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

Abstract

Bayesian inference has been used to determine rigorous estimates of hydroxyl radical concentrations ([OH]) 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 [OH], K and α following each air mass. Median [OH] values are typically between 0.5 and 2.0 × 10 6 molecules cm -3, but are elevated to between 2.5 and 3.5 × 10 6 molecules cm -3, in low-level pollution. A comparison of [OH] 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. Copyright 2007 by the American Geophysical Union.