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Atmospheric aerosols have important in uence on the radiation balance of the Earth, on visibility and human health. Secondary organic aerosol is formed from gas-to-particle conversion of oxidized volatile organic compounds. A dominant fraction of the gases originates from plant emissions, making biogenic secondary organic aerosol (BSOA) an especially important constituent of the atmosphere. Knowing the chemical composition of BSOA particles is crucial for a thorough understanding of aerosol processes in the environment. In this work, the chemical composition of BSOA particles was measured with aerosol mass spectrometry and analyzed with statistical methods. The experimental part of the work comprises process studies of the formation and aging of biogenic aerosols in simulation chambers. Using a plant chamber, real tree emissions were used to produce particles in a way close to conditions in forest environments. In the outdoor chamber SAPHIR, OH-radicals were produced from the photooxidation of ozone under illumination with natural sunlight. Here, BSOA was produced from defined mixtures of mono- and sesquiterpenes that represent boreal forest emissions. A third kind of experiments was performed in the indoor chamber AIDA. Here, particles were produced from ozonolysis of single monoterpenes and aged by condensing OH-oxidation products.

Two aerosol mass spectrometers (AMS) were used to measure the chemical composition of the particles. One of the instruments is equipped with a quadrupole mass spectrometer providing unit mass resolution. The second instrument contains a time-of-flight mass spectrometer and provides mass resolution sufficient to distinguish different fragments with the same nominal mass.

Aerosol mass spectra obtained with these instruments are strongly fragmented due to electron impact ionization of the evaporated molecules. In addition, typical BSOA mass spectra are very similar to each other. In order to get a more detailed knowledge about the mass spectral characteristics of aerosol from different precursor mixtures or of different age, statistical methods comprise a major part of the analysis performed in this work. First, hierarchical cluster analysis is used to classify similar mass spectra. This method is based on the distances between pairs of mass spectra and is helpful to distinguish between groups of very similar data sets. Cluster analysis operates on static mass spectra and does not incorporate time-dependent processes. As a result it is found that the chemical composition of BSOA is almost independent from the detailed composition of the terpene precursor mixture.

Second, elemental analysis of the mass spectra is performed using the high resolving power of the time-of-flight AMS. For each mass spectrum, the ratio of oxygen to carbon atoms, O/C, can be calculated by knowing the chemical composition of the individual fragments and counting the respective elements. This analysis helps interpreting the results from the statistical methods. The temporal evolution of O/C can be directly interpreted as an aging process. The evolution is further compared to the oxidation conditions of the respective experiments. It is found that the temporal O/C evolution in SAPHIR experiments is strongly dependent on the abundance of OH.

Finally, a matrix factorization method constraining the entries in the solution matrices to positive values (PMF) is applied to determine factors in aging experiments. The results are linked to fragment distributions in high-resolved mass spectra and to external measurements of terpene oxidation products. A main result from PMF is that the chemical composition of BSOA particles is a combination of many parallel processes with different time constants.

Additional measurements were performed on heated aerosol to infer the volatility and changes in the chemical composition with evaporation of the most volatile compounds. The discussion of the results from these measurements forms the final chapter of this work.

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