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Volume 18, issue 9 | Copyright
Atmos. Chem. Phys., 18, 6367-6380, 2018
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 04 May 2018

Research article | 04 May 2018

Amines in boreal forest air at SMEAR II station in Finland

Marja Hemmilä1, Heidi Hellén1, Aki Virkkula1,2, Ulla Makkonen1, Arnaud P. Praplan1, Jenni Kontkanen2, Lauri Ahonen2, Markku Kulmala2, and Hannele Hakola1 Marja Hemmilä et al.
  • 1Finnish Meteorological Institute, P.O. Box 503, 00101 Helsinki, Finland
  • 2Institute for Atmospheric and Earth System Research/Physics, Faculty of Science, University of Helsinki, P.O. Box 64, 00014 Helsinki, Finland

Abstract. We measured amines in boreal forest air in Finland both in gas and particle phases with 1h time resolution using an online ion chromatograph (instrument for Measuring AeRosols and Gases in Ambient Air – MARGA) connected to an electrospray ionization quadrupole mass spectrometer (MS). The developed MARGA-MS method was able to separate and detect seven different amines: monomethylamine (MMA), dimethylamine (DMA), trimethylamine (TMA), ethylamine (EA), diethylamine (DEA), propylamine (PA), and butylamine (BA). The detection limits of the method for amines were low (0.2–3.1ngm−3), the accuracy of IC-MS analysis was 11–37%, and the precision 10–15%. The proper measurements in the boreal forest covered about 8 weeks between March and December 2015. The amines were found to be an inhomogeneous group of compounds, showing different seasonal and diurnal variability. Total MMA (MMA(tot)) peaked together with the sum of ammonia and ammonium ions already in March. In March, monthly means for MMA were  < 2.4 and 6.8±9.1ngm−3 in gas and aerosol phases, respectively, and for NH3 and NH4+ these were 52±16 and 425±371ngm−3, respectively. Monthly medians in March for MMA(tot), NH3, and NH4+ were  < 2.4, 19 and 90ngm−3, respectively. DMA(tot) and TMA(tot) had summer maxima indicating biogenic sources. We observed diurnal variation for DMA(tot) but not for TMA(tot). The highest concentrations of these compounds were measured in July. Then, monthly means for DMA were  < 3.1 and 8.4±3.1ngm−3 in gas and aerosol phases, respectively, and for TMA these were 0.4±0.1 and 1.8±0.5ngm−3. Monthly medians in July for DMA were below the detection limit (DL) and 4.9ngm−3 in gas and aerosol phases, respectively, and for TMA these were 0.4 and 1.4ngm−3. When relative humidity of air was  > 90%, gas-phase DMA correlated well with 1.1–2nm particle number concentration (R2 = 0.63) suggesting that it participates in atmospheric clustering. EA concentrations were low all the time. Its July means were  < 0.36 and 0.4±0.4ngm−3 in gas and aerosol phases, respectively, but individual concentration data correlated well with monoterpene concentrations in July. Monthly means of PA and BA were below detection limits at all times.

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Short summary
We measured gas- and particle-phase amine and ammonia concentrations in a boreal forest site in 2015 with online ion chromatography coupled with mass spectrometry. We wanted to know how much and which kinds of amines there are, and how they behave and could affect nucleation. We observed seasonal and diurnal variations for different amines. Amines turned out to be a heterogeneous group of compounds. To our best knowledge, our amine measurements are the longest time series that has been made.
We measured gas- and particle-phase amine and ammonia concentrations in a boreal forest site in...