Abstract. Highly oxygenated compounds are important contributors to the formation and growth of atmospheric organic aerosol, and thus have an impact on Earth’s radiation balance and global climate. However, knowledge of the contribution of highly oxygenated compounds to organic aerosol and their fate after condensing into the particle phase has been limited by the lack of suitable detection techniques. Here, we present a new online method for measuring highly oxygenated compounds from organic aerosol. The method includes thermal evaporation of particles in a new inlet, Vocus inlet for aerosols (VIA), followed by identification of the evaporated highly oxygenated compounds by a nitrate chemical ionization mass spectrometer (NO3-CIMS). The method does not require sample collection, enabling highly time-resolved measurements of particulate compounds. We evaluate the performance of the method by measuring the detection limit and performing background measurements. We estimate a detection limit of below 1 ng m−3 for a single compound and below 1 μg m−3 for SOA with the sampling set-up used here. These detection limits can be improved upon by optimizing the flow setup. Furthermore, we detect hundreds of particulate highly oxygenated compounds from organic aerosol generated from different precursors. Our results are consistent with previous studies showing that the volatility of organic compounds decreases with increasing m/z ratio and higher level of oxygenation, and that organic aerosol consists of monomers and oligomeric compounds. By comparing the gas- and particle-phase compounds, we found indications of potential particle-phase reactions occurring in organic aerosol. Future work will focus both on further improving the sampling design, as well as on better understanding the evaporation dynamics of the system, but already these initial tests show that VIA coupled to the NO3-CIMS is a promising method for investigating the transformations and fate of the compounds after condensing into the particle phase.

Abstract. Highly oxygenated organic molecules (HOMs) are important for the formation of secondary organic aerosol (SOA), which poses serious health risks and exerts great influence on Earth's climate. However, the speciation of particle-phase HOMs and its relationship with gas-phase HOM formation has been limited by the lack of suitable analytical techniques. Here, combining a novel particle evaporation inlet, the VIA (Vaporization Inlet for Aerosols), with a nitrate chemical ionization mass spectrometer (NO3-CIMS), gas- and particle-phase HOM products of α-pinene ozonolysis were studied under different conditions. Within the 50 min residence time of our Teflon chamber, we observed enhancement of C16–C19 HOM dimers in particles compared to the HOMs that were condensing. In particular, gas-phase dimer formation was considerably suppressed in experiments with the addition of CO or NO, but dimers still made up a considerable fraction of the observed SOA. In addition to the generally shorter carbon skeletons of the particle-phase dimers (i.e., C16–C19) compared to the gas phase (C19–C20), average O/C ratios of the HOMs (especially in the dimer range) also decreased slightly in the particle phase. C17H26Oz compounds, which have often been reported by previous offline measurements, dominate the particle-phase HOM mass spectra in α-pinene ozonolysis experiments. Our results indicate that these C17 compounds might be related to particle-phase processes within 1 h after HOM condensation. However, the new VIA–NO3-CIMS system used in this work will require more detailed characterization to better understand how the thermal desorption and wall effects may modify the measured particle-phase HOM distributions. Nevertheless, organic nitrate, for example, measured by this novel VIA–NO3-CIMS system was consistent with the measurements of an Aerodyne aerosol mass spectrometer (AMS), showing the capability of this system as a promising technique for particle-phase HOM measurements. Taken together, we believe that this system is a promising technique for combined online gas- and particle-phase HOM measurements.

Abstract. As a major source of ultrafine particles, new particle formation (NPF) occurs frequently in various environments. However, the survival of new particles and the frequent occurrence of NPF events in polluted environments have long been perplexing, since new particles are expected to be scavenged by high coagulation sinks. Towards solving these problems, we establish an experimental method and directly measure the effectiveness of the size-dependent coagulation sink of monodisperse 3–10 nm particles in well-controlled chamber experiments. Based on the chamber experiments and long-term atmospheric measurements from Beijing, we then discuss the survival of new particles in polluted environments. In the chamber experiments, the measured coagulation coefficient increases significantly with a decreasing particle size, whereas it is not sensitive to the compositions of test particles. Comparison between the measured coefficient with theoretical predictions shows that almost every coagulation leads to the scavenging of one particle, and the coagulation sink exceeds the hard-sphere kinetic limit due to van der Waals attractive force. For urban Beijing, the effectiveness of coagulation sink and a moderate or high (e.g., > 3 nm h-1) growth rate of new particles can explain the occurrence of measured NPF events; the moderate growth rate further implies that in addition to gaseous sulfuric acid, other gaseous precursors also contribute to the growth of new particles.

Abstract. Highly oxygenated organic molecules (HOM) are important for the formation of secondary organic aerosol (SOA), which poses serious health risks and exerts great influence on Earth’s climate. However, the speciation of particle-phase HOM and its relationship with gas-phase HOM formation has been limited by the lack of suitable analytical techniques. Here, combining a novel particle evaporation inlet VIA (Volatilization Inlet for Aerosols) with a nitrate chemical ionization mass spectrometer (NO3-CIMS), gas- and particle-phase HOM products of α-pinene ozonolysis were studied under different conditions. Within the 50-min residence time of our Teflon chamber, we observed enhancement of C16-C19 HOM dimers in particles compared to the HOM that were condensing. In particular, gas-phase dimer formation was considerably suppressed in experiments with the addition of CO or NO, but dimers still made up a considerable fraction of the observed SOA. In addition to the generally shorter carbon skeletons of the particle phase dimers (i.e. C16-C19) compared to the gas phase (C19-C20), average O / C ratios of the HOM (especially in the dimer range) also decreased slightly in the particle phase. C17H26Oz compounds, which have often been reported by previous offline measurements, dominate the particle-phase HOM mass spectra in α-pinene ozonolysis experiments. Our results indicate that these C17 compounds might be related to particle-phase processes within one hour after HOM condensation. However, the new VIA-NO3-CIMS system used in this work will require more detailed characterization to better understand how the thermal desorption and wall effects may modify the measured particle-phase HOM distributions. Nevertheless, for example organic nitrate measured by this novel VIA-NO3-CIMS system was consistent with the measurements of an Aerodyne Aerosol Mass Spectrometer (AMS), showing the capability of this system as a promising technique for particle-phase HOM measurements. Taken together, we believe that this system is a promising technique for combined online gas- and particle-phase HOM measurements.

Abstract. As a major source of ultrafine particles, new particle formation (NPF) occurs frequently in various environments. However, the survival of new particles and the frequent occurrence of NPF events in polluted environments have long been perplexing, since new particles are expected to be scavenged by high coagulation sinks. Towards solving these problems, we establish an experimental method and directly measure the effectiveness of the size-dependent coagulation sink of monodisperse 3–10 nm particles in well-controlled chamber experiments. Based on the chamber experiments and long-term atmospheric measurements from Beijing, we then discuss the survival of new particles in polluted environments. In the chamber experiments, the measured coagulation sink of 3–10 nm particles increases significantly with a decreasing particle size, whereas it is not sensitive to the compositions of test particles. Comparison between the measured coagulation coefficient with theoretical predictions shows that almost every coagulation leads to the scavenging of one particle, and the coagulation sink exceeds the hard-sphere kinetic limit due to van der Waals attractive force. For urban Beijing, the effectiveness of the coagulation sink and a moderate or high (e.g., > 3 nm h−1) growth rate of new particles can explain the occurrence of measured NPF events; the moderate growth rate further implies that, in addition to gaseous sulfuric acid, other gaseous precursors also contribute to the growth of new particles.