Abstract
Abstract. Biogenic organic precursors play an important role in atmospheric new particle formation (NPF). One of the major precursor species is α-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 α-pinene oxidation, including in the presence of isoprene, at temperatures (−50 and −30 ∘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 ionization–atmospheric 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 ∼ 100 nm). Particularly, for the system with isoprene added, C5 (C5H10O5−7) and C15 compounds (C15H24O5−10) were detected. This observation is consistent with the previously observed formation of such compounds in the gas phase. However, although the C5 and C15 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 (J1.7 nm) and compared with previous studies, we found lower J1.7 nm values, very likely due to the higher α-pinene and ozone mixing ratios used in the present study.
Highlights
Half of the global cloud condensation nuclei (CCN) are produced by nucleation (Merikanto et al, 2009; Gordon et al, 2017)
The chemical reactions involving volatile organic compounds (VOCs) can lead to the formation of highly oxygenated organic molecules (HOMs), which can be described as a class of organic compounds that are formed under atmospherically relevant conditions by gas-phase autoxidation involving peroxy radicals (Ehn et al, 2014; Bianchi et al, 2019)
We demonstrated the suitability of a thermal desorption differential mobility analyzer (TD-DMA) coupled to a nitrate chemical ionization–atmospheric pressure interface–time-of-flight (CI-APi-TOF) mass spectrometer for measuring HOMs in newly formed nano aerosol particles
Summary
Half of the global cloud condensation nuclei (CCN) are produced by nucleation (Merikanto et al, 2009; Gordon et al, 2017). The chemical reactions involving VOCs can lead to the formation of highly oxygenated organic molecules (HOMs), which can be described as a class of organic compounds that are formed under atmospherically relevant conditions by gas-phase autoxidation involving peroxy radicals (Ehn et al, 2014; Bianchi et al, 2019). These compounds possess low-saturation vapor pressures and are relevant for secondary organic aerosol (SOA) formation, including new particle formation (NPF), due to gas-to-particle partitioning. Much less is known about the particle-phase composition of HOMs in these systems and the specific controls particle formation and growth rates, including as a function of temperature and the ratio of isoprene to α-pinene
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