Predicting Atmospheric Particle Phase State Using an Explainable Machine Learning Approach Based on Particle Rebound Measurements.

The particle phase state plays a vital role in the gas-particle partitioning, multiphase reactions, ice nucleation activity, and particle growth in the atmosphere. However, the characterization of the atmospheric phase state remains challenging. Herein, based on measured aerosol chemical composition and ambient relative humidity (RH), a machine learning (ML) model with high accuracy (R2 = 0.952) and robustness (RMSE = 0.078) was developed to predict the particle rebound fraction, f, which is an indicator of the particle phase state. Using this ML model, the f of particles in the urban atmosphere was predicted based on seasonal average aerosol chemical composition and RH. Regardless of seasons, aerosols remain in the liquid state of mid-high latitude cities in the northern hemisphere and in the semisolid state over semiarid regions. In the East Asian megacities, the particles remain in the liquid state in spring and summer and in the semisolid state in other seasons. The effects of nitrate, which is becoming dominant in fine particles in several urban areas, on the particle phase state were evaluated. More nitrate led the particles to remain in the liquid state at an even lower RH. This study proposed a new approach to predict the particle phase state in the atmosphere based on RH and aerosol chemical composition.

Observational evidence for the non-suppression effect of atmospheric chemical modification on the ice nucleation activity of East Asian dust.

Airborne mineral dust triggers ice formation in clouds and alters cloud microphysical properties by acting as ice-nucleating particles (INPs), potentially influencing weather and climate at regional and global scales. Anthropogenic pollution would modify natural mineral dust during the atmospheric transport process. However, the effects of anthropogenic pollution aging on the ice nucleation activity (INA) of mineral dust remain not well-understood. In this study, we investigated the immersion mode ice nucleation properties and particle chemical characterizations of collected size-resolved Asian dust samples (eight particle size classes ranging from 0.18 to 10.0 µm), and testified the chemical modification of aged dust particles via particle chemistry and morphology analyses including the mass concentrations of particulate matter, the water-soluble ion concentrations, the mental element concentrations, and single-particle morphology. The mass fraction of Ca2+ in element Ca and the mean relative mass proportions of supermicron Ca2+ increased by 67.0 % and 3.5-11.2 % in aged Asian dust particles, respectively, suggesting the occurrence of heterogeneous reactions. On the other hand, the total INP concentrations (total NINP) and total ice nucleation active site densities (total ns(T)) were consistent between aged and normal dust particles (0.62-1.18 times) without a statistically significant difference. And the NINP and ns(T) of chemically aged supermicron dust (1.0-10.0 µm) in each particle size class were nearly equal to or slightly higher than those of normal Asian dust, which were 0.70-2.45 times and 0.64-4.34 times at -18 °C, respectively. These results reveal that anthropogenic air pollution does not notably change the INP concentrations and does not impair the INA of Asian dust. Our work provides direct observational evidence and clarifies the non-suppression effect of anthropogenic air pollution on the INA of East Asian dust, advancing the understanding of the ice nucleation of airborne aged mineral dust.

Comparison of Phase States of PM2.5 over Megacities, Seoul and Beijing, and Their Implications on Particle Size Distribution.

Although the particle phase state is an important property, there is scant information on it, especially, for real-world aerosols. To explore the phase state of fine mode aerosols (PM2.5) in two megacities, Seoul and Beijing, we collected PM2.5 filter samples daily from Dec 2020 to Jan 2021. Using optical microscopy combined with the poke-and-flow technique, the phase states of the bulk of PM2.5 as a function of relative humidity (RH) were determined and compared to the ambient RH ranges in the two cities. PM2.5 was found to be liquid to semisolid in Seoul but mostly semisolid to solid in Beijing. The liquid state was dominant on polluted days, while a semisolid state was dominant on clean days in Seoul. These findings can be explained by the aerosol liquid water content related to the chemical compositions of the aerosols at ambient RH; the water content of PM2.5 was much higher in Seoul than in Beijing. Furthermore, the overall phase states of PM2.5 observed in Seoul and Beijing were interrelated with the particle size distribution. The results of this study aid in a better understanding of the fundamental physical properties of aerosols and in examining how these are linked to PM2.5 in polluted urban atmospheres.

The relative humidity-dependent viscosity of single quasi aerosol particles and possible implications for atmospheric aerosol chemistry.

Viscosity is a fundamental physicochemical property of aerosol particles that influences chemical evolution, mass transfer rates, particle formation, etc. and also changes with ambient relative humidity (RH). However, the viscosity of real individual aerosol particles still remains less understood. Here, we developed a novel optical system based on dual optical tweezers to measure the viscosity of single suspending aerosol droplets under different RH conditions. In our experiment, a pair of quasi atmospheric aerosol droplets composed of organic and inorganic chemical substances were trapped and levitated by dual laser beams, respectively, and then collided and coalesced. The backscattering light signals and bright-field images of the dynamic coalescence process were recorded to infer the morphological relaxation time and the diameter of the composited droplet. Then, the viscosity of the droplet was calculated based on these measured values. The ambient RH of the aerosol droplets was controlled by varying the relative flow rates of dry and humidified nitrogen gas in a self-developed aerosol chamber. The viscosities of single aqueous droplets nebulized with solutes of sucrose, various sulfates and nitrates, and organic/inorganic mixtures were measured over the atmospheric RH range. Besides, the viscosities of the proxies of actual ambient aerosols in Beijing were investigated, which reasonably interpreted the aerosol chemistry transforming from sulfate dominating to nitrate dominating at the PM10 (particulate matter with an aerodynamic diameter of less than 10 µm) level in the last decade in Beijing. Furthermore, the hygroscopicity of droplets with a solute of organic/inorganic mixtures was researched to obtain a deep insight into the relationship between the viscosity and mass transfer process. Hence, we provide a robust approach for investigating the viscosity and hygroscopicity of the actual individual liquid PM10 aerosols.

The particle phase state during the biomass burning events.

The phase state of biomass burning aerosols (BBA) remains largely unclear, impeding our understanding of their effects on air quality, climate and human health, due to its profound roles in mass transfer between gaseous and particulate phase. In this study, the phase state of BBA was investigated by measuring the particle rebound fraction ƒ combining field observations and laboratory experiments. We found that both ambient and laboratory-generated BBA had unexpectedly lower rebound fraction ƒ (<0.6) under the dry conditions (RH = 20-50%), indicating that BBA were in non-solid state at such low RH. This was obviously different from the secondary organic aerosols (SOA) derived from the oxidation of both anthropogenic and biogenic volatile organic compounds, typically with a rebound fraction ƒ larger than 0.8 at RH below 50%. Therefore, we proposed that the diffusion coefficient of gaseous molecular in the bulk of BBA might be much higher than SOA under the dry conditions.

Humidity-Dependent Phase State of Gasoline Vehicle Emission-Related Aerosols.

The phase states of primarily emitted and secondarily formed aerosols from gasoline vehicle exhausts were investigated by quantifying the particle rebound fraction (f). The rebound behaviors of gasoline vehicle emission-related aerosols varied with engines, fuel types, and photochemical aging time, showing distinguished differences from biogenic secondary organic aerosols. The nonliquid-to-liquid phase transition of primary aerosols emitted from port fuel injection (PFI) and gasoline direct injection (GDI) vehicles started at a relative humidity (RH) = 50 and 60%, and liquefaction was accomplished at 60 and 70%, respectively. The RH at which f declined to 0.5 decreased from 70 to 65% for the PFI case with 92# fuel, corresponding to the photochemical aging time from 0.37 to 4.62 days. For the GDI case, such RH enhanced from 60 to 65%. Our results can be used to imply the phase state of traffic-related aerosols and further understand their roles in urban atmospheric chemistry. Taking Beijing, China, as an example, traffic-related aerosols were mainly nonliquid during winter with the majority ambient RH below 50%, whereas they were mostly liquid during the morning rush hour of summer, and traffic-related secondary aerosols fluctuated between nonliquid and liquid during the daytime and tended to be liquid at night with increased ambient RH.

Aerosol Phase State and Its Link to Chemical Composition and Liquid Water Content in a Subtropical Coastal Megacity.

Particle phase state plays a key role in gas-particle partitioning, heterogeneous and multiphase reactions, and secondary aerosol formation. In this work, the rebound fraction and chemical composition of submicron particles were simultaneously measured to investigate the particle phase state and its link to chemical composition in a subtropical coastal urban city (Shenzhen, China). Submicron particles were found to be in the liquid state for most of the measurement period in spring. During the sampling time, both high relative humidity (RH, ranged from 40% to 93%) and inorganic mass fraction in particles (62.6 ± 12.4% of dry particles, on average) resulted in abundant aerosol liquid water (43 ± 6% in the wet PM1, on average), which may liquefy the particles. Considering the high frequency of ambient RH > 60% and large inorganic mass fraction in aerosol particles, we deduced that particles were in the liquid state throughout the year in coastal urban areas, where this study was performed. The liquid phase particles may accelerate the mass transfer of reactive trace gases and multiphase reactions, thereby enhanced secondary aerosol formation, further resulting in a rapid growth in aerosol mass. Our work suggested that in regions heavily impacted by SO2 and NO x emissions, especially in developing countries, the presence of inorganics could significantly impact the phase state of ambient aerosol particles, and thus the mixing state of inorganic and organic matter should be taken into account for the investigation of the aerosol phase state in urban environments.