Light absorption of fine particle (PM_2.5) aqueous extracts between wavelengths of 200 and 800 nm were investigated from two data sets: 24-h Federal Reference Method (FRM) filter extracts from 15 Southeastern US monitoring sites over the year of 2007 (900 filters), and online measurements from a Particle-Into-Liquid Sampler deployed from July to mid-August 2009 in Atlanta, Georgia. Three main sources of soluble chromophores were identified: biomass burning, mobile source emissions, and compounds linked to secondary organic aerosol (SOA) formation. Absorption spectra of aerosol solutions from filter extracts were similar for different sources. Angstrom exponents were ~7±1 for biomass burning and non-biomass burning-impacted 24-h filter samples (delineated by a levoglucosan concentration of 50 ng m⁻³) at both rural and urban sites. The absorption coefficient from measurements averaged between wavelength 360 and 370 nm (Abs₃₆₅, in units m⁻¹) was used as a measure of overall brown carbon light absorption. Biomass-burning-impacted samples were highest during winter months and Abs₃₆₅ was correlated with levoglucosan at all sites. During periods of little biomass burning in summer, light absorbing compounds were still ubiquitous and correlated with fine particle Water-Soluble Organic Carbon (WSOC), but comprised a much smaller fraction of the WSOC, where Abs₃₆₅/WSOC (i.e., mass absorption efficiency) was typically ~3 times higher in biomass burning-impacted samples. Factor analysis attributed 50% of the yearly average Abs₃₆₅ to biomass burning sources. Brown carbon from primary urban emissions (mobile sources) was also observed and accounted for ~10% of the regional yearly average Abs₃₆₅. Summertime diurnal profiles of Abs₃₆₅ and WSOC showed that morning to midday increases in WSOC from photochemical production were associated with a decrease in Abs₃₆₅/WSOC. After noon, this ratio substantially increased, indicating that either some fraction of the non-light absorbing fresh SOA was rapidly (within hours) converted to chromophores heterogeneously, or that SOA from gas-particle partitioning later in the day was more light-absorbing. Factor analysis on the 24-h integrated filter data associated ~20 to 30% of Abs₃₆₅ over 2007 with a secondary source that was highest in summer and also the main source for oxalate, suggesting that aqueous phase reactions may account for the light-absorbing fraction of WSOC observed throughout the Southeastern US in summer

In this work, we evaluate ambient ozone trends at urban, suburban, and rural monitoring sites across the United States over a period of decreasing NOx and VOC emissions (1998-2013). We find that decreasing ozone trends generally occur in the summer, in less urbanized areas, and at the upper end of the ozone distribution. Conversely, increasing ozone trends generally occur in the winter, in more urbanized areas, and at the lower end of the ozone distribution. The 95(th) percentile ozone concentrations decreased at urban, suburban, and rural monitors by 1-2 ppb/yr in the summer and 0.5-1 ppb/yr in the winter. In the summer, there are both increasing and decreasing trends in fifth percentile ozone concentrations of less than 0.5 ppb/yr at urban and suburban monitors, while fifth percentile ozone concentrations at rural monitors decreased by up to 1 ppb/yr. In the winter, fifth percentile ozone concentrations generally increased by 0.1-1 ppb/yr. These results demonstrate the large scale success of U.S. control strategies targeted at decreasing peak ozone concentrations. In addition, they indicate that as anthropogenic NOx emissions have decreased, the ozone distribution has been compressed, leading to less spatial and temporal variability.

Speciated aerosol composition data from the rural Interagency Monitoring for Protected Visual Environments (IMPROVE) network and the Environmental Protection Agency's urban/suburban Chemical Speciation Network (CSN) were combined to evaluate and contrast the PM2.5 composition and its seasonal patterns at urban and rural locations throughout the United States. We examined the 2005–2008 monthly and annual mean mass concentrations of PM2.5 ammonium sulfate (AS), ammonium nitrate (AN), particulate organic matter (POM), light‐absorbing carbon (LAC), mineral soil, and sea salt from 168 rural and 176 urban sites. Urban and rural AS concentrations and seasonality were similar, and both were substantially higher in the eastern United States. Urban POM and LAC concentrations were higher than rural concentrations and were associated with very different seasonality depending on location. The highest urban and rural POM and LAC concentrations occurred in the southeastern and northwestern United States. Wintertime peaks in AN were common for both urban and rural sites, but urban concentrations were several times higher, and both were highest in California and the Midwest. Fine soil concentrations were highest in the Southwest, and similar regional patterns and seasonality in urban and rural concentrations suggested impacts from long‐range transport. Contributions from sea salt to the PM2.5 budget were non‐negligible only at coastal sites. This analysis revealed spatial and seasonal variability in urban and rural aerosol concentrations on a continental scale and provided insights into their sources, processes, and lifetimes.