Characterization of the Vaporization Inlet for Aerosols (VIA) for online measurements of particulate highly oxygenated organic molecules (HOMs)

• Published in: Atmospheric measurement techniques 2024-03, Vol.17 (5), p.1527-1543
• Main Authors: Zhao, Jian, Mickwitz, Valter, Luo, Yuanyuan, Häkkinen, Ella, Graeffe, Frans, Zhang, Jiangyi, Timonen, Hilkka, Canagaratna, Manjula, Krechmer, Jordan E., Zhang, Qi, Kulmala, Markku, Kangasluoma, Juha, Worsnop, Douglas, Ehn, Mikael
• Format: Article
• Language: English
• Subjects: Activated carbon; Aerosols; Ammonium; Ammonium compounds; Ammonium sulfate; Climate and health; Decomposition; Evaporation; Gases; High flow; High temperature; Inlets; Investigations; Ionization; Mass spectrometry; One dimensional models; Organic chemistry; Organic compounds; Oxidation; Oxygenation; Particulate matter; Peroxides; Polyethylene glycol; Residence time; Residence time distribution; Secondary aerosols; Sheaths; Sulfate particles; Sulfates; Suspended particulate matter; Temperature dependence; Vaporization; VOCs; Volatile organic compounds
• ISSN: 1867-8548; 1867-1381; 1867-8548
• DOI: 10.5194/amt-17-1527-2024

Particulate matter has major climate and health impacts, and it is therefore of utmost importance to be able to measure the composition of these particles to gain insights into their sources and characteristics. Many methods, both offline and online, have been employed over the years to achieve this goal. One of the most recent developments is the Vaporization Inlet for Aerosols (VIA) coupled to a nitrate Chemical Ionization Mass Spectrometer (NO3-CIMS), but a thorough understanding of the VIA–NO3-CIMS system remains incomplete. In this work, we ran a series of tests to assess the impacts from different systems and sampling parameters on the detection efficiency of highly oxygenated organic molecules (HOMs) in the VIA–NO3-CIMS system. Firstly, we found that the current VIA system (which includes an activated carbon denuder and a vaporization tube) efficiently transmits particles (> 90 % for particles larger than 50 nm) while also removing gaseous compounds (> 97% for tested volatile organic compounds – VOCs). One of the main differences between the VIA and traditional thermal desorption (TD) techniques is the very short residence time in the heating region, on the order of 0.1 s. We found that this short residence time, and the corresponding short contact with heated surfaces, is likely one of the main reasons why relatively reactive or weakly bound peroxides, for example, were observable using the VIA. However, the VIA also requires much higher temperatures in order to fully evaporate the aerosol components. For example, the evaporation temperature of ammonium sulfate particles using the VIA was found to be about 100–150 °C higher than in typical TD systems. We also observed that the evaporation of particles with larger sizes occurred at slightly higher temperatures compared to smaller particles. Another major aspect that we investigated was the gas-phase wall losses of evaporated molecules. With a more optimized interface between the VIA and the NO3-CIMS, we were able to greatly decrease wall losses and thus improve the sensitivity compared to our earlier VIA work. This interface included a dedicated sheath flow unit to cool the heated sample and provide the NO3-CIMS with the needed high flow (10 L min−1). Our results indicate that most organic molecules observable by the NO3-CIMS can evaporate and be transported efficiently in the VIA system, but upon contact with the hot walls of the VIA, the molecules are instantaneously lost. This loss potentially le