Search Results
Hydroxyl radical-induced formation of highly oxidized organic compounds
2016, Berndt, Torsten, Richters, Stefanie, Jokinen, Tuija, Hyttinen, Noora, Kurtén, Theo, Otkjær, Rasmus V., Kjaergaard, Henrik G., Stratmann, Frank, Herrmann, Hartmut, Sipila, Mikko, Kulmala, Markku, Ehn, Mikael
Explaining the formation of secondary organic aerosol is an intriguing question in atmospheric sciences because of its importance for Earth’s radiation budget and the associated effects on health and ecosystems. A breakthrough was recently achieved in the understanding of secondary organic aerosol formation from ozone reactions of biogenic emissions by the rapid formation of highly oxidized multifunctional organic compounds via autoxidation. However, the important daytime hydroxyl radical reactions have been considered to be less important in this process. Here we report measurements on the reaction of hydroxyl radicals with a- and b-pinene applying improved mass spectrometric methods. Our laboratory results prove that the formation of highly oxidized products from hydroxyl radical reactions proceeds with considerably higher yields than previously reported. Field measurements support these findings. Our results allow for a better description of the diurnal behaviour of the highly oxidized product formation and subsequent secondary organic aerosol formation in the atmosphere.
Photosensitized production of functionalized and unsaturated organic compounds at the air-sea interface
2015, Ciuraru, Raluca, Fine, Ludovic, van Pinxteren, Manuela, D’Anna, Barbara, Herrmann, Hartmut, George, Christian
The sea-surface microlayer (SML) has different physical, chemical and biological properties compared to the subsurface water, with an enrichment of organic matter i.e., dissolved organic matter including UV absorbing humic substances, fatty acids and many others. Here we present experimental evidence that dissolved organic matter, such as humic acids, when exposed to sunlight, can photosensitize the chemical conversion of linear saturated fatty acids at the air-water interface into unsaturated functionalized gas phase products (i.e. saturated and unsaturated aldehydes and acids, alkenes and dienes,…) which are known precursors of secondary organic aerosols. These functionalized molecules have previously been thought to be of biological origin, but here we demonstrate that abiotic interfacial photochemistry has the potential to produce such molecules. As the ocean is widely covered by the SML, this new understanding will impact on our ability to describe atmospheric chemistry in the marine environment.