Photochemistry Experiment. J Geophys Res 97: 10311-10330. View
  30. Kourtidis KA, Fabian P, Zeefos C, Rappenglück B (1993) Peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN) and PAN/ozone ratio measurements at three sites in Germany. Tellus 45B: 442-457. View
  31. Rappenglück B, Kourtidis K, Fabian P (1993) Measurements of ozone and peroxyacetyl nitrate (PAN) in Munich. Atmos Environ 27: 293-305. View
  32. Gaffney JS, Marley NA, Prestbo EW (1993) Measurements of peroxyacetyl nitrate (PAN) at a remote site in the southwestern United States: Tropospheric implications. Environ Sci Technol 27: 1905-1910. View
  33. Gaffney JS, Marley NA, Cunningham MM, Doskey PV (1999) Measurements of peroxyacyl nitrates (PANs) in Mexico City: implications for megacity air quality impacts on regional scales. Atmos Environ 33: 5003-5012. View
  34. Hartsell BE, Aneja VP, Lonneman WA (1994) Relationships between peroxyacetyl nitrate, O3, and NOy at the rural Southern Oxidants study site in central Piedmont, North Carolina, site SONIA. J Geophys Res 99: 21033-21041. View
  35. Jacobi H-W, Schrems O (1999) Perosyacetyl nitrate (PAN) distribution over the South Atlantic Ocean. Phys Chem Chem Phys 1: 5517-5521. View
  36. Beine HJ, Krognes T (2000) The seasonal cycle of peroxyacetyl nitrate (PAN) in the European Arctic. Atmos Environ 34: 933-940. View
  37. Jacobi HW, Weller R, Jones AE, Anderson PS, Schrems O (2000) Peroxyacetyl nitrate (PAN) concentrations in the Arctic troposphere measured during the photochemical experiment at Neumayer (PEAN’99). Atmos Environ 34: 5235-5247. View
  38. Grosjean E, Grosjean D, Woodhouse LF (2001) Peroxyacetyl nitrate and peroxypropionyl nitrate during SCOS 97-NARSTO. Environ Sci Technol 35: 4007-4014. View
  39. Grosjean E, Grosjean D, Woodhouse LF, Yang YJ (2002) Peroxyacetyl nitrate and peroxypropionyl nitrate in Porto Alegre, Brazil. Atmos Environ 36: 2405-2419. View
  40. Ford KM, Campbell BM, Shepson PB, Bertman SB, Honrath RE, et al. (2002) Studies of Peroxyacetyl nitrate (PAN) and its interaction with the snowpack at Summit, Greenland. J Geophys Res Atm 107: 4102. View
  41. Roberts JM, Flocke F, Chen G, de Gouw J, Holloway JS, et al. (2004) Measurement of peroxycarboxylic nitric anhydrides (PANs) during the ITCT 2K2 aircraft intensive experiment. J Geophys Res 109: D23S21. View
  42. Roberts JM, Marchewka M, Bertman SB, Sommariva R, Warneke C, et al. (2007) Measurements of PANs during the New England Air Quality Study 2002. J Geophys Res 112: D20306. View
  43. Coheur PF, Herbin H, Clerbaux C, Hurtmans D, Wespes C, et al. (2007) ACE-FTS observation of a young biomass burning plume: first reported measurements of C2H4, C3H6O, H2CO and PAN by infrared occultation from space. Atmos Chem Phys 7: 5437-5446. View
  44. Glatthor N, von Clarmann T, Fischer H, Funke B, Grabowski U, et al. (2007) Global peroxyacetyl nitrate (PAN) retrieval in the upper troposphere from limb emission spectra of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS). Atmos Chem Phys 7: 2775-2787. View
  45. Marley NA, Gaffney JS, Ramos-Villegas R, González BC (2007) Comparison of measurements of peroxyacyl nitrates and primary carbonaceous aerosol concentrations in Mexico City determined in 1997 and 2003. Atmos Chem Phys 7: 2277-2285. View
  46. Lee G, Jang Y, Lee H, Han JS, Kim KR, Lee M (2008) Characteristic behaviour of peroxyacetyl nitrate (PAN) in Seoul megacity, Korea. Chemosphere 73: 619-628. View
  47. Zhang JM, Wang T, Ding AJ, Zhou XH, Xue LK, et al. (2009) Continuous measurement of peroxyacetyl nitrate (PAN) in suburban and remote areas of western China. Atmos Environ 43: 228-237. View
  48. Liu Z, Wang Y, Gu D, Zhao C, Huey LG, et al. (2010) Evidence of reactive aromatics as a major source of peroxy acetyl nitrate over China. Environ Sci Technol 44: 7017-7022. View
  49. Moore DP, Remedios JJ (2010) Seasonality of Peroxyacetyl nitrate (PAN) in the upper troposphere and lower stratosphere using the MIPAS-E instrument. Atmos Chem Phys 10: 6117-6128. View
  50. Lee JB, Yoon JS, Jung K, Eom SW, Chae YZ, et al. (2013) Peroxyacetyl nitrate (PAN) in the urban atmosphere. Chemosphere 93: 1796-1803. View
  51. Phillips GJ, Pouvesle N, Thieser J, Schuster G, Axinte R, et al. (2013) Peroxyacetyl nitrate (PAN) and peroxyacetic acid (PAA) measurements by iodide chemical ionisation mass spectrometry: first analysis of results in the boreal forest and implications for the measurement of PAN fluxes. Atmos Chem Phys 13: 1129-1139. View
  52. Tereszchuk KA, Moore DP, Harrison JJ, Boone CD, Park M, et al. (2013) Observations of peroxyacetyl nitrate (PAN) in the upper troposphere by the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS). Atmos Chem Phys 13: 5601-5613. View
  53. Zhang G, Mu Y, Liu J, Zhang C, Zhang Y, et al. (2014) Seasonal and diurnal variations of atmospheric peroxyacetyl nitrate, peroxypropionyl nitrate, and carbon tetrachloride in Beijing. J Environ Sci(china) 26: 65-74. View
  54. Emmons LK, Hauglustaine DA, Müller JF, Carroll MA, Brasseur GP, et al. (2000) Data composites of airborne observations of tropospheric ozone and its precursors. J Geophys Res 105: 20497-20538. View
  55. Horowitz LW, Walters S, Mauzerall DL, Emmons LK, Rasch PJ, et al. (2003) A global simulation of tropospheric ozone and related tracers: Description and evaluation of MOZART, version 2. J Geophys Res 108: 4784. View
  56. Fischer EV, Jacob DJ, Yantosca RM, Sulprizio MP, Millet DB, et al. (2014) Atmospheric peroxyacetyl nitrate (PAN): a global budget and source attribution. Atmos Chem Phys 14: 2679-2698. View
  57. Peeters J, Nguyen TL, Vereecken L (2009) HOx radical regeneration in the oxidation of isoprene. Phys Chem Chem Phys 11: 5935-5939. View
  58. Hasson AS, Tyndall GS, Orlando JJ, Singh S, Hernandez SQ, et al. (2012) Branching ratios for the reaction of selected carbonyl-containing peroxy radicals with hydroperoxy radicals. J Phys Chem A 116: 6264-6281. View
  59. Collins WJ, Stevenson DS, Johnson CE, Derwent RG (1997) Tropospheric ozone in a Global-Scale Three-Dimensional Lagrangian Model and its response to NOx emission controls. J Atmos Chem 26: 223-274. View
  60. Utembe SR, Cooke MC, Archibald AT, Jenkin ME, Derwent RG, Shallcross DE (2010) Using a reduced Common Representative Intermediates (CRI v2-R5) mechanism to simulate tropospheric ozone in a 3-D Lagrangian chemistry transport model. Atmos Environ 13: 1609-1622.
  61. Derwent RG, Stevenson DS, Doherty RM, Collins WJ, Sanderson MG (2008) How is surface ozone in Europe linked to Asian and North American NOx emissions? Atmos Environ 42: 7412-7422. View
  62. Cooke MC (2010) Global modelling of atmospheric trace gases using the CRI mechanism. PhD Thesis, University of Bristol, UK.
  63. Watson LA (2007) Development and application of chemical mechanisms in atmospheric modelling. PhD thesis, University of Bristol, UK.
  64. Watson LA, Shallcross DE, Utembe SR, Jenkin ME (2008) A Common Representative Intermediate (CRI) mechanism for VOC degradation. Part 2: gas phase mechanism reduction. Atmos Environ 42: 7196-7204.
  65. Jenkin ME, Watson LA, Utembe SR, Shallcross DE (2008) A Common Representative Intermediate (CRI) mechanism for VOC degradation. Part- 1: gas phase mechanism development. Atmos Environ 42: 7185-7195.
  66. Utembe SR, Watson LA, Shallcross DE, Jenkin ME (2009) A Common Representative Intermediates (CRI) mechanism for VOC degradation. Part 3: Development of a secondary organic aerosol module. Atmos Environ 43: 1982-1990. View
  67. Granier C, Lamarque JF, Mieville A, Muller JF, Olivier J, et al. (2005) POET, a database of surface emissions of ozone precursors. View
  68. Khan MAH, Cooke MC, Utembe SR, Xiao P, Derwent RG, et al. (2014) Reassessing the photochemical production of methanol from peroxy radical self and cross reactions using the STOCHEM-CRI global chemistry and transport model. Atmos Environ 99: 77-84. View
  69. Archibald AT, Cooke MC, Utembe SR, Shallcross DE, Derwent RG, et al. (2010) Impacts of mechanistic changes on HOx formation and recycling in the oxidation of isoprene. Atmos Chem Phys 10: 8097-8118. View
  70. Peeters J, Müller J-F, Stavrakou T, Nguyen VS (2014) Hydroxyl radical recycling in isoprene oxidation driven by hydrogen bonding and hydrogen tunneling: The upgraded LIM1 mechanism. J Phys Chem A 118: 8625- 8643. View
  71. Khan MAH, Cooke MC, Utembe SR, Archibald AT, Derwent RG, et al. (2015) Global modelling of the nitrate radical (NO3) for present and preindustrial scenarios. Atmos Res 164-165: 347-357. View
  72. Lelieveld J, Butler TM, Crowley JN, Dillon TJ, Fischer H, et al. (2008) Atmospheric oxidation capacity sustained by a tropical forest. Nature 452: 737-740. View
  73. Pugh TAM, MacKenzie AR, Hewitt CN, Langford B, Edwards PM, et al. (2010) Simulating atmospheric composition over a south-east Asian tropical rainforest: performance of a chemistry box model. Atmos Chem Phys 10: 279-298. View
  74. Canosa-Mas CE, King MD, Lopez R, Percival CJ, Wayne RP, et al. (1996) Is the reaction between CH3C(O)O2 and NO3 important in the night-time troposphere? J Chem Soc Faraday Trans 92: 2211-2222. View
  75. von Kuhlmann R, Lawrence MG, Crutzen PJ (2003) A model for studies of tropospheric ozone and nonmethane hydrocarbons: Model evaluation of ozone-related species. J Geophys Res 108: 4729. View
  76. Khan MAH, Cooke MC, Utembe SR, Xiao P, Morris WC, et al. (2015) The global budgets of organic hydroperoxides for present and pre-industrial scenarios. Atmos Environ 110: 65-74. View
  77. Brice KA, Bottenheim JW, Anlauf KG, Wiebe HA (1988) Long-term measurements of atmospheric peroxyacetylnitrate (PAN) at rural sites in Ontario and Nova Scotia; seasonal variations and long-range transport. Tellus B 40: 408-425. View
  78. Penkett SA, Brice KA (1986) The spring maximum in photooxidants in the Northern Hemisphere troposphere. Nature 319: 655-657. View
  79. Iversen T (1993) Meteorology and transport of air masses in Arctic regions. In: Niki H, Becker KH (Eds.). The tropospheric chemistry of ozone in the polar regions NATO ASI series 17. Springer Berlin, pp. 57-75. View