Transformation of logwood combustion emissions in a smog chamber: formation
of secondary organic aerosol and changes in the primary organic aerosol upon
daytime and nighttime aging
Petri Tiitta1,Ari Leskinen2,3,Liqing Hao2,Pasi Yli-Pirilä1,2,Miika Kortelainen1,Julija Grigonyte1,Jarkko Tissari1,Heikki Lamberg1,Anni Hartikainen1,Kari Kuuspalo1,Aki-Matti Kortelainen2,Annele Virtanen2,Kari E. J. Lehtinen2,3,Mika Komppula3,Simone Pieber4,André S. H. Prévôt4,Timothy B. Onasch5,Douglas R. Worsnop5,Hendryk Czech6,Ralf Zimmermann6,7,8,Jorma Jokiniemi1,and Olli Sippula1,8Petri Tiitta et al.Petri Tiitta1,Ari Leskinen2,3,Liqing Hao2,Pasi Yli-Pirilä1,2,Miika Kortelainen1,Julija Grigonyte1,Jarkko Tissari1,Heikki Lamberg1,Anni Hartikainen1,Kari Kuuspalo1,Aki-Matti Kortelainen2,Annele Virtanen2,Kari E. J. Lehtinen2,3,Mika Komppula3,Simone Pieber4,André S. H. Prévôt4,Timothy B. Onasch5,Douglas R. Worsnop5,Hendryk Czech6,Ralf Zimmermann6,7,8,Jorma Jokiniemi1,and Olli Sippula1,8
1Department of Environmental and Biological Sciences, University of Eastern
Finland, P.O. Box 1627, 70211 Kuopio, Finland
2Department of Applied Physics, University of Eastern Finland, P.O. Box
1627, 70211 Kuopio, Finland
3Finnish Meteorological Institute, P.O. Box 1627, 70211 Kuopio, Finland
4Laboratory of Atmospheric Chemistry, Paul Scherrer Institute,
Villigen, Switzerland
5Aerodyne Research, Inc., Billerica, MA 08121, USA
6Joint Mass Spectrometry Centre, University at Rostock, Institut für
Chemie, Lehrstuhl für Analytische Chemie, Dr.-Lorenz-Weg 1, 18059
Rostock, Germany
7Joint Mass Spectrometry Centre, Cooperation Group Comprehensive
Molecular Analytics, Helmholtz Zentrum München, Germany
8Helmholtz Virtual Institute of Complex Molecular Systems in
Environmental Health (HICE), Aerosols and Health, Neuherberg, Germany
1Department of Environmental and Biological Sciences, University of Eastern
Finland, P.O. Box 1627, 70211 Kuopio, Finland
2Department of Applied Physics, University of Eastern Finland, P.O. Box
1627, 70211 Kuopio, Finland
3Finnish Meteorological Institute, P.O. Box 1627, 70211 Kuopio, Finland
4Laboratory of Atmospheric Chemistry, Paul Scherrer Institute,
Villigen, Switzerland
5Aerodyne Research, Inc., Billerica, MA 08121, USA
6Joint Mass Spectrometry Centre, University at Rostock, Institut für
Chemie, Lehrstuhl für Analytische Chemie, Dr.-Lorenz-Weg 1, 18059
Rostock, Germany
7Joint Mass Spectrometry Centre, Cooperation Group Comprehensive
Molecular Analytics, Helmholtz Zentrum München, Germany
8Helmholtz Virtual Institute of Complex Molecular Systems in
Environmental Health (HICE), Aerosols and Health, Neuherberg, Germany
Correspondence: Petri Tiitta (petri.tiitta@uef.fi)
Received: 19 Apr 2016 – Discussion started: 02 May 2016 – Revised: 24 Sep 2016 – Accepted: 11 Oct 2016 – Published: 28 Oct 2016
Abstract. Organic aerosols (OA) derived from small-scale wood combustion emissions are not well represented by current emissions inventories and models, although they contribute substantially to the atmospheric particulate matter (PM) levels. In this work, a 29 m3 smog chamber in the ILMARI facility of the University of Eastern Finland was utilized to investigate the formation of secondary organic aerosol (SOA) from a small-scale modern masonry heater commonly used in northern Europe. Emissions were oxidatively aged in the smog chamber for a variety of dark (i.e., O3 and NO3) and UV (i.e., OH) conditions, with OH concentration levels of (0.5–5) × 106 molecules cm−3, achieving equivalent atmospheric aging of up to 18 h. An aerosol mass spectrometer characterized the direct OA emissions and the SOA formed from the combustion of three wood species (birch, beech and spruce) using two ignition processes (fast ignition with a VOC-to-NOx ratio of 3 and slow ignition with a ratio of 5).
Dark and UV aging increased the SOA mass fraction with average SOA productions 2.0 times the initial OA mass loadings. SOA enhancement was found to be higher for the slow ignition compared with fast ignition conditions. Positive matrix factorization (PMF) was used to separate SOA, primary organic aerosol (POA) and their subgroups from the total OA mass spectra. PMF analysis identified two POA and three SOA factors that correlated with the three major oxidizers: ozone, the nitrate radical and the OH radical. Organonitrates (ONs) were observed to be emitted directly from the wood combustion and additionally formed during oxidation via NO3 radicals (dark aging), suggesting small-scale wood combustion may be a significant ON source. POA was oxidized after the ozone addition, forming aged POA, and after 7 h of aging more than 75 % of the original POA was transformed. This process may involve evaporation and homogeneous gas-phase oxidation as well as heterogeneous oxidation of particulate organic matter. The results generally prove that logwood burning emissions are the subject of intensive chemical processing in the atmosphere, and the timescale for these transformations is relatively short, i.e., hours.
Real-time measurements of OA aging and SOA formation from logwood combustion were conducted under dark and UV oxidation. Substantial SOA formation was observed in all experiments, leading to twice the initial OA mass emphasizing the importance of the burning conditions for the aging processes. The results prove that emissions are subject to intensive chemical processing in the atmosphere; e.g. the most of the POA was found to become oxidized after the ozone addition, forming aged POA.
Real-time measurements of OA aging and SOA formation from logwood combustion were conducted...
