Molecular composition of organic aerosols formed in the α‐pinene/O3 reaction: Implications for new particle formation processes

The molecular composition of particle phase ozonolysis products of α-pinene is investigated to comprehend the aerosol formation process following the VOC oxidation, focusing on an understanding of new particle formation. Two analytical approaches are applied to identify low-volatile oxidation products in the particle phase; off-line investigations using preconcentration on Tenax TA© followed by solvent extraction and liquid chromatography/mass spectrometry as well as an on-line technique, in which the organic aerosols are introduced directly into the ion source of a mass spectrometer (atmospheric pressure chemical ionization / mass spectrometry (APCI/MS)). Both techniques showed the formation of difunctional carboxylic acids, compounds whose physico-chemical properties will govern most of their mass into the particle phase. Furthermore, stable binary diacid adducts could be identified by MSn-experiments. These observations might give insight into the process of new particle formation by heteromolecular homogeneous nucleation, indicating that the initial cluster formation cannot be described by macroscopic properties of single oxidation products. Instead, strong intermolecular forces between different diacids might play a key role in the formation of initial nuclei and their subsequent growth.