A chemical climatology of lower tropospheric trace gases and aerosols over the Mid-Atlantic region

Abstract

Ozone and aerosols affect air quality, visibility and human health. The University of Maryland research aircraft conducted flights over the Mid-Atlantic region between 1995 and 2005 to characterize pollution events. I developed a chemical climatology of trace gases and aerosols that can be used to validate and improve models. O3 and SO2 measured aboard the aircraft were compared with O3 and SO2 generated with the Community Multiscale Air Quality (CMAQ). In general, CMAQ under-estimates O3 above 500 m and over-estimates O3 below 500 m (possible reasons for this include chemistry not being properly represented in the model). A sensitivity test of the rate of photolysis of NO2 was performed and improving the photochemistry did improve the modeled O3. CMAQ over-predicts the SO2 column content by about 50%, possibly because the model gives SO2 too long a lifetime. To test this theory I developed a method for calculating the SO2 lifetime using in-situ measurements. The mean SO2 lifetime was 19 ± 7 hours for measurements made in the daytime in the summer in the Mid-Atlantic region with in-cloud processes responsible for ~80% of the removal. I made comparisons of three aerosol sampling systems and found the uncertainty of PM2.5, sulfate, and ammonium measured with the Speciation Trends Network is larger than what has been reported and is at least 20%. I have developed clustering methodologies to group back trajectories associated with aircraft profiles as well as group trace gas and aerosol profiles by size and shape. The first clustering method produced eight distinct meteorological regimes associated with pollution and haze events. I quantified the amount of O3 transported for each meteorological regime. Using the second method, I found a strong correlation between O3 profiles and point source NOx emissions. The comparisons of model and measured profiles, comparisons of surface measurements, and clustering methods are used to explain sources, sinks and distributions of trace gases and aerosols in the mid-Atlantic thus improving the understanding of the lower atmospheric composition in this area.