Concurrent Temporal and Spatial Trends in Sulfate and Organic Mass Concentrations Measured in the IMPROVE Monitoring Program

Recent modeling and field studies have highlighted a relationship between sulfate concentrations and secondarily formed organic aerosols related to isoprene and other volatile biogenic gaseous emissions. The relationship between these biogenic emissions and sulfate is thought to be primarily associated with the effect of sulfate on aerosol acidity, increased aerosol water at high relative humidities, and aerosol volume. The Interagency Monitoring of Protected Visual Environments (IMPROVE) program provides aerosol concentration levels of sulfate (SO4) and organic carbon (OC) at 136 monitoring sites in rural and remote areas of the United States over time periods of between 15 and 28 years. This data set allows for an examination of relationships between these variables over time and space. The relative decreases in SO4 and OC were similar over most of the eastern United States, even though concentrations varied dramatically from one region to another. The analysis implied that for every unit decrease in SO4 there was about a 0.29 decrease in organic aerosol mass (OA = 1.8 x OC). This translated to a 2 mu g/m(3) decrease in biogenically derived secondary organic aerosol over 15 years in the southeastern United States. The analysis further implied that 35% and 27% in 2001 and 2015, respectively, of average total OA may be biogenically derived secondary organic aerosols and that there was a small but significant decrease in OA not linked to changes in SO4 concentrations. The analysis yields a constraint on ambient SO4-OC relationships that should help to refine and improve regional-scale chemical transport models.