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AGU: Journal of Geophysical Research, Atmospheres

 

Keywords

  • Lagrangian
  • hydroxyl radical
  • photochemistry

Index Terms

  • Atmospheric Composition and Structure: Troposphere: composition and chemistry
  • Atmospheric Composition and Structure: Troposphere: constituent transport and chemistry
  • Atmospheric Composition and Structure: Constituent sources and sinks
Abstract
Cited By (3)
 

Abstract

Statistical inference of OH concentrations and air mass dilution rates from successive observations of nonmethane hydrocarbons in single air masses

S. R. Arnold

Institute for Atmospheric Science, School of Earth and Environment, University of Leeds, Leeds, UK

J. Methven

Department of Meteorology, University of Reading, Reading, UK

M. J. Evans

Institute for Atmospheric Science, School of Earth and Environment, University of Leeds, Leeds, UK

M. P. Chipperfield

Institute for Atmospheric Science, School of Earth and Environment, University of Leeds, Leeds, UK

A. C. Lewis

Department of Chemistry, University of York, York, UK

J. R. Hopkins

Department of Chemistry, University of York, York, UK

J. B. McQuaid

Institute for Atmospheric Science, School of Earth and Environment, University of Leeds, Leeds, UK

N. Watson

Department of Chemistry, University of York, York, UK

R. M. Purvis

Department of Chemistry, University of York, York, UK

J. D. Lee

Department of Chemistry, University of York, York, UK

E. L. Atlas

Division of Marine and Atmospheric Chemistry, Rosenstiel School of Marine and Atmospheric Science, University of Miami, Miami, Florida, USA

D. R. Blake

Department of Chemistry, University of California, Irvine, California, USA

B. Rappenglück

Institute of Meteorology and Climate Research, Forschungszentrum Karlsruhe, Garmisch-Partenkirchen, Germany

Bayesian inference has been used to determine rigorous estimates of hydroxyl radical concentrations (inline equation) and air mass dilution rates (K) averaged following air masses between linked observations of nonmethane hydrocarbons (NMHCs) spanning the North Atlantic during the Intercontinental Transport and Chemical Transformation (ITCT)-Lagrangian-2K4 experiment. The Bayesian technique obtains a refined (posterior) distribution of a parameter given data related to the parameter through a model and prior beliefs about the parameter distribution. Here, the model describes hydrocarbon loss through OH reaction and mixing with a background concentration at rate K. The Lagrangian experiment provides direct observations of hydrocarbons at two time points, removing assumptions regarding composition or sources upstream of a single observation. The estimates are sharpened by using many hydrocarbons with different reactivities and accounting for their variability and measurement uncertainty. A novel technique is used to construct prior background distributions of many species, described by variation of a single parameter α. This exploits the high correlation of species, related by the first principal component of many NMHC samples. The Bayesian method obtains posterior estimates of inline equation, K and α following each air mass. Median inline equation values are typically between 0.5 and 2.0 × 106 molecules cm−3, but are elevated to between 2.5 and 3.5 × 106 molecules cm−3, in low-level pollution. A comparison of inline equation estimates from absolute NMHC concentrations and NMHC ratios assuming zero background (the “photochemical clock” method) shows similar distributions but reveals systematic high bias in the estimates from ratios. Estimates of K are ∼0.1 day−1 but show more sensitivity to the prior distribution assumed.

Received 31 May 2006; accepted 10 January 2007; published 3 May 2007.

Citation: Arnold, S. R., et al. (2007), Statistical inference of OH concentrations and air mass dilution rates from successive observations of nonmethane hydrocarbons in single air masses, J. Geophys. Res., 112, D10S40, doi:10.1029/2006JD007594.

Cited By

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