Seasonal variations of fine particulate organosulfates derived from biogenic and anthropogenic hydrocarbons in the mid-Atlantic United States

- Biogenic and anthropogenic organosulfates (OSs) are characterized at molecular level.
- Seasonal trends demonstrate biogenic-derived OSs peak in warmer months.
- Biogenic OSs derived from atmospheric oxidations of isoprene and monoterpenes.
- Anthropogenic-derived OSs are also characterized and tend to peak in winter months.
- HYSPLIT back trajectories lend insights to sources of OS species.

Organosulfates (OSs) are an important and ubiquitous class of organic compounds found in ambient fine particulate matter (PM2.5) that serves as markers for multiphase chemical processes leading to secondary organic aerosol (SOA) formation. In this study, high-volume filter sampling was implemented to collect PM2.5 samples during the August 2012-June 2013 time period in suburban Towson, MD. By utilizing ultra-performance liquid chromatography coupled with high-resolution quadrupole time-of-flight mass spectrometry employing an electrospray ionization source (UPLC/ESI-HR-QTOFMS), 58 OSs were characterized and quantified in PM2.5 collected across all seasons. The selection of the extraction solvent was also found to be important for OS characterization. Seasonal trends demonstrate that the atmospheric oxidation of biogenic volatile organic compounds (VOCs) dominates OS formation in early fall and spring, with substantial contributions from isoprene OS (∼15 ng/m3), and limonene and α-pinene OS (∼5 ng/m3). From November to March anthropogenic OSs, including polycyclic aromatic hydrocarbon (PAH)- and alkane-derived OSs recently characterized in laboratory-generated SOA, reached their highest levels averaging 4 ng/m3. Nitrogen-containing OSs derived from terpene chemistry remain consistent over the sampling period averaging 2 ng/m3 and do not demonstrate strong seasonal fluctuations. Correlations between the identified OSs and known organic acids that arise from either the atmospheric oxidation of biogenic or anthropogenic VOCs assist in source apportionment. Meteorological data coupled with air mass back-trajectory analyses using HYSPLIT provide insight into meteorological and transport conditions that promote the formation/occurrence of OSs within the mid-Atlantic U.S. region.