Gas/particle partitioning of total alkyl nitrates observed with TD‐LIF in Bakersfield

Abstract

Limitations in the chemical characterization of tropospheric organic aerosol (OA) continue to impede attempts to fully understand its chemical sources and sinks. To assess the role of organic nitrates in OA, we used a new thermal dissociation‐laser induced fluorescence‐based (TD‐LIF) technique to obtain a high‐time‐resolution record of total aerosol organic nitrates (hereafter ΣANs aer ) at the Bakersfield, CA supersite during the 2010 CalNex campaign. The TD‐LIF measurements compare well with Fourier transform infrared measurements from collocated filter samples. These measurements show that ΣANs are a ubiquitous component of the OA with the –ONO 2 subunit comprising on average 4.8% of the OA mass. Scaling this fraction by an estimate of the organic backbone mass yields an estimate that 17–23% of OA molecules contain nitrate functional groups. Measurements of both total ΣAN (gas + aerosol) and ΣAN aer show that on average 21% of ΣANs are in the condensed phase, suggesting atmospheric organic nitrates have similar volatilities to analogous non‐nitrate oxidized organic compounds. The fraction of ΣAN that is in the condensed phase increases with total OA concentration, providing direct evidence from the atmosphere that absorptive partitioning into OA has some control over the ΣAN phase partitioning. The specific molecular identity of the ΣAN is incompletely understood. Both biogenic hydrocarbons and long chain alkanes are calculated to be significant sources of low volatility nitrates in Bakersfield, and ultra performance liquid chromatography coupled to an electrospray ionization high‐resolution quadrupole time‐of‐flight mass spectrometer measurements confirm the existence of particulate nitrooxy organosulfates derived from gas‐phase oxidation of both isoprene and monoterpenes.