Journal of Atmospheric Chemistry

, Volume 68, Issue 4, pp 331–362 | Cite as

Modelled and measured concentrations of peroxy radicals and nitrate radical in the U.S. Gulf Coast region during TexAQS 2006

  • Roberto Sommariva
  • Tim S. Bates
  • Daniel Bon
  • Daniel M. Brookes
  • Joost A. de Gouw
  • Jessica B. Gilman
  • Scott C. Herndon
  • William C. Kuster
  • Brian M. Lerner
  • Paul S. Monks
  • Hans D. Osthoff
  • Alex E. Parker
  • James M. Roberts
  • Sara C. Tucker
  • Carsten Warneke
  • Eric J. Williams
  • Mark S. Zahniser
  • Steven S. Brown
Article
First Online:
Received:
Accepted:

Abstract

Measurements of total peroxy radicals (HO2 + RO2) and nitrate radical (NO3) were made on the NOAA research vessel R/V Brown along the U.S. Gulf Coast during the TexAQS 2006 field campaign. The measurements were modelled using a constrained box-model based upon the Master Chemical Mechanism (MCM). The agreement between modelled and measured HO2 + RO2 was typically within ∼40% and, in the unpolluted regions, within 30%. The analysis of the model results suggests that the MCM might underestimate the concentrations of some acyl peroxy radicals and other small peroxy radicals. The model underestimated the measurements of NO3 by 60–70%, possibly because of rapid heterogeneous uptake of N2O5. The MCM model results were used to estimate the composition of the peroxy radical pool and to quantify the role of DMS, isoprene and alkenes in the formation of RO2 in the different regions. The measurements of HO2 + RO2 and NO3 were also used to calculate the gas-phase budget of NO3 and quantify the importance of organic peroxy radicals as NO3 sinks. RO2 accounted, on average, for 12–28% of the total gas-phase NO3 losses in the unpolluted regions and for 1–2% of the total gas-phase NO3 losses in the polluted regions.

Keywords

Peroxy radicals RO2 Nitrate radical NO3 MCM TexAQS 2006 
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Notes

Acknowledgements

We thank the crew of the NOAA R/V Brown for their contribution to the field work. Thanks to M.J. Pilling and C.J. Martin for assistance in setting up the MCM model and to A. Bonzanini for help in assembling the appendix. This work was funded in part by NOAA’s Air Quality and Atmospheric Chemistry and Climate Programs and in part by the Texas Commission on Environmental Quality (TCEQ).

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Copyright information

© Springer Science+Business Media B.V. 2012

Authors and Affiliations

  • Roberto Sommariva
    • 1
    • 2
    • 6
  • Tim S. Bates
    • 3
  • Daniel Bon
    • 1
    • 2
    • 7
  • Daniel M. Brookes
    • 4
    • 8
  • Joost A. de Gouw
    • 1
    • 2
  • Jessica B. Gilman
    • 1
    • 2
  • Scott C. Herndon
    • 5
  • William C. Kuster
    • 1
    • 2
  • Brian M. Lerner
    • 1
    • 2
  • Paul S. Monks
    • 4
  • Hans D. Osthoff
    • 1
    • 2
    • 9
  • Alex E. Parker
    • 4
    • 10
  • James M. Roberts
    • 1
  • Sara C. Tucker
    • 1
    • 2
    • 11
  • Carsten Warneke
    • 1
    • 2
  • Eric J. Williams
    • 1
    • 2
  • Mark S. Zahniser
    • 5
  • Steven S. Brown
    • 1
  1. 1.Earth System Research LaboratoryNOAABoulderUSA
  2. 2.CIRESUniversity of ColoradoBoulderUSA
  3. 3.Pacific Marine Environmental LaboratoryNOAASeattleUSA
  4. 4.Department of ChemistryUniversity of LeicesterLeicesterUK
  5. 5.Aerodyne Research, Inc.BillericaUSA
  6. 6.School of Environmental SciencesUniversity of East AngliaNorwichUK
  7. 7.Department of Civil & Environmental EngineeringWashington State UniversityPullmanUSA
  8. 8.Air Quality Practice, AEA plc.HarwellUK
  9. 9.Department of ChemistryUniversity of CalgaryCalgaryCanada
  10. 10.PC2AUniversité des Sciences et Technologies de LilleLilleFrance
  11. 11.Ball Aerospace & Technologies Corp.BoulderUSA

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