Comparison of free tropospheric western Pacific air mass classification schemes for the PEM-West A experiment

During September/October 1991, NASA's Global Tropospheric Experiment (GTE) conducted an airborne field measurement program (PEM-West A) in the troposphere over the western Pacific Ocean. In this paper we describe and use the relative abundance of the combustion products C2H2 and CO to classify air masses encountered during PEM-West A based on the degree that these tracers were processed by the combined effects of photochemical reactions and dynamical mixing (termed the degree of atmospheric processing). A large number of trace compounds (e.g., C2H6, C3H8, C6H6, NOy, and O-3) are found to be well correlated with the degree of atmospheric processing that is reflected by changes in the ratio of C2H2/CO over the range of values from similar to 0.3 to 2.0 (parts per trillion volume) C2H2/ (parts per billion volume) CO. This C2H2/CO-based classification scheme is compared to model simulations and to two independent classification schemes based on air mass back-trajectory analyses and lidar profiles of O-3 and aerosols. In general, these schemes agree well, and in combination they suggest that the functional dependence that other observed species exhibit with respect to the C2H2/CO atmospheric processing scale can be used to study the origin, sources, and sinks of trace species and to derive several important findings. First, the degree of atmospheric processing is found to be dominated by dilution associated with atmospheric mixing, which is found to primarily occur through the vertical mixing of relatively recent emissions of surface layer trace species. Photochemical reactions play their major role by influencing the background concentrations of trace species that are entrained during the mixing (i.e., dilution) process. Second, a significant noncontinental source(s) of NO (and NOx) in the free troposphere is evident. In particular, the enhanced NO mixing ratios that were observed in convected air masses are attributed to either emissions from lightning or the rapid recycling of NOy compounds. Third, nonsoluble trace species emitted in the continental boundary layer, such as CO and hydrocarbons, are vertically transported to the upper troposphere as efficiently as they are td the midtroposphere. In addition, the mixing ratios of CO and hydrocarbons in the upper troposphere over the western Pacific may reflect a significant contribution from northern hemisphere land areas other than Asia. Finally, we believe that these results can be valuable for the quantitative evaluation of the vertical transport processes that are usually parameterized in models.