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

TY - JOUR

T1 - Statistical inference of OH concentrations and air mass dilution rates from successive observations of nonmethane hydrocarbons in single air masses

AU - Arnold, S. R.

AU - Methven, J.

AU - Evans, Mathew John

AU - Chipperfield, M. P.

AU - Lewis, A. C.

AU - Hopkins, J. R.

AU - McQuaid, J. B.

AU - Watson, N.

AU - Purvis, R. M.

AU - Lee, J. D.

AU - Atlas, E. L.

AU - Blake, D. R.

AU - Rappenglueck, B.

PY - 2007/5/3

Y1 - 2007/5/3

N2 - [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.

AB - [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.

KW - HYDROXYL RADICAL CONCENTRATIONS

KW - FIELD-MEASUREMENTS

KW - UPPER TROPOSPHERE

KW - ATMOSPHERE

KW - PHOTOCHEMISTRY

KW - CHEMISTRY

KW - TRANSPORT

KW - ATLANTIC

KW - ACETONE

KW - RATIOS

U2 - 10.1029/2006JD007594

DO - 10.1029/2006JD007594

M3 - Article

SN - 0148-0227

VL - 112

SP - -

JO - Journal of Geophysical Research

JF - Journal of Geophysical Research

IS - D10

ER -