Aerosol Nucleation Research Articles

Molecular Mechanisms of Aerosol Nucleation: from CLOUD Chamber Experiments to Field Observations

Atmospheric aerosol particles contribute to over four million premature deaths annually and play a critical role in modulating Earth’s climate. Most atmospheric particles and more than 50% of the cloud condensation nuclei are formed through a secondary process named new particle formation involving unique precursor vapors. This article summarizes current knowledge of how new atmospheric particles form, based on experiments at the CERN CLOUD chamber. While the role of sulfuric acid has long been known, other vapors like highly oxygenated organic molecules and iodine oxoacids are also important, along with stabilizers like ammonia, amines, and ions from cosmic rays. We explain how findings from CLOUD experiments help us understand particle formation in various atmospheric conditions and improve air quality and climate models.

Enhancement of atmospheric nucleation precursors on formic sulfuric anhydride induced nucleation: Theoretical mechanism

As an intermediate formed by H2SO4 (SA), formic sulfate anhydride (FSA) has been hypothesized to play a role in the nucleation of atmospheric aerosols. It is the first time that the clusters (SA)x(A)y(W)n and (FSA)x(A)y(W)n (x = 1–2; y = 1–2; n = 0–4) were systematically studied in theory on the structures, thermodynamics, intermolecular interactions, humidity dependence, atmospheric dependence and optical properties. FSA is predicted to be more stronger to promote the clustering with ammonia (A) than SA, suggesting that substituent group enhances nucleation capability of FSA. Whereas, the substituent group does not influence the humidity sensitivity of hydrated clusters. The clusters trend to form small hydrated clusters (nwater≦3). The study on atmospheric dependence indicates that the stability of the clusters depends more on temperature other than pressure. Moreover, FSA shows a stronger ability on reducing atmospheric visibility than A, SA and water molecules. This finding aims to draw attention to FSA about atmospheric nucleation.

Global modeling of aerosol nucleation with a semi-explicit chemical mechanism for highly oxygenated organic molecules (HOMs)

Abstract. New particle formation (NPF) involving organic compounds has been identified as an important process affecting aerosol particle number concentrations in the global atmosphere. Laboratory studies have shown that highly oxygenated organic molecules (HOMs) can make a substantial contribution to NPF, but there is a lack of global model studies of NPF with detailed HOM chemistry. Here, we incorporate a state-of-the-art biogenic HOM chemistry scheme with 96 chemical reactions to a global chemistry–climate model and quantify the contribution to global aerosols through HOM-driven NPF. The updated model captures the frequency of NPF events observed at continental surface sites (normalized mean bias changes from −96 % to −15 %) and shows reasonable agreement with measured rates of NPF and sub-20 nm particle growth. Sensitivity simulations show that compared to turning off the organic nucleation rate, turning off organic initial growth results in a more substantial decrease in aerosol number concentrations. Globally, organics contribute around 45 % of the annual mean vertically integrated nucleation rate (at 1.7 nm) and 25 % of the vertically averaged growth rate. The inclusion of HOM-related processes leads to a 39 % increase in the global annual mean aerosol number burden and a 33 % increase in cloud condensation nuclei (CCN) burden at 0.5 % supersaturation compared to a simulation with only inorganic nucleation. Our work predicts a greater contribution of organic nucleation to NPF than previous studies due to the semi-explicit HOM mechanism and an updated inorganic NPF scheme. The large contribution of biogenic HOMs to NPF on a global scale could make aerosol sensitive to changes in biogenic emissions.

Validating a microphysical prognostic stratospheric aerosol implementation in E3SMv2 using observations after the Mount Pinatubo eruption

Abstract. This paper describes the addition of a stratospheric prognostic aerosol (SPA) capability – developed with the goal of accurately simulating sulfate aerosol formation and evolution in the stratosphere – in the Department of Energy (DOE) Energy Exascale Earth System Model, version 2 (E3SMv2). The implementation includes changes to the four-mode Modal Aerosol Module microphysics in the stratosphere to allow for larger particle growth and more accurate stratospheric aerosol lifetime following the Pinatubo eruption. E3SMv2-SPA reasonably reproduces stratospheric aerosol lifetime, burden, aerosol optical depth, and top-of-atmosphere flux when compared to remote sensing observations. E3SMv2-SPA also has close agreement with the interactive chemistry–climate model CESM2-WACCM (Community Earth System Model version 2–Whole Atmosphere Community Climate Model) – which has a more complete chemical treatment – and the observationally constrained, prescribed volcanic aerosol treatment in E3SMv2. Global stratospheric aerosol size distributions identify the nucleation and growth of sulfate aerosol from volcanically injected SO2 from both major and minor volcanic eruptions from 1991 to 1993. The modeled aerosol effective radius is consistently lower than satellite and in situ measurements (max differences of ∼ 30 %). Comparisons with in situ size distribution samples indicate that this simulated underestimation in both E3SMv2-SPA and CESM2-WACCM is due to overly small accumulation and coarse-mode aerosols 6–18 months post-eruption, with E3SMv2-SPA simulating ∼ 50 % of the coarse-mode geometric mean diameters of observations 11 months post-eruption. Effective radii from the models and observations are used to calculate offline scattering and absorption efficiencies to explore the implications of smaller simulated aerosol size for the Pinatubo climate impacts. Scattering efficiencies at wavelengths of peak solar irradiance (∼ 0.5 µm) are 10 %–80 % higher for daily samples in models relative to observations through 1993, suggesting higher diffuse radiation at the surface and a larger cooling effect in the models due to the smaller simulated aerosol; absorption efficiencies at the peak wavelengths of outgoing terrestrial radiation (∼ 10 µm) are 15 %–40 % lower for daily samples in models relative to observations, suggesting an underestimation in stratospheric heating in the models due to the smaller simulated aerosol. These potential biases are based on aerosol size alone and do not take into account differences in the aerosol number. The overall agreement of E3SMv2-SPA with observations and its similar performance to the well-validated CESM2-WACCM makes E3SMv2-SPA a viable alternative to simulating climate impacts from stratospheric sulfate aerosols.

Supersaturation and Critical Size of Cloud Condensation Nuclei in Marine Stratus Clouds

AbstractObservations of marine stratus clouds in clean air off the Californian coast reveal a functional relationship between the number of cloud condensation nuclei (CCN) and supersaturation. Satellite‐derived liquid droplet density estimates the number density of CCN. Combining the estimated supersaturation using Köhler theory, global maps of supersaturation and the critical activation size of CCN are estimated. Here, we show that high supersaturation >0.5% persists over the oceans with a critical CCN size of 25–30 nm, which is smaller than the conventional wisdom of 60 nm. Independent support for such high supersaturation in the marine cloud is obtained from CCN measurements provided by the “Atmospheric Tomography Mission.” Higher supersaturation implies smaller activation size for CCN making cloud formation more sensitive to changes in aerosol nucleation.

Low-temperature ice nucleation of sea spray and secondary marine aerosols under cirrus cloud conditions

Abstract. Sea spray aerosols (SSAs) represent one of the most abundant aerosol types on a global scale and have been observed at all altitudes including the upper troposphere. SSA has been explored in recent years as a source of ice-nucleating particles (INPs) in cirrus clouds due to the ubiquity of cirrus clouds and the uncertainties in their radiative forcing. This study expands upon previous works on low-temperature ice nucleation of SSA by investigating the effects of atmospheric aging of SSA and the ice-nucleating activity of newly formed secondary marine aerosols (SMAs) using an oxidation flow reactor. Polydisperse aerosol distributions were generated from a marine aerosol reference tank (MART) filled with 120 L of real or artificial seawater and were dried to very low relative humidity to crystallize the salt constituents of SSA prior to their subsequent freezing, which was measured using a continuous flow diffusion chamber (CFDC). Results show that for primary SSA (pSSA), as well as aged SSA and SMA (aSSA+SMA) at temperatures >220 K, homogeneous conditions (92 %–97 % relative humidity with respect to water – RHw) were required to freeze 1 % of the particles. However, below 220 K, heterogeneous nucleation occurs for both pSSA and aSSA+SMA at much lower RHw, where up to 1 % of the aerosol population freezes between 75 % and 80 % RHw. Similarities between freezing behaviors of the pSSA and aSSA+SMA at all temperatures suggest that the contributions of condensed organics onto the pSSA or alteration of functional groups in pSSA via atmospheric aging did not hinder the major heterogeneous ice nucleation process at these cirrus temperatures, which have previously been shown to be dominated by the crystalline salts. Occurrence of a 1 % frozen fraction of SMA, generated in the absence of primary SSA, was observed at or near water saturation below 220 K, suggesting it is not an effective INP at cirrus temperatures, similar to findings in the literature on other organic aerosols. Thus, any SMA coatings on the pSSA would only decrease the ice nucleation behavior of pSSA if the organic components were able to significantly delay water uptake of the inorganic salts, and apparently this was not the case. Results from this study demonstrate the ability of lofted primary sea spray particles to remain an effective ice nucleator at cirrus temperatures, even after atmospheric aging has occurred over a period of days in the marine boundary layer prior to lofting. We were not able to address aging processes under upper-tropospheric conditions.

HIO3-HIO2-Driven Three-Component Nucleation: Screening Model and Cluster Formation Mechanism.

Iodine oxoacids (HIO3 and HIO2)-driven nucleation has been suggested to efficiently contribute to new particle formation (NPF) in marine atmospheres. Abundant atmospheric nucleation precursors may further enhance HIO3-HIO2-driven nucleation through various multicomponent nucleation mechanisms. However, the specific enhancing potential (EP) of different precursors remains largely unknown. Herein, the EP-based screening model of precursors and enhancing mechanism of the precursor with the highest EP on HIO3-HIO2 nucleation were investigated. The formation free energies (ΔG), as critical parameters for evaluating EP, were calculated for the dimers of 63 selected precursors with HIO2. Based on the ΔG values, (1) a quantitative structure-activity relationship model was developed for evaluating ΔG of other precursors and (2) atmospheric concentrations of 63 (precursor)1(HIO2)1 dimer clusters were assessed to identify the precursors with the highest EP for HIO3-HIO2-driven nucleation by combining with earlier results for the nucleation with HIO3 as the partner. Methanesulfonic acid (MSA) was found to be one of the precursors with the highest EP. Finally, we found that MSA can effectively enhance HIO3-HIO2 nucleation at atmospheric conditions by studying larger MSA-HIO3-HIO2 clusters. These results augment our current understanding of HIO3-HIO2 and MSA-driven nucleation and may suggest a larger impact of HIO2 in atmospheric aerosol nucleation.

Development of the Reiss theory for binary homogeneous nucleation of aerosols

Development of the Reiss theory for binary homogeneous nucleation of aerosols

Evidence of nitrate-based nighttime atmospheric nucleation driven by marine microorganisms in the South Pacific.

Our understanding of ocean-cloud interactions and their effect on climate lacks insight into a key pathway: do biogenic marine emissions form new particles in the open ocean atmosphere? Using measurements collected in ship-borne air-sea interface tanks deployed in the Southwestern Pacific Ocean, we identified new particle formation (NPF) during nighttime that was related to plankton community composition. We show that nitrate ions are the only species for which abundance could support NPF rates in our semicontrolled experiments. Nitrate ions also prevailed in the natural pristine marine atmosphere and were elevated under higher sub-10 nm particle concentrations. We hypothesize that these nucleation events were fueled by complex, short-term biogeochemical cycling involving the microbial loop. These findings suggest a new perspective with a previously unidentified role of nitrate of marine biogeochemical origin in aerosol nucleation.

Cyclic Appearance and Disappearance of Aerosol Nucleation in the Boundary Layer of Drops of Volatile Liquid

The cyclic appearance and disappearance of nucleation was observed in the boundary layer of drops of 1,3-propanediol, 1,2-propanediol, and glycerol, close to the boiling point and exposed to a cooler airflow. Although continuous nucleation has previously been widely observed, the cyclic nature of the phenomenon observed here is unusual. It was observed in experiments with free-falling drops and fixed drops in an upflow of air. To investigate this unexpected phenomenon further, the phenomenon was reproduced in two finite volume models. The first model used 1D potential flow solutions to approximate the airflow around the spherical windward face of the droplet. The second model used CFD to model the airflow. Both models used classical nucleation theory, the Stefan–Fuchs model of droplet growth by condensation, mass transfer by evaporation, diffusion, convection, and heat transfer by diffusion and convection. Despite several simplifications, the most important being the assumption that the drop has a uniform temperature, both models predict the frequency of nucleation to be better than the order of magnitude. These models also predict the experimentally observed power law dependence of nucleation frequency on air speed. It is proposed that the cyclic nature of the phenomenon is caused by the following process: the depletion of condensable vapour around the freshly nucleated aerosol due to condensation onto the aerosol results in reduced supersaturation, which stops further nucleation, and then the replenishment of this vapour by diffusion and convection from the parent drop, with nucleation of aerosol recommencing when the supersaturation has recovered sufficiently—then, the repetition of these steps in a cycle. It is proposed that the process depends mostly on the maximum saturation ratio in the boundary layer, which itself is determined by four key dimensionless numbers: the Lewis number, the Peclet number, the Reynolds number, and the ratio of the vapour pressure of the condensable compound at drop surface temperature to the vapour pressure of the same species at ambient temperature. A practical application of the phenomenon may be as a means of validation of thermo-fluid models, which include nucleation.

Description and performance of a sectional aerosol microphysical model in the Community Earth System Model (CESM2)

Abstract. We implemented the Community Aerosol and Radiation Model for Atmospheres (CARMA) in both the high- and low-top model versions of the Community Earth System Model Version 2 (CESM2). CARMA is a sectional microphysical model, which we use for aerosol in both the troposphere and stratosphere. CARMA is fully coupled to chemistry, clouds, radiation, and transport routines in CESM2. This development enables the comparison of simulations with a sectional (CARMA) and a modal (MAM4) aerosol microphysical model in the same modeling framework. The new implementation of CARMA has been adopted from previous work, with some additions that align with the current CESM2 Modal Aerosol Model (MAM4) implementation. The main updates include an interactive secondary organic aerosol description in CARMA, using the volatility basis set (VBS) approach, updated wet removal, and the use of transient emissions of aerosols and trace gases. In addition, we implemented an alternative aerosol nucleation scheme in CARMA, which is also used in MAM4. Detailed comparisons of stratospheric aerosol properties after the Mount Pinatubo eruption reveal the importance of prescribing sulfur injections in a larger region rather than in a single column to better represent the observed evolution of aerosols. Both CARMA and MAM4 in CESM2 are able to represent stratospheric and tropospheric aerosol properties reasonably well when compared to observations. Several differences in the performance of the two aerosol models show, in general, an improved representation of aerosols when using the sectional aerosol model in CESM2. These include a better representation of the aerosol size distribution after the Mount Pinatubo volcanic eruption in CARMA compared to MAM4. MAM4 produces on average smaller aerosols and less removal than CARMA, which results in a larger total mass. Both CARMA and MAM4 reproduce the stratospheric aerosol optical depth (AOD) within the error bar of the observations between 2001 and 2020, except for recent larger volcanic eruptions that are overestimated by both model configurations. The CARMA background surface area density and aerosol size distribution in the stratosphere and troposphere compare well to observations, with some underestimation of the Aitken-mode size range. MAM4 shows shortcomings in reproducing coarse-mode aerosol distributions in the stratosphere and troposphere. This work outlines additional development needs for CESM2 CARMA to improve the model compared to observations in both the troposphere and stratosphere.

Enthalpy effect on the kinetics of concurrent nucleation and chemical aging of aqueous organic aerosols: The stage of thermal relaxation

The size and composition distribution of an ensemble of aqueous organic droplets, evolving via nucleation and concomitant chemical aging, may be affected by the latent heat of condensation and enthalpy of heterogeneous chemical reactions, so the temperature of the droplet may deviate from the air temperature and thus become an independent variable of its state (additional to its size and composition variables). Using the formalism of the classical nucleation theory, we derive a partial differential equation for the temporal evolution of the distribution of an ensemble of such droplets with respect to all their variables of state via Taylor series expansions of the corresponding multidimensional discrete equation of balance, describing the material and heat exchange between droplets and air. The resulting kinetic equation goes beyond the framework of the Fokker-Planck approximation with respect to the temperature variable. A hierarchy of time scales of nonisothermal nucleation and concomitant chemical aging of aqueous organic aerosols is established and an analytical description of their thermal relaxation stage is developed, allowing one to estimate the characteristic time of the establishment of the equilibrium distribution of aerosol particles with respect to their temperatures. Theoretical results are illustrated with numerical calculations for the concurrent nucleation and chemical aging of model aqueous hydrophilic-hydrophobic organic aerosols in air.

Contribution of regional aerosol nucleation to low-level CCN in an Amazonian deep convective environment: results from a regionally nested global model

Abstract. Global model studies and observations have shown that downward transport of aerosol nucleated in the free troposphere is a major source of cloud condensation nuclei (CCN) to the global boundary layer. In Amazonia, observations show that this downward transport can occur during strong convective activity. However, it is not clear from these studies over what spatial scale this cycle of aerosol formation and downward supply of CCN is occurring. Here, we aim to quantify the extent to which the supply of aerosol to the Amazonian boundary layer is generated from nucleation within a 1000 km regional domain or from aerosol produced further afield and the effectiveness of the transport by deep convection. We run the atmosphere-only configuration of the HadGEM3 climate model incorporating a 440 km × 1080 km regional domain over Amazonia with 4 km resolution. Simulations were performed over several diurnal cycles of convection. Below 2 km altitude in the regional domain, our results show that new particle formation within the regional domain accounts for only between 0.2 % and 3.4 % of all Aitken and accumulation mode aerosol particles, whereas nucleation that occurred outside the domain (in the global model) accounts for between 58 % and 81 %. The remaining aerosol is primary in origin. Above 10 km, the regional-domain nucleation accounts for up to 66 % of Aitken and accumulation mode aerosol, but over several days very few of these particles nucleated above 10 km in the regional domain are transported into the boundary layer within the 1000 km region, and in fact very little air is mixed that far down. Rather, particles transported downwards into the boundary layer originated from outside the regional domain and entered the domain at lower altitudes. Our model results show that CCN entering the Amazonian boundary layer are transported downwards gradually over multiple convective cycles on scales much larger than 1000 km. Therefore, on a 1000 km scale in the model (approximately one-third the size of Amazonia), trace gas emission, new particle formation, transport and CCN production do not form a “closed loop” regulated by the biosphere. Rather, on this scale, long-range transport of aerosol is a much more important factor controlling CCN in the boundary layer.

The neglected autoxidation pathways for the formation of highly oxygenated organic molecules (HOMs) and the nucleation of the HOMs generated by limonene

Recent ambient atmospheric measurements have observed highly oxygenated organic molecules (HOMs) at a number of sites. Monoterpenes, in particular, are inclined to autoxidize to form HOMs with different oxidants such as OH and O3. However, little is known about the formation and nucleation of the HOMs in the presence of water (W). In this study, we investigated oxidation mechanism of O3 addition to limonene in the gas and water phase by theoretical chemistry calculations. Besides, the mechanism of the formation of HOMs from photochemical reactions of limonene and the role of HOMs in new particle formation (NPF) with aerosol nucleation precursors, including sulfuric acid (SA), W and ions were investigated by means of molecular dynamics (MD) simulations and theoretical chemistry calculations. The rate constants of initiation reactions for O3 addition to limonene are suppressed as the temperature increases. In the process of ion-induced nucleation, HOMs can dominate the initial nucleation steps. The MD results indicated that HOMs can self-aggregate into clusters and W molecules are beneficial to promote the NPF of HOMs. In addition, the nucleation ability of HOMs have significant correlation with the oxygen-to-carbon (O/C) ratio of HOMs. The theoretical results proved the neglected autoxidation pathways including (i) the formation of an endoperoxide moiety in HOMs (ii) a CO2 elimination in presence of an unsaturated peroxy acyl radical. The current study provide valuable insight into NPF mechanism of (HOMs) (SA) and (HOMs) (ion) in the presence of W.

Role of Methanesulfonic Acid in Sulfuric Acid-Amine and Ammonia New Particle Formation.

Aerosol nucleation accounts for over half of all seed particles for cloud droplet formation. In the atmosphere, sulfuric acid (SA) nucleates with ammonia, amines, oxidized organics, and many more compounds to form particles. Studies have also shown that methanesulfonic acid (MSA) nucleates independently with amines and ammonia. MSA and SA are produced simultaneously via dimethyl sulfide oxidation in the marine atmosphere. However, limited knowledge exists on how MSA and SA nucleate together in the presence of various atmospherically relevant base compounds, which is critical to predicting marine nucleation rates accurately. This work provides experimental evidence that SA and MSA react to form particles with amines and that the SA-MSA-base nucleation has different reaction pathways than SA-base nucleation. Specifically, the formation of the SA-MSA heterodimer creates more energetically favorable pathways for SA-MSA-methylamine nucleation and an enhancement of nucleation rates. However, SA-trimethylamine nucleation is suppressed by MSA, likely due to the steric hindrance of the MSA and trimethylamine. These results display the importance of including nucleation reactions between SA, MSA, and various amines to predict particle nucleation rates in the marine atmosphere.

Simulation of Cocrystal Formation in Planetary Atmospheres: The C6H6:C2H2 Cocrystal Produced by Gas Deposition.

The formation of molecular cocrystals in condensed aerosol particles has been recently proposed as an efficient pathway for generation of complex organics in Titan's atmosphere. It follows that cocrystal precipitation may facilitate the transport of biologically important precursors to the surface to be sequestered in an organic karstic and sand environment. Recent laboratory studies on these planetary minerals have predominantly synthesized cocrystals by the controlled freezing of binary mixtures from the liquid phase, allowing for their structural and spectroscopic characterization. However, these techniques are perhaps not best representative of aerosol nucleation and growth microphysics in planetary atmospheres. Herein, we report the first synthesis of the known 1:1 C6H6:C2H2 cocrystal using vapor deposition methods onto a cryogenically cooled substrate. Subsequent transmission FTIR spectroscopy has confirmed the formation of the empirical C6H6:C2H2 cocrystal structure via the observation of diagnostic infrared spectral features. Predicted by periodic-DFT calculations, altered vibrational profiles depict a changing site symmetry of the C6H6 and C2H2 components after transition to the cocrystal unit cell geometry. The 80 K temperature of the cocrystal phase transition overlaps with the condensation curves obtained for both species in Titan's lower stratosphere, revealing that the cocrystal may act as an important environment for photo- and radio-lytic processes leading to the formation of higher order organics in Titan's atmosphere. Such solid-state astrochemistry can now be pursued in oxygen-free laboratory settings under (ultra)high vacuum using standard surface science setups.

Benchmarking general neural network potential ANI‐2x on aerosol nucleation molecular clusters

AbstractNew particle formation including atmospheric aerosol nucleation and subsequent growth, contributes to about half of cloud condensation nuclei and can grow to form haze under certain conditions, so its role in climate change and air quality is indispensable. However, various kinds of nucleation precursors create vast combinations of molecular clustering, hindering the understanding the detailed picture of nucleation mechanism. The recently appeared general neural network potential, ANI‐2x, covering most of elements composing nucleation clusters, looks promising to be embedded into the nucleation theoretical workflows to improve the nucleation simulation accuracy. Here we benchmarked ANI‐2x's performance on both low and high energy isomers based workflows through comparing it with semi‐empirical (PM7) and DFT (ωB97XD/6‐31++G(d,p)) methods. Results show that ANI‐2x is superior to PM7 in single point energy and geometry optimization calculations when compared against DFT. However, generally ANI‐2x's accuracy on high energy isomers is still far less than that on low energy isomers. Besides, force comparison indicates that PM7's accuracy is better than that of ANI‐2x. After all, accuracy of the workflow that focuses on low energy isomers can be benefitted from ANI‐2x while for high energy isomers based workflow, PM7 is still the better choice than ANI‐2x due to the more important role of force labels than that of energy labels in preparing machine learning dataset. However, due to the linear relation between the ANI‐2x force and DFT force, a scale factor of approximately 0.50 is expected to greatly improve the ANI‐2x force performance.

Enhancing acid-base-water ternary aerosol nucleation with organic acid: a case of tartaric acid.

The new particle formation (NPF) process has been observed globally in clean and polluted environments, where the fundamental mechanisms leading to multicomponent aerosol formation remain elusive. Dicarboxylic acids play an important role in atmospheric NPF. In this study, theoretical calculations are performed to assess the effect of tartaric acid (TA) on the formation of clusters consisting of sulfuric acid (SA), ammonia (AM) or amines (methylamine or dimethylamine, MA/DMA) in the presence of water. Both carboxyl groups and hydroxyl groups in the carbon chain of TA could be involved in hydrogen bonds. The presence of TA triggers proton transfer from SA to the base molecule to form new covalent bonds or strengthens the preexisting covalent bonds, hence, all the hydrated (SA)(TA)(base) cluster formations by adding one TA molecule to the (SA)(base) hydrates are energetically favorable. The dipole-dipole interaction is not only related to the Gibbs energy change for acid affinity reactions to (SA)(W)n and (SA)(base)(W)n (n = 0-4) clusters but also positively related to the reaction rate constant. These results combined with preliminary kinetic results indicate that TA is very likely to participate in clustering and promote subsequent growth involving hydrated SA and (SA)(base) clusters. In addition, our results further indicate that the NPF process can be promoted by multicomponent nucleation involving organic acids, SA, and base species, which will help in understanding NPF in polluted areas and improving global and regional models.

Towards fully ab initio simulation of atmospheric aerosol nucleation

Atmospheric aerosol nucleation contributes to approximately half of the worldwide cloud condensation nuclei. Despite the importance of climate, detailed nucleation mechanisms are still poorly understood. Understanding aerosol nucleation dynamics is hindered by the nonreactivity of force fields (FFs) and high computational costs due to the rare event nature of aerosol nucleation. Developing reactive FFs for nucleation systems is even more challenging than developing covalently bonded materials because of the wide size range and high dimensional characteristics of noncovalent hydrogen bonding bridging clusters. Here, we propose a general workflow that is also applicable to other systems to train an accurate reactive FF based on a deep neural network (DNN) and further bridge DNN-FF-based molecular dynamics (MD) with a cluster kinetics model based on Poisson distributions of reactive events to overcome the high computational costs of direct MD. We found that previously reported acid-base formation rates tend to be significantly underestimated, especially in polluted environments, emphasizing that acid-base nucleation observed in multiple environments should be revisited.

Contribution of regional aerosol nucleation to low-level CCN in an Amazonian deep convective environment: results from a regionally nested global model

Contribution of regional aerosol nucleation to low-level CCN in an Amazonian deep convective environment: results from a regionally nested global model