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. The molecular composition and volatility of gaseous organiccompounds were investigated during April–July 2019 at the Station forMeasuring Ecosystem – Atmosphere Relations (SMEAR) II situated in a borealforest in Hyytiälä, southern Finland. In order to obtain a morecomplete picture and full understanding of the molecular composition andvolatility of ambient gaseous organic compounds (from volatile organiccompounds, VOCs, to highly oxygenated organic molecules, HOMs), twodifferent instruments were used. A Vocus proton-transfer-reactiontime-of-flight mass spectrometer (Vocus PTR-ToF; hereafter Vocus) wasdeployed to measure VOCs and less oxygenated VOCs (i.e., OVOCs). Inaddition, a multi-scheme chemical ionization inlet coupled to an atmosphericpressure interface time-of-flight mass spectrometer (MION API-ToF) was usedto detect less oxygenated VOCs (using Br− as the reagent ion; hereafterMION-Br) and more oxygenated VOCs (including HOMs; using NO3- asthe reagent ion; hereafter MION-NO3). The comparison among differentmeasurement techniques revealed that the highest elemental oxygen-to-carbonratios (O : C) of organic compounds were observed by the MION-NO3 (0.9 ± 0.1, average ± 1 standard deviation), followed by the MION-Br(0.8 ± 0.1); lowest O : C ratios were observed by Vocus (0.2 ± 0.1). Diurnal patternsof the measured organic compounds were found to vary among differentmeasurement techniques, even for compounds with the same molecular formula,suggesting contributions of different isomers detected by the differenttechniques and/or fragmentation from different parent compounds inside theinstruments. Based on the complementary molecular information obtained fromVocus, MION-Br, and MION-NO3, a more complete picture of the bulkvolatility of all measured organic compounds in this boreal forest wasobtained. As expected, the VOC class was the most abundant (about 53.2 %), followed by intermediate-volatility organic compounds (IVOCs, about45.9 %). Although condensable organic compounds (low-volatility organiccompounds, LVOCs; extremely low volatility organic compounds, ELVOCs; andultralow-volatility organic compounds, ULVOCs) only comprised about 0.2 %of the total gaseous organic compounds, they play an important role in newparticle formation as shown in previous studies in this boreal forest. Ourstudy shows the full characterization of the gaseous organic compounds inthe boreal forest and the advantages of combining Vocus and MION API-ToF formeasuring ambient organic compounds with different oxidation extents (fromVOCs to HOMs). The results therefore provide a more comprehensiveunderstanding of the molecular composition and volatility of atmosphericorganic compounds as well as new insights into interpreting ambientmeasurements or testing/improving parameterizations in transport and climatemodels.

atmospheric chemistry and physics

Measurement report: Molecular composition and volatility of gaseous organic compounds in a boreal forest – from volatile organic compounds to highly oxygenated organic molecules