Detecting and Characterizing Particulate Organic Nitrates with an Aerodyne Long-ToF Aerosol Mass Spectrometer

Abstract

Particulate organic nitrate (pON) can be a major part of secondary organic aerosol (SOA) and is commonly quantified by indirect means from aerosol mass spectrometer (AMS) data. However, pON quantification remains challenging. Here, we set out to quantify and characterize pON in the boreal forest, through direct field observations at Station for Measuring Ecosystem Atmosphere Relationships (SMEAR) II in Hyytiälä, Finland, and targeted single-precursor laboratory studies. We utilized a long time-of-flight AMS (LToF-AMS) for aerosol chemical characterization, with a particular focus to identify C _x H _y O _z N ⁺ (“CHON ⁺”) fragments. We estimate that during springtime at SMEAR II, pON (including both the organic and nitrate part) accounts for ∼10% of the particle mass concentration (calculated by the NO ⁺/NO ₂ ⁺ method) and originates mainly from the NO ₃ radical oxidation of biogenic volatile organic compounds. The majority of the background nitrate aerosol measured is organic. The CHON ⁺ fragment analysis was largely unsuccessful at SMEAR II, mainly due to low concentrations of the few detected fragments. However, our findings may be useful at other sites as we identified 80 unique CHON ⁺ fragments from the laboratory measurements of SOA formed from NO ₃ radical oxidation of three pON precursors (β-pinene, limonene, and guaiacol). Finally, we noted a significant effect on ion identification during the LToF-AMS high-resolution data processing, resulting in too many ions being fit, depending on whether tungsten ions (W ⁺) were used in the peak width determination. Although this phenomenon may be instrument-specific, we encourage all (LTOF-) AMS users to investigate this effect on their instrument to reduce the possibility of incorrect identifications.