Chemical indicators of sulfate sensitivity to nitrogen oxides and volatile organic compounds

The formation of aerosol sulfate (SO42-) in eastern North America is chemically linked to the emissions of nitrogen oxides (NOx) and volatile organic compounds (VOC) through oxidation of the gaseous precursor, sulfur dioxide (SO2). The response of sulfate production to controls in NOx and VOC emissions depends, in part, on the resulting changes in oxidant levels and the competition that naturally exists between the gas- and aqueous-phase pathways for SO2 oxidation. We propose the use of a combination of concentrations of nitric acid, particulate nitrate, hydrogen peroxide, and ambient sulfate as a nondimensional indicator of the effectiveness of VOC or NOx controls in decreasing SO42- abundance. The concentrations of these indicator species were calculated from a series of photochemical model simulations with varying rates of NOx and VOC emissions using a three-dimensional Eulerian model (MODELS-3) that covers the northeastern United States. This study shows that ambient sulfate concentrations are likely to decrease more effectively as VOC emissions are reduced, when the nondimensional indicator is less than a certain threshold. However, a higher value of the indicator identifies a regime in which NOx emissions reductions are more effective for reducing sulfate than are VOC emissions. In addition, a description of the sulfate-formation pathways, along with a theoretical analysis of the transition between NOx- and VOC-sensitive regimes, provides a strong rationale for the use of the sulfate sensitivity indicator.