Chemical composition of nanoparticles from alpha-pinene nucleation and the influence of isoprene and relative humidity at low temperature

Biogenic organic precursors play an important role in atmospheric new particle formation (NPF). One of the major precursor species is alpha-pinene, which upon oxidation can form a suite of products covering a wide range of volatilities. Highly oxygenated organic molecules (HOMs) comprise a fraction of the oxidation products formed. While it is known that HOMs contribute to secondary organic aerosol (SOA) formation, including NPF, they have not been well studied in newly formed particles due to their very low mass concentrations. Here we present gas- and particle-phase chemical composition data from experimental studies of alpha-pinene oxidation, including in the presence of isoprene, at temperatures (-50 and -30 degrees C) and relative humidities (20% and 60 %) relevant in the upper free troposphere. The measurements took place at the CERN Cosmics Leaving Outdoor Droplets (CLOUD) chamber. The particle chemical composition was analyzed by a thermal desorption differential mobility analyzer (TD-DMA) coupled to a nitrate chemical ionizationatmospheric pressure interface-time-of-flight (CI-APi-TOF) mass spectrometer. CI-APi-TOF was used for particle- and gas-phase measurements, applying the same ionization and detection scheme. Our measurements revealed the presence of C8-10 monomers and C18-20 dimers as the major compounds in the particles (diameter up to similar to 100 nm). Particularly, for the system with isoprene added, C-5 (C5H10O5-7) and C-15 compounds (C15H24O5-10) were detected. This observation is consistent with the previously observed formation of such compounds in the gas phase. However, although the C-5 and C-15 compounds do not easily nucleate, our measurements indicate that they can still contribute to the particle growth at free tropospheric conditions. For the experiments reported here, most likely isoprene oxidation products enhance the growth of particles larger than 15 nm. Additionally, we report on the nucleation rates measured at 1.7 nm (J(1.7 nm)) and compared with previous studies, we found lower J(1.7 nm) values, very likely due to the higher alpha-pinene and ozone mixing ratios used in the present study.