## Abstract

[1] Bayesian inference has been used to determine rigorous estimates of hydroxyl radical concentrations ([(OH) over bar]) 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 a. 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) over bar], K and alpha following each air mass. Median [(OH) over bar] values are typically between 0.5 and 2.0 x 10(6) molecules cm(-3), but are elevated to between 2.5 and 3.5 x 10(6) molecules cm(-3), in low-level pollution. A comparison of [(OH) over bar] 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 similar to 0.1 day(-1) but show more sensitivity to the prior distribution assumed.

Original language | English |
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Pages (from-to) | - |

Number of pages | 15 |

Journal | Journal of Geophysical Research |

Volume | 112 |

Issue number | D10 |

DOIs | |

Publication status | Published - 3 May 2007 |

## Keywords

- HYDROXYL RADICAL CONCENTRATIONS
- FIELD-MEASUREMENTS
- UPPER TROPOSPHERE
- ATMOSPHERE
- PHOTOCHEMISTRY
- CHEMISTRY
- TRANSPORT
- ATLANTIC
- ACETONE
- RATIOS