Online atmospheric pressure chemical ionization ion trap mass spectrometry (APCI-IT-MSn) for measuring organic acids in concentrated bulk aerosol - a laboratory and field study

The field application of an aerosol concentrator in conjunction with an atmospheric pressure chemical ionization ion trap mass spectrometer (APCI-IT-MS) at the boreal forest station SMEAR II at Hyytiala, Finland, is demonstrated in this study. APCI is a soft-ionization technique allowing online measurements of organic acids in the gas and particle phase. The detection limit for the acid species in the particle phase was improved by a factor of 7.5 to 11 (e. g. similar to 40 ngm(3) for pinonic acid) by using the miniature versatile aerosol concentration enrichment system (mVACES) upstream of the mass spectrometer. The APCI-IT-MS was calibrated in the negative ion mode with two biogenic organic acid standards -pinic acid and pinonic acid. Pinic acid was used as a surrogate for the quantification of the total amount of organic acids in the ambient aerosol based on the total signal intensities in the negative ion mode. The results were compared with the total organic signal of a CToF-AMS during the HUMPPA-COPEC 2010 field campaign. The campaign average contribution of organic acids measured by APCI-IT-MS to the total submicron organic aerosol mass was estimated to be about 60 %, based on the response of pinic acid. Very good correlation between APCIIT-MS and C-ToF-AMS (Pearson's R = 0.94) demonstrates soft-ionization mass spectrometry as a complimentary technique to AMS with electron impact ionization. MS2 studies of specific m/z ratios recorded during the HUMPPA-COPEC 2010 field campaign were compared to MS2 studies of se-lected monoterpene oxidation products formed in simulation chamber experiments. The comparison of the resulting fragments shows that oxidation products of the main VOCs emitted at Hyytiala (alpha-pinene and 1 3-carene) cannot account for all of the measured fragments. Possible explanations for those unaccounted fragments are the presence of unidentified or underestimated biogenic SOA precursors, or that different products are formed by a different oxidant mixture of the ambient air compared to the chamber ozonolysis.