Skip to main content
Article thumbnail
Location of Repository

Peroxy radical chemistry and the control of ozone photochemistry at Mace Head, Ireland, during the summer of 2002

By Zoe L. Fleming, Paul S. Monks, Andrew R. Rickard, Dwayne E. Heard, William J. Bloss, Paul W. Seakins, T.J. Still, R. Sommariva, Michael J. Pilling, R. Morgan, T.J. Green, N. Brough, Graham P. Mills, Stuart A. Penkett, Alastair C. Lewis, James D. Lee, A. Saiz-Lopez and J.M.C. Plane


This work is licensed under a Creative Commons License and is also available from, along with further discussion.Peroxy radical (HO2 +ΣRO2) measurements, using the PEroxy Radical Chemical Amplification (PERCA) technique at the North Atlantic Marine Boundary Layer EXperiment (NAMBLEX) at Mace Head in summer 2002, are presented and put into the context of marine, boundary-layer\ud chemistry. A suite of other chemical parameters (NO, NO2, NO3, CO, CH4, O3, VOCs, peroxides), photolysis frequencies and meteorological measurements, are used to\ud present a detailed analysis of the role of peroxy radicals in tropospheric oxidation cycles and ozone formation. Under the range of conditions encountered the peroxy radical\ud daily maxima varied from 10 to 40 pptv. The diurnal cycles showed an asymmetric shape typically shifted to the afternoon.\ud Using a box model based on the master chemical mechanism the average model measurement agreement was 2.5 across the campaign. The addition of halogen oxides to\ud the model increases the level of odel/measurement agreement, apparently by respeciation of HOx. A good correlation\ud exists between j(HCHO).[HCHO] and the peroxy radicals indicative of the importance of HCHO in the remote atmosphere\ud as a HOx source, particularly in the afternoon. The peroxy radicals showed a strong dependence on [NOx] with a break point at 0.1 ppbv, where the radicals increased concomitantly with the reactive VOC loading, this is a lower value than seen at representative urban campaigns. The\ud HO2/(HO2 + ΣRO2) ratios are dependent on [NOx] ranging between 0.2 and 0.6, with the ratio increasing linearly with NOx. Significant night-time levels of peroxy radicals were measured up to 25 pptv. The contribution of ozone-alkenes and NO3-alkene chemistry to night-time peroxy radical production was shown to be on average 59 and 41%. The campaign mean net ozone production rate was 0.11±0.3 ppbv\ud h−1. The ozone production rate was strongly dependent on [NO] having linear sensitivity (dln(P(O3))/dln(NO)=1.0). The results imply that the N(O3) (the in-situ net photochemical rate of ozone production/destruction) will be strongly\ud sensitive in the marine boundary layer to small changes in [NO] which has ramifications for changing NOx loadings in\ud the European continental boundary layer

Publisher: European Geosciences Union
Year: 2006
OAI identifier:

Suggested articles


  1. (2000). A detailed study of isoprene chemistry during the EASE 96 campaign, doi
  2. (2000). A seasonal comparison of ozone photochemistry in the remote marine boundary layer, doi
  3. A simplified apparatus for ambient formaldehyde detection via GC-PHID, doi
  4. (1997). A study of peroxy radicals and ozone photochemistry at coastal sites in the northern and southern hemispheres, doi
  5. A.: A Two Column Method for Long-term Monitoring of Non-Methane Hydrocarbons (NMHCs) and Oxygenated Volatile Organic Compounds, doi
  6. (2003). Airborne measurements of peroxy radicals using the PERCA technique, doi
  7. (2003). Application of a compact all solid-state laser system to the in-situ detection of atmospheric OH, HO2, NO and IO by laser-induced fluorescence, doi
  8. (2002). ATMOS env The regional distribution of ozone across the British Isles and its response to control strategies, doi
  9. (1996). Atmospheric monitoring of volatile organic compounds using programmed temperature vaporisation injection, doi
  10. (2004). Attenuation of spectral actinic flux and photolysis frequencies at the surface through homogeneous cloud fields, doi
  11. (2005). Boundary layer structure and decoupling from synoptic scale flow during NAMBLEX, doi
  12. (2003). Chapter 6, Tropospheric photochemistry, in: “Handbook of Atmospheric science: Principle and Application”, edited by: doi
  13. (2002). Comparison of measured ozone production efficiencies in the marine boundary layer at two European coastal sites under different pollution regimes,
  14. (2006). Concentrations of OH and HO2 radicals during NAMBLEX: Measurement and steady-state analysis, doi
  15. (1999). Direct measurement of atmospheric formaldehyde using gas chromatography-pulsed discharge ionisation detection, doi
  16. (1996). Dual-inlet Chemical amplifier for atmospheric peroxy radical measurements, doi
  17. (1997). Eastern Atlantic Spring Experiment
  18. Evaluation of detailed aromatic mechanisms (MCMv3 and MCMv3.1) against environmental chamber data, doi
  19. (1992). Evidence for photochemical control of ozone concentrations in unpolluted air, doi
  20. (1998). Field measurements of atmospheric photolysis frequencies for doi
  21. (2004). Field studies of atmospheric peroxides and the development of sampling methods,
  22. Fleming et al.: Peroxy radical chemistry at Mace Head, doi
  23. (2006). Fleming et al.: Peroxy radical chemistry at Mace Head, Ireland doi
  24. (1990). Formaldehyde measurements methods evaluation and ambient concentrations during the carbonaceous species comparison study, doi
  25. (2006). Fundamental ozone photochemistry in the remote boundary layer: The SOAPEX experiAtmos.
  26. (2005). Gas-phase radical chemistry in the troposphere, doi
  27. (2003). Hydrogen peroxide, organic peroxides, carbonyl compounds and organic acids measured at Pabstthum during BERLIOZ,
  28. Impact of halogen monoxide chemistry upon boundary layer OH and HO2 concentrations at a coastal site,
  29. (1997). Implementation and initial deployment of a field instrument for measurement of OH and HO2 in the troposphere by laser-induced fluorescence, doi
  30. (2000). Intercomparison of aircraft instruments on board the C-130 and Falcon 20 over Southern Germany during EXPORT doi
  31. (2000). Intercomparison of formaldehyde measurements in clean and polluted atmospheres, doi
  32. (1997). Investigation into the kinetics and mechanism of the reaction of NO3 with CH3O2 at 298 K and 2.5 Torr: A potential source of OH in the nighttime troposphere?, doi
  33. (2003). Investigation of the effect of water complexes in the determination of peroxy radical ambient concentrations: Implications for the atmosphere, doi
  34. (2001). Marine boundary layer peroxy radical chemistry during the AEROSOLS99 campaign: Measurements and analysis, doi
  35. (2003). mbox Sillman, S.: The use of NOy, H2O2 and HNO3 as indicators for ozone-hydrocarbon sensitivity in urban locations,
  36. (2006). Measurements and modelling of doi
  37. (2002). Measurements of gas-phase hydrogen peroxide and methyl hydroperoxide in the coastal environment during the PARFORCE project, doi
  38. (1994). Measurements of NO3, N2O5, OIO, I2, water vapour and aerosol optical depth by broadband cavity ringdown spectroscopy during the NAMBLEX campaign,
  39. (2003). Measurements of OH and HO2 radical concentrations and photolysis frequencies during BERLIOZ, doi
  40. (1999). Modelling OH, HO2 and RO2 radicals in the marine boundary layer 1. Model construction and comparison with field measurements, doi
  41. (1996). Night-time peroxy radical chemistry in the remote marine boundary layer over the Southern ocean, doi
  42. (2006). Night-time radical chemistry during the NAMBLEX campaign, doi
  43. (2003). Nightime formation of peroxy and hydroxy radicals during the BERLIOZ campaign: observations and modelling studies,
  44. (1990). Observation and interpretation of the seasonal cycles in the surface concentrations of ozone and carbon monoxide at Mace Head, Ireland from doi
  45. (1998). Observations of isoprene chemistry and its role in ozone production at a semirural site during the 1995 Southern Oxidants Study, doi
  46. (1999). Observations of the nitrate radical in the marine boundary layer,
  47. (2006). OH and HO2 chemistry during NAMBLEX: roles of oxygenates, halogen oxides and heterogeneous uptake, doi
  48. (1997). OH and HO2 measurements using laser-induced fluorescence, doi
  49. (1990). Ozone and carbon monoxide measurements at a remote maritime location, doi
  50. (1997). Ozone in the Marine Boundary Layer at Cape Grim: Model Simulation,
  51. (2001). Ozone photochemistry and the role of peroxyacetlynitrate in the springtime Pacific troposphere: Results from the Photochemical Ozone Budget of the Eastern North Pacific Atmosphere (PHOBEA) campaign, doi
  52. (1996). Ozone, hydroperoxides, oxides of nitrogen, and hydrocarbon budgets in the marine boundary layer over the South Atlantic, doi
  53. (1996). Peroxy radical concentrations measured and calculated from trace-gas measurements in the Mauna Loa Observatory Photochemistry Experiment 2, doi
  54. (2003). Peroxy radicals during BERLIOZ at Pabstthum: Measurements, radical budgets and ozone production,
  55. (1990). Peroxy radicals from nighttime reaction of NO3 with organic compounds, doi
  56. (1993). Peroxy radicals from photostationary-state deviations and steady-state calculations during the Tropospheric OH Photochemistry Experiment at Idaho Hill, doi
  57. (2003). Photochemical ozone formation in north west Europe and its control, doi
  58. (2002). Photochemical ozone production at a subtropical island of Okinawa, Japan: Implications from simultaneous observations of HO2 radical and NOx, doi
  59. (2006). Plane3 Atmos.
  60. (2001). Production of peroxy radicals at night via reactions of ozone and the nitrate radical in the marine boundary layer, doi
  61. (2003). Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds (Part B): tropospheric degradation of aromatic volatile organic compounds, doi
  62. (2002). Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds, doi
  63. (1987). Significant growth in surface ozone at Mace Head, doi
  64. (1993). Simultaneous measurements of peroxy and nitrate radicals at Schauinsland, doi
  65. (1997). Simultaneous observations of nitrate and peroxy radicals in the marine boundary layer, 1. Model construction and comparison with field measurements, doi
  66. (2005). Sources and sinks of acetaldehyde, acetone and methanol in north Atlantic marine boundary layer air, doi
  67. (1997). Studies of oxidant production at the Weybourne Atmospheric observatory in summer and winter conditions,
  68. (2002). The Eastern Atlantic Spring Experiment (EASE) 1997: (1) OH and HO2 radical measurements at Mace Head, doi
  69. (2006). The measurement of peroxy radicals in the marine boundary layer using the PERCA technique, PhD thesis,
  70. (2000). The nitrate radical in the marine boundary layer, doi
  71. (1991). The nitrate radical: Physics, chemistry and the environment, doi
  72. (2002). The North Atlantic Marine Boundary Layer Experiment (NAMBLEX). Overview of the campaign held at Mace Head, Ireland, in summer doi
  73. (1993). The seasonal variation of non-methane hydrocarbons in the free troposphere over the North Atlantic Ocean: possible evidence for extensive reaction of hydrocarbons with the nitrate radical, doi
  74. (1998). The sensitivity of the amplifier to ambient water vapour, doi
  75. (1997). The tropospheric degradation of volatile organic compounds: A protocol for mechanism development, doi
  76. (2005). this issue, doi
  77. (2003). TROTREP Synthesis and Integration Report, Report to the EU FPV Energy, Environment and Sustainable Development Program,
  78. (2006). Understanding field measurements through a Master Chemical Mechanism, PhD thesis,

To submit an update or takedown request for this paper, please submit an Update/Correction/Removal Request.