References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-12-2189-2012

A new method to discriminate secondary organic aerosols from different sources using high-resolution aerosol mass spectra

Heringa

M. F.

¹ DeCarlo

P. F.

¹ ³ Chirico

¹ ⁴ Tritscher

¹ ⁵ Clairotte

² Mohr

¹ ⁶ Crippa

¹ Slowik

J. G.

¹ Pfaffenberger

¹ Dommen

¹ Weingartner

¹ Prévôt

A. S. H.

¹ Baltensperger

Laboratory of Atmospheric Chemistry, Paul Scherrer Institut, 5232 Villigen PSI, Switzerland

European Commission Joint Research Centre Ispra, Institute for Energy and Transport, Sustainable Transport Unit, 21027 Ispra (VA), Italy

now at: Department of Civil, Architectural and Environmental Engineering, Drexel University, Philadelphia, USA

now at: Italian National Agency for New Technologies, Energy and Sustainable Economic Development (ENEA), UTAPRAD-DIM, Via E. Fermi 45, 00044 Frascati, Italy

now at: TSI GmbH, Particle Instruments, Neuköllner Str. 4, 52068 Aachen, Germany

now at: Department of Atmospheric Sciences, University of Washington, Seattle, USA

28 02 2012

12 4 2189 2203

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

This article is available from http://www.atmos-chem-phys.net/12/2189/2012/acp-12-2189-2012.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/2189/2012/acp-12-2189-2012.pdf

Organic aerosol (OA) represents a significant and often major fraction of the non-refractory PM1 (particulate matter with an aerodynamic diameter da < 1 μm) mass. Secondary organic aerosol (SOA) is an important contributor to the OA and can be formed from biogenic and anthropogenic precursors. Here we present results from the characterization of SOA produced from the emissions of three different anthropogenic sources. SOA from a log wood burner, a Euro 2 diesel car and a two-stroke Euro 2 scooter were characterized with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) and compared to SOA from α-pinene. The emissions were sampled from the chimney/tailpipe by a heated inlet system and filtered before injection into a smog chamber. The gas phase emissions were irradiated by xenon arc lamps to initiate photo-chemistry which led to nucleation and subsequent particle growth by SOA production. Duplicate experiments were performed for each SOA type, with the averaged organic mass spectra showing Pearson's r values >0.94 for the correlations between the four different SOA types after five hours of aging. High-resolution mass spectra (HR-MS) showed that the dominant peaks in the MS, m/z 43 and 44, are dominated by the oxygenated ions C2H3O+ and CO2+, respectively, similarly to the relatively fresh semi-volatile oxygenated OA (SV-OOA) observed in the ambient aerosol. The atomic O:C ratios were found to be in the range of 0.25–0.55 with no major increase during the first five hours of aging. On average, the diesel SOA showed the lowest O:C ratio followed by SOA from wood burning, α-pinene and the scooter emissions. Grouping the fragment ions revealed that the SOA source with the highest O:C ratio had the largest fraction of small ions. The HR data of the four sources could be clustered and separated using principal component analysis (PCA). The model showed a significant separation of the four SOA types and clustering of the duplicate experiments on the first two principal components (PCs), which explained 79% of the total variance. Projection of ambient SV-OOA spectra resolved by positive matrix factorization (PMF) showed that this approach could be useful to identify large contributions of the tested SOA sources to SV-OOA. The first results from this study indicate that the SV-OOA in Barcelona is strongly influenced by diesel emissions in winter while in summer at SIRTA at the southwestern edge of Paris SV-OOA is more similar to alpha-pinene SOA. However, contributions to the ambient SV-OOA from SOA sources that are not covered by the model can cause major interference and therefore future expansions of the PCA model with additional SOA sources is recommended.

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