Search

This study introduces an innovative outdoor nephelometer system designed to monitor the dynamic hygroscopic behavior of aerosols in ambient air. Field measurements conducted in the Pearl River Delta region of China unveil significant roles of relative humidity (RH) swings on aerosol phase states. Highlighting the occurrence of aerosol crystallization in the afternoon followed by gradual deliquescence as RH increases, particularly when minimum afternoon RH drops below 35%, with no such behavior observed when it exceeds 40%. Emphasizing that aerosol phase states are shaped not only by RH and chemical composition but also by their RH history, illustrating that RH levels of 70% in the morning or evening may correspond to fully dissolved metastable or partially dissolved metastable states of ambient aerosols. These findings underscore the need to account for RH history when predicting aerosol phase states and have broader implications for comprehending aerosol behavior and its atmospheric impacts. Plain Language Summary: This research introduces a new device to study how tiny particles called atmospheric aerosols in the air behave when they encounter moisture. We tested it in a region of China and discovered that relative humidity fluctuations from morning to evening impact significantly on phase state of atmospheric aerosols. In the afternoon, some of the particles might become solid, like tiny crystals, and later turn into liquid gradually as humidity increases. This phenomenon occurs when the afternoon minimum relative humidity is low, below 35%, but does not take place when it exceeds 40%. Suggesting that relative humidity history matters for aerosol phase. For example, relative humidity of 70% in the morning or evening, particles may be in a liquid or semi‐liquid state. This study helps us understand phase changes of atmospheric particles and their effects on our environment. Key Points: Innovative outdoor nephelometer system was developed to monitor aerosol hygroscopic behavior in ambient airAerosol crystallization in the afternoon followed by gradual deliquescence observedRelative humidity history plays significant roles in determining aerosol phase state [ABSTRACT FROM AUTHOR]

Activation of biomass burning aerosols (BBA) and fossil fuel combustion aerosols (FFA) in fogs and clouds significantly impact regional air quality through aqueous chemistry and climate by affecting cloud microphysics. However, we lack direct observations of how these aerosols behave in fogs and clouds. Using a newly developed aerosol‐cloud sampling system, we conducted observations during fog events and found that BBA, despite their high organic content, effectively contributed to super‐micron interstitial aerosols and fog droplets in low supersaturation fogs. In contrast, FFA, predominantly externally mixed organic, did not grow beyond the super‐micron size in fogs due to their near‐hydrophobic nature. Measurements conducted under supersaturations relevant for cloud formation revealed that portions of FFA could serve as cloud condensation nuclei, but only when supersaturation exceeded ∼0.14%. These findings have broad implications for future investigations into the influence of BBA and FFA on fog and cloud chemistry and their interactions with clouds. Plain Language Summary: Tiny particles, known as aerosols, emitted from combustion of biomass and fossil fuels, can impact air quality and global climate by interacting with fog and clouds. However, we lack direct observational evidence of how these aerosols behave in these conditions. In our study, we developed an advanced aerosol‐cloud sampling system to observe aerosol activation during fog events. Our findings highlight a crucial factor of aerosol activation: the mixing of these aerosols. Biomass burning aerosols with an internal mixture of organic and inorganic components activate more easily, even in conditions with low supersaturation like fog. In contrast, fossil fuel combustion aerosols are often externally mixed and almost water‐repellent, requiring higher supersaturation to become cloud condensation nuclei. Understanding these distinctions has significant implications for regional air quality and the intricate interactions between aerosols and clouds. By gaining insights into how various aerosols interact with fog and clouds, we can enhance our understanding of their impact on our environment and climate. Key Points: Advanced Aerosol‐Cloud sampling system was developed to characterize aerosol activation in fogsBiomass burning aerosols efficiently form fog droplets, while fossil fuel combustion aerosols are almost hydrophobic and don't contributeFossil fuel combustion organic aerosols can serve as CCN in high supersaturation conditions (>0.14%) [ABSTRACT FROM AUTHOR]

The commercial continuous‐flow streamwise thermal‐gradient cloud condensation nuclei (CCN) counter is widely used in aerosol CCN activity measurements which are critical for investigating aerosol‐cloud interactions. In CCN measurements, a critical threshold is needed for distinguishing interstitial aerosols and activated droplets, and a default threshold of 0.75 μm was set in CCN counter. Theoretically, interstitial aerosols could also grow larger than 0.75 μm in CCN counter at low supersaturations, thus theoretical thresholds derived from the Köhler theory were suggested. Here, we report that droplet growth in the CCN counter is kinetically limited and CCN‐active droplets does not reach their theoretical diameters under low supersaturations. Neglecting the kinetic growth limitation in CCN identification would count less CCN and underestimate the aerosol hygroscopicity parameter κ $\kappa $ by up to 50% for supersaturations lower than 0.1%. We recommend that thresholds considering kinetic limitations should be used as new criteria for CCN identification under low supersaturations. Plain Language Summary: Accurate Cloud Condensation Nuclei (CCN) predictions in climate and regional models are crucial for the assessment of climate effects of aerosol‐cloud interactions. Direct measurements of CCN activity, varied by aerosol size, hygroscopicity, and supersaturation, are important for model verifications and improvements. The commercial continuous‐flow streamwise thermal‐gradient CCN counter (CCNC) is widely used in CCN activity measurements. We found that the droplet growth in the CCNC is kinetically limited under low supersaturations (<0.14%), thus not reaching the theoretical critical activation diameter, which significantly affect CCN identification. Kinetic model results revealed that the wet diameter thresholds of CCN identification that took the kinetic limitations of droplet growth into account were independent of dry aerosol size and hygroscopicity thus could be directly used as new criteria for CCN identification. Neglecting the kinetic growth limitation in CCN identification would result in significant bias in CCN activity measurements and thus supersaturated aerosol hygroscopicity retrievals. Findings of this research have significant impacts on CCN activity measurements and supersaturated aerosol hygroscopicity investigations. Key Points: Limited hygroscopic growth of cloud condensation nuclei (CCN) in CCN counter is recognized and evaluated based on model analysisKinetic limitations in CCN counter impacts significantly on size‐resolved CCN activity measurementsKinetic limitations in CCN counter impacts significantly on aerosol hygroscopicity measurements under low supersaturation [ABSTRACT FROM AUTHOR]

Submicron aerosol (PM1) species measured by aerosol mass spectrometers have been widely used to validate chemical transport models; however, the uncertainties due to chemical differences between PM1 and PM2.5 are poorly constrained. Here we characterized such differences in a highly polluted environment in north China in winter. Our results showed that the changes in PM1/PM2.5 ratios as a function of relative humidity (RH) were largely different for primary and secondary species. Secondary organic and inorganic aerosol (SOA and SIA) presented clear decreases in PM1/PM2.5 ratios at RH > 60% during periods with high SIA contributions (>50%), likely driven by the changes in aerosol hygroscopicity and phase states, while the traffic and coal combustion OA had limited dependence on RH. Thermodynamic modeling showed negligible impacts of PM differences on predictions of particle acidity, yet these impacts can cause a difference in aerosol water content by up to 50–70%. Plain Language Summary: Current air pollution studies rely largely upon aerosol mass spectrometers that provide real‐time measurements of submicron aerosol (PM1) species, and in many studies, PM1 aerosol species are used to validate those of PM2.5 in chemical transport models and estimate particle acidity and aerosol water content which are key parameters in studying heterogeneous reactions. However, the uncertainties in air pollution studies due to the chemical differences of PM1 and PM2.5 are poorly constrained, particularly in highly polluted environment, for example, China and India. We found that the changes in PM1/PM2.5 ratios as a function of relative humidity were largely different for primary and secondary aerosol species in highly polluted environment, which was likely driven by the changes in aerosol hygroscopicity and phase states. The chemical differences of PM1/PM2.5 ratios were also found to have negligible impacts on predictions of particle acidity, yet these impacts can cause a difference in aerosol water content by up to 50–70%. Considering the rapid increases in the deployments of aerosol mass spectrometers worldwide, the results in this study are of great importance for a better understanding of the uncertainties in both modelling and observations. Key Points: We observed large chemical differences between PM1 and PM2.5 under high relative humidity periods in highly polluted environmentThe RH dependence of PM1/PM2.5 ratios of primary and secondary species was largely different due to different hygroscopicityThe chemical differences between PM1 and PM2.5 have negligible influences on particle acidity prediction, yet have a large impact on AWC [ABSTRACT FROM AUTHOR]