| Autor: |
Zhao, Defeng, Kaminski, M., Wang, Mingjin, Wegener, R., Wildt, J., Wahner, A., Mentel, T. F., Schlag, P., Fuchs, H., Acir, I.-H., Bohn, B., Häseler, R., Kiendler-Scharr, A., Rohrer, F., Tillmann, R. |
| Jazyk: |
angličtina |
| Rok vydání: |
2014 |
| Předmět: |
|
| Zdroj: |
Atmospheric chemistry and physics / Discussions 14(9), 12591-12634 (2014). doi:10.5194/acpd-14-12591-2014 |
| DOI: |
10.5194/acpd-14-12591-2014 |
| Popis: |
Oxidation by hydroxyl radical (OH) and ozonolysis are the two major pathways of daytime biogenic volatile organic compounds (VOCs) oxidation and secondary organic aerosol (SOA) formation. In this study, we investigated the particle formation of several common monoterpenes (α-pinene, β-pinene, and limonene) by OH dominated oxidation, which has seldom been investigated. OH oxidation experiments were carried out in the SAPHIR chamber in Jülich, Germany, at low NOx (0.01–1 ppbV) and low ozone (O3) concentration. OH concentration and OH reactivity were measured directly so that the overall reaction rates of organic compounds with OH were quantified. Multi-generation reaction process, particle growth, new particle formation, particle yield, and chemical composition were analyzed and compared with that of monoterpene ozonolysis. Multi-generation products were found to be important in OH dominated SOA formation. The relative role of functionalization and fragmentation in the reaction process of OH oxidation was analyzed by examining the particle mass and the particle size as a function of OH dose. We developed a novel method which quantitatively links particle growth to the reaction of OH with organics in a reaction system. This method was also used to analyze the evolution of functionalization and fragmentation of organics in the particle formation by OH oxidation. It shows that functionalization of organics was dominant in the beginning of the reaction (within two lifetimes of the monoterpene) and fragmentation started to be dominant after that. We compared particle formation from OH oxidation with that from pure ozonolysis. In individual experiments, growth rates of the particle size did not necessarily correlate with the reaction rate of monoterpene with OH and O3. Comparing the size growth rates at the similar reaction rates of monoterpene with OH or O3 indicates that generally, OH oxidation and ozonolysis had similar efficiency in particle growth. The SOA yield of α-pinene and limonene by ozonolysis was higher than that of OH oxidation. Aerosol mass spectrometry (AMS) shows SOA elemental composition from OH oxidation follows a slope shallower than −1 in the O / C vs. H / C diagram, indicating that oxidation proceeds without significant loss of hydrogen. SOA from OH oxidation had higher H / C ratios than SOA from ozonolysis. In ozonolysis, a process with significant hydrogen loss seemed to play an important role in SOA formation. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
|
