Constraining the response factors of an extractive electrospray ionization mass spectrometer for near-molecular aerosol speciation

Abstract. Online characterization of aerosol composition at the near-molecular level is key to understanding chemical reaction mechanisms, kinetics, and sources under various atmospheric conditions. The recently developed extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) is capable of detecting a wide range of organic oxidation products in the particle phase in real time with minimal fragmentation. Quantification can sometimes be hindered by a lack of available commercial standards for aerosol constituents, however. Good correlations between the EESI-TOF and other aerosol speciation techniques have been reported, though no attempts have yet been made to parameterize the EESI-TOF response factor for different chemical species. Here, we report the first parameterization of the response factors of the EESI-TOF for secondary organic aerosol (SOA) at the near-molecular level based on their elemental composition. SOA was formed by ozonolysis of monoterpenes or OH-oxidation of aromatics inside an oxidation flow reactor (OFR) using ammonium nitrate as seed particles. A Vocus proton-transfer reaction mass spectrometer (Vocus-PTR) and a high-resolution aerosol mass spectrometer (AMS) were used to determine the gas phase molecular composition and the particle phase bulk chemical composition, respectively. The EESI response factors towards bulk SOA and the inorganic coating were constrained by intercomparison with the AMS. The highest bulk EESI response factor was observed for SOA produced from 1,3,5-trimethylbenzene, followed by those produced from d-limonene and o-cresol, consistent with previous findings. The near-molecular EESI response factors were derived from intercomparisons with Vocus-PTR measurements, and were found to vary from 103 to 106 ions s−1 ppb−1, mostly within ±1 order of magnitude of their geometric mean of 104.5 ions s−1 ppb−1. For aromatic SOA components, the EESI response factors correlated with molecular weight and oxygen content, and inversely correlated with volatility. The near-molecular response factors agreed within a factor of 20 for isomers observed across the aromatics and biogenic systems. Parameterization of the near-molecular response factors based on the measured elemental formulae could reproduce the empirically determined response factor for a single VOC system to within a factor of 5 for the configuration of our mass spectrometers. Results demonstrate that standard-free quantification using EESI-TOF is possible.