Characterization of the organic matter in submicron urban aerosols using a Thermo-Desorption Proton-Transfer-Reaction Time-of-Flight Mass Spectrometer (TD-PTR-TOF-MS)

Abstract Organic matter is the most complicated and unresolved major component of atmospheric aerosol particles. Its sources and global budget are still highly uncertain and thereby necessitate further research efforts with state-of-the-art instrument. This study employed a Thermo-Desorption Proton-Transfer-Reaction Time-of-Flight Mass Spectrometer (TD-PTR-TOF-MS) for characterization of ambient organic aerosols. First, five authentic standard substances, which include phthalic acid, levoglucosan, arabitol, cis -pinonic acid and glutaric acid, were utilized to examine the response of the instrument. The results demonstrated the linearity of the TD-PTR-TOF-MS signals against a range of mass loading of specific species on filters. However, it was found that significant fragmentation happened to those challenging compounds, although the proton-transfer-reaction (PTR) was recognized as a soft ionization technique. Consequently, quantitative characterization of aerosols with the TD-PTR-TOF-MS depended on the availability of the fragmentation pattern in mass spectra and the recovery rate with the quantification ion peak(s). The instrument was further deployed to analyze a subset of submicron aerosol samples collected at the TARO (Taipei Aerosol and Radiation Observatory) in Taipei, Taiwan during August 2013. The results were compared with the measurements from a conventional DRI thermo-optical carbon analyzer. The inter-comparison indicated that the TD-PTR-TOF-MS underestimated the mass of total organic matter (TOM) in aerosol samples by 27%. The underestimation was most likely due to the thermo-decomposition during desorption processes and fragmentation in PTR drift tube, where undetectable fragments were formed. Besides, condensation loss of low vapor pressure species in the transfer components was also responsible for the underestimation to a certain degree. Nevertheless, it was showed that the sum of the mass concentrations of the major detected ion peaks correlated strongly with the TOM determined by DRI analyzer (R 2  = 0.8578), suggesting that the TD-PTR-TOF-MS measurements explained more than 85% of the variance in the time series of TOM. In addition to identification by comparing with the fragmentation pattern obtained from the mass spectra of the authentic substances, most of the major ions were attributed to protonated or acylium ions of specific parent compounds. Amongst the quantified species with full calibration with authentic standard, phthalic acid was found accounting for 7.0% of the mass loading of TOM. In addition, a high-end estimation of 9.4% was suggested for the mass contribution from glutaric acid, which was made by assuming that the ion with m/z of 73.027 was totally produced from fragmentation of glutaric acid as characterization of authentic standard despite of the formation of protonated methyl-glyoxal ion. Moreover, a substantial contribution from ions corresponding to protonated acetic acid and acetone was measured, which could be produced from fragmentation of larger oxygenated molecules. The TD-PTR-TOF-MS measurements suggested that low molecular weight carboxylic acid (LMWCA), products of photochemical oxidation of gaseous hydrocarbons and fatty acids, constituted a major fraction of secondary organic aerosols in Taipei, Taiwan, a typical subtropical urban area.