NMOC, ozone, and organic aerosol in the southeastern United States, 1999-2007: 1. Spatial and temporal variations of NMOC concentrations and composition in Atlanta, Georgia

摘要

Volatile organic compounds (VOCs) are emitted from anthropogenic and natural (biogenic) sources into the atmosphere. Characterizing their ambient mixing ratios or concentrations is a challenge because VOCs comprise hundreds of species, and accurate measurements are difficult. Long-term hourly and daily-resolution data have been collected in the metropolitan area of Atlanta, Georgia, a major city dominated by motor vehicle emissions. A series of observations of daily, speciated C_2-C_(10) non-methane organic compounds (NMOC) and oxygenated hydrocarbons (OVOC) in mid-town Atlanta (Jefferson Street, JST) are compared with data from three urban-suburban sites and a nearby non-urban site. Annual-average mixing ratios of NMOC and OVOC at JST declined from 1999 through 2007. Downward trends in NMOC, CO, and NO_y corroborate expected emission changes as reflected in emission inventories for Atlanta's Fulton County. Comparison of the JST NMOC composition with data from roadside and tunnel sampling reveals similarities to motor vehicle dominated samples. The JST annual average VOC-OH reactivities from 1999 to 2007 were relatively constant compared with the decline in annual-average NMOC mixing ratios. Mean reactivity at JST, in terms of concentration'koH. was approximately 40% alkenes, 22% aromatics, 16% isoprene and 6% other biogenics, 13% C_7-C_(10) alkanes and 3% C_2-C_6 alkanes, indicating that biogenic NMOCs are important but not dominant contributors to the urban reactive NMOC mix. In contrast, isoprene constituted ~50% of the VOC-OH reactivities at two non-urban sites. Ratios of 24-hour average CO/benzene, CO/isopentane, and CO/acetylene concentrations indicate that such species are relatively conserved, consistent with their low reactivity. Ratios of more-reactive to less-reactive species show diurnal variability largely consistent with expected emission patterns, transport and mixing of air, and chemical processing.