Source apportionment of submicron organic aerosols at an urban site by factor analytical modelling of aerosol mass spectra

Submicron ambient aerosol was characterized in summer 2005 at an urban background site in Zurich, Switzerland, during a three-week measurement campaign. Highly time-resolved samples of non-refractory aerosol components were analyzed with an Aerodyne aerosol mass spectrometer (AMS). Positive matrix factorization (PMF) was used for the first time for aerosol mass spectra to identify the main components of the total organic aerosol and their sources. The PMF retrieved factors were compared to measured reference mass spectra and were correlated with tracer species of the aerosol and gas phase measurements from collocated instruments. Six factors were found to explain virtually all variance in the data and could be assigned either to sources or to aerosol components such as oxygenated organic aerosol (OOA). Our analysis suggests that at the measurement site only a small (<10%) fraction of organic PM1 originates from freshly emitted fossil fuel combustion. Other primary sources identified to be of similar or even higher importance are charbroiling (10-15%) and wood burning (similar to 10%). The fraction of all identified primary sources is considered as primary organic aerosol (POA). This interpretation is supported by calculated ratios of the modelled POA and measured primary pollutants such as elemental carbon (EC), NOx, and CO, which are in good agreement to literature values. A high fraction (60-69%) of the measured organic aerosol mass is OOA which is interpreted mostly as secondary organic aerosol (SOA). This oxygenated organic aerosol can be separated into a highly aged fraction, OOA I, (40-50%) with low volatility and a mass spectrum similar to fulvic acid, and a more volatile and probably less processed fraction, OOA II (on average 20%). This is the first publication of a multiple component analysis technique to AMS organic spectral data and also the first report of the OOA II component.