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Journal of Atmospheric Chemistry

, Volume 55, Issue 2, pp 147–166 | Cite as

Measurement and investigation of chamber radical sources in the European Photoreactor (EUPHORE)

  • Judit ZádorEmail author
  • Tamás Turányi
  • Klaus Wirtz
  • Michael J. Pilling
Original Article

Abstract

It is essential to quantify the background reactivity of smog-chambers, since this might be the major limitation of experiments carried out at low pollutant concentrations typical of the polluted atmosphere. Detailed investigation of three chamber experiments at zero-NO x in the European Photoreactor (EUPHORE) were carried out by means of rate-of-production analysis and two uncertainty analysis tools: local uncertainty analysis and Monte Carlo simulations with Latin hypercube sampling. The chemical mechanism employed was that for methane plus the inorganic subset of the Master Chemical Mechanism (MCMv3.1). Newly installed instruments in EUPHORE allowed the measurement of nitrous acid and formaldehyde at sub-ppb concentrations with high sensitivity. The presence of HONO and HCHO during the experiments could be explained only by processes taking place on the FEP Teflon walls. The HONO production rate can be described by the empirical equation W(HONO)EUPHORE dry = a × j NO 2× exp (− T 0/T) in the low relative humidity region (RH < 2%, a = 7.3×1021 cm−3, T 0 = 8945K), and by the equation W(HONO)EUPHORE humid = W(HONO)EUPHORE dry+ j NO 2× b × RH q in the higher relative humidity region (2% < RH < 15%, b = 5.8×108 cm−3 and q = 0.36, and RH is the relative humidity in percentages). For HCHO the expression W(HCHO)EUPHORE = c × j NO 2exp (− T0/T) is applicable (c = 3.1×1017 cm−3 and T0 = 5686 K). In the 0–15% relative humidity range OH production from HONO generated at the wall is about a factor of two higher than that from the photolysis of 100 ppb ozone. Effect of added NO2 was found to be consistent with the dark HONO formation rate coefficient of MCMv3.1.

Keywords

European Photoreactor Master Chemical Mechanism Radical sources Smog chamber Uncertainty analysis Formaldehyde Nitrous acid 

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Copyright information

© Springer Science + Business Media B.V. 2006

Authors and Affiliations

  • Judit Zádor
    • 1
    Email author
  • Tamás Turányi
    • 1
  • Klaus Wirtz
    • 2
  • Michael J. Pilling
    • 3
  1. 1.Department of Physical ChemistryEötvös University (ELTE)BudapestHungary
  2. 2.Centro de Estudios Ambientales del Mediterraneo (CEAM)ValenciaSpain
  3. 3.Department of ChemistryUniversity of LeedsLeedsU.K.

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