2006, Fisseha, Rebeka, Dommen, Josef, Gutzwiller, Lukas, Weingartner, Ernest, Gysel, Martin, Emmenegger, C., Kalberer, Markus, Baltensperger, Urs

Gas and aerosol samples were taken using a wet effluent diffusion denuder/aerosol collector (WEDD/AC) coupled to ion chromatography (IC) in the city of Zurich, Switzerland from August to September 2002 and in March 2003. Major water soluble inorganic ions; nitrate, sulfate, and nitrite were analyzed online with a time resolution of two hours for the gas and aerosol phase. The fraction of water soluble inorganic anions in PM10 varied from 15% in August to about 38% in March. Seasonal and diurnal variations of nitrate in the gas and aerosol phase were observed with more than 50% of the total nitrate in the gas phase during August and more than 80% of nitrate in the aerosol phase during March exceeding the concentration of sulfate by a factor of 2. Aerosol sulfate, on the other hand, did not show significant variability with season. However, in the gas phase, the SO2 concentration was 6.5 times higher in winter than in summer. Nitrous acid (HONO) also showed a diurnal variation in both the gas and aerosol phase with the lowest concentration (0.2–0.6 µg/m³) in the afternoon. The primary pollutants, NO, CO and SO2 mixing ratios were often at their highest between 04:00–10:00 local time due to the build up of fresh vehicle emission under a nocturnal inversion.

2004-10-15, Fisseha, Rebeka, Dommen, Josef, Sax, Mirjam, Paulsen, Dwane, Kalberer, Markus, Maurer, Rolf, Höfler, Frank, Weingartner, Ernest, Baltensperger, Urs

Organic acids in the gas and aerosol phase from photooxidation of 1,3,5-trimethylbenzene in the presence of 300 ppb propene and 300 ppb NOx in smog chamber experiments were determined using a wet effluent diffusion denuder/aerosol collector coupled to ion chromatography (IC) with conductivity detection. Behind the IC, the samples were collected using a fraction collector, for identification of unresolved/unidentified organic acids with IC-mass spectrometry (MS). In total, 20 organic acids were found with MS of which 10 were identified. The organic acids identified offline by IC-MS were then further quantified based on the online IC data. The identification was additionally confirmed with gas chromatography-mass spectrometry. At the maximum aerosol concentration, organic acids comprised 20-45% of the total aerosol mass. The method has a detection limit of 10-100 ng/m3 for the identified carboxylic acids.

2006, Fisseha, Rebeka, Dommen, Josef, Gäggeler, Kathrin, Weingartner, Ernest, Samburova, Vera, Kalberer, Markus, Baltensperger, Urs

We discuss the diurnal and seasonal variability of low molecular weight organic acids in Zurich city on the basis of online quasi‐continuous measurement in the gas and aerosol phase using a wet effluent diffusion denuder/aerosol collector (WEDD/AC) coupled to ion chromatography. The measurements were performed during August–September 2002 and March 2003. Acetic acid exhibited the highest concentration in the gas phase during all the measurement periods, followed by formic acid. Oxalic acid was predominantly found in the aerosol phase and often below the detection limit in the gas phase. In addition, filter samples were analyzed using ion chromatography–mass spectrometry (IC‐MS) to provide more information on organic acids in the aerosol phase. From the offline IC‐MS measurements, 20 monocarboxylic, dicarboxylic, and tricarboxylic acids were determined. In addition, more than 20 different masses were detected with the MS; however, identification of the organic acids was not possible. The sum of the carboxylic acids contributed on average 2% to the water soluble organic carbon (WSOC). The fraction of dicarboxylic acids to the WSOC was higher in summer compared to winter suggesting that dicarboxylic acids are mainly a result of photochemical reactions in summer whereas in winter they mainly result from primary sources.

2004, Kalberer, Markus, Paulsen, Dwane, Sax, Mirjam, Steinbacher, Martin, Dommen, Josef, Prévôt, André S.H., Fisseha, Rebeka, Weingartner, Ernest, Frankevich, Vladimir, Zenobi, Renato, Baltensperger, Urs

Results from photooxidation of aromatic compounds in a reaction chamber show that a substantial fraction of the organic aerosol mass is composed of polymers. This polymerization results from reactions of carbonyls and their hydrates. After aging for more than 20 hours, about 50% of the particle mass consists of polymers with a molecular mass up to 1000 daltons. This results in a lower volatility of this secondary organic aerosol and a higher aerosol yield than a model using vapor pressures of individual organic species would predict.

2005, Baltensperger, Urs, Kalberer, Markus, Dommen, Josef, Paulsen, Dwane, Alfarra, M. Rami, Coe, Hugh, Fisseha, Rebeka, Gascho, Astrid, Gysel, Martin, Nyeki, Stephan, Sax, Mirjam, Steinbacher, Martin, Prévôt, André S.H., Sjögren, Staffan, Weingartner, Ernest, Zenobi, Renato

Secondary organic aerosol (SOA) formation from the photooxidation of an anthropogenic (1,3,5-trimethylbenzene) and a biogenic (α-pinene) precursor was investigated at the new PSI smog chamber. The chemistry of the gas phase was followed by proton transfer reaction mass spectrometry, while the aerosol chemistry was investigated with aerosol mass spectrometry, ion chromatography, laser desorption ionization mass spectrometry, and infrared spectroscopy, along with volatility and hygroscopicity studies. Evidence for oligomer formation for SOA from both precursors was given by an increasing abundance of compounds with a high molecular weight (up to 1000 Da) and by an increasing thermal stability with increasing aging time. The results were compared to data obtained from ambient aerosol samples, revealing a number of similar features.