Contribution of organosulfur compounds to organic aerosol mass.

Organosulfates have been proposed as products of secondary organic aerosol formation. While organosulfates have been identified in ambient aerosol samples, a question remains as to the magnitude of their contribution to particulate organic mass. At the same time, discrepancies have been observed between total particulate sulfur measured by X-ray fluorescence (XRF) spectroscopy and sulfur present as inorganic sulfate measured by ion chromatography (IC) in fine particulate matter. These differences could be attributed to measurement bias and/or the contribution of other sulfur compounds, including organosulfates. Using the National Park Service IMPROVE PM(2.5) database, we examined the disparity between the sulfur and sulfate measurements at 12 sites across the United States to provide upper-bound estimates for the annual average contributions of organosulfates to organic mass. The data set consists of over 150000 measurements. The 12 sites include Brigantine, NJ, Cape Cod, MA, Washington, DC, Chassahowitzka, FL, Great Smoky Mountains National Park, NC, Okefenokee, GA, Bondville, IL, Mingo, MO, Phoenix, AZ, San Gabriel, CA, Crater Lake National Park, OR, and Spokane, WA. These sites are representative of the different regions of the country: Northeast, Southeast, Midwest, Southwest and Northwest. We estimate that organosulfur compounds could comprise as much as 5-10% of the organic mass at these sites. The contribution varies by season and location and appears to be higher during warm months when photochemical oxidation chemistry is most active.