Abstract
Statistical inference of OH concentrations and air mass dilution rates from successive observations of nonmethane hydrocarbons in single air masses
Institute for Atmospheric Science, School of Earth and Environment, University of Leeds, Leeds, UK
Department of Meteorology, University of Reading, Reading, UK
Institute for Atmospheric Science, School of Earth and Environment, University of Leeds, Leeds, UK
Institute for Atmospheric Science, School of Earth and Environment, University of Leeds, Leeds, UK
Department of Chemistry, University of York, York, UK
Department of Chemistry, University of York, York, UK
Institute for Atmospheric Science, School of Earth and Environment, University of Leeds, Leeds, UK
Department of Chemistry, University of York, York, UK
Department of Chemistry, University of York, York, UK
Department of Chemistry, University of York, York, UK
Division of Marine and Atmospheric Chemistry, Rosenstiel School of Marine and Atmospheric Science, University of Miami, Miami, Florida, USA
Department of Chemistry, University of California, Irvine, California, USA
Institute of Meteorology and Climate Research, Forschungszentrum Karlsruhe, Garmisch-Partenkirchen, Germany
Bayesian inference has been used to determine rigorous estimates of hydroxyl radical concentrations (
) 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
, K and α following each air mass. Median
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
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: (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.
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