Hydrocarbon ratios during PEM‐WEST A: A model perspective

Abstract

A useful application of the hydrocarbon measurements collected during the Pacific Exploratory Mission (PEM‐West A) is as markers or indices of atmospheric processing. Traditionally, ratios of particular hydrocarbons have been interpreted as photochemical indices, since much of the effect due to atmospheric transport is assumed to cancel by using ratios. However, an ever increasing body of observatonial and theoretical evidence suggests that turbulent mixing associated with atmospheric transport influences certain hydrocarbon ratios significantly. In this study a three‐dimensional mesoscale photochemical model is used to study the interaction of photochemistry and atmospheric mixing on select hydrocarbons. In terms of correlations and functional relationships between various alkanes, the model results and PEM‐West A hydrocarbon observations share many similar characteristics as well as explainable differences. When the three‐dimensional model is applied to inert tracers, hydrocarbon ratios andother relationships exactly follow those expected by simple dilution with model‐imposed “background air,” and the three‐dimensional results for reactive hydrocarbons are quite consistent with a combined influence of photochemistry and simple dilution. Analogous to these model results, relationships between various hydrocarbons collected during the PEM‐West A experiment appear to be consistent with this simplified picture of photochemistry and dilution affecting individual air masses. When hydrocarbons are chosen that have negligible contributions to clean background air, unambiguous determinations of the relative contributions to photochemistry and dilution can be estimated from the hydrocarbon samples. Both the three‐dimensional model results and the observations imply an average characteristic lifetime for dilution with background air roughly equivalent to the photochemical lifetime of butane for the western Pacific lower troposphere. Moreover, the dominance of OH as the primary photochemical oxidant downwind of anthropogenic source regions can be inferred from correlations between the highly reactive alkane ratios. By incorporating back‐trajectory information within the three‐dimensional model analysis, a correspondence between time and a particular hydrocarbon or hydrocarbon ratio can be determined, and the influence of atmospheric mixing or photochemistry can be quantified. Results of the three‐dimensional model study are compared and applied to the PEM‐West A hydrocarbon dataset, yielding a practical methodology for determining average OH concentrations and atmospheric mixing rates from the hydrocarbon measurements. Aircraft data taken below 2 km during wall flights east of Japan imply a diurnal average OH concentration of ∼3 × 106 cm−3. The characteristic time for dilution with background air is estimated to be ∼2.5 days for the two study areas examined in this work.