Imaging Dissolution Dynamics of Individual NaCl Nanoparticles during Deliquescence with In Situ Transmission Electron Microscopy.

Water vapor condensation on hygroscopic aerosol particles plays an important role in cloud formation, climate change, secondary aerosol formation, and aerosol aging. Conventional understanding considers deliquescence of nanosized hygroscopic aerosol particles a nearly instantaneous solid to liquid phase transition. However, the nanoscale dynamics of water condensation and aerosol particle dissolution prior to and during deliquescence remain obscure due to a lack of high spatial and temporal resolution single particle measurements. Here we use real time in situ transmission electron microscopy (TEM) imaging of individual sodium chloride (NaCl) nanoparticles to demonstrate that water adsorption and aerosol particle dissolution prior to and during deliquescence is a multistep dynamic process. Water condensation and aerosol particle dissolution was investigated for lab generated NaCl aerosols and found to occur in three distinct stages as a function of increasing relative humidity (RH). First, a < 100 nm water layer adsorbed on the NaCl cubes and caused sharp corners to dissolve and truncate. The water layer grew to several hundred nanometers with increasing RH and was rapidly saturated with solute, as evidenced by halting of particle dissolution. Adjacent cube corners displayed second-scale curvature fluctuations with no net particle dissolution or water layer thickness change. We propose that droplet solute concentration fluctuations drove NaCl transport from regions of high local curvature to regions of low curvature. Finally, we observed coexistence of a liquid water droplet and aerosol particle immediately prior to deliquescence. Particles dissolved discretely along single crystallographic directions, separated by few second lag times with no dissolution. This work demonstrates that deliquescence of simple pure salt particles with sizes in the range of 100 nm to several microns is not an instantaneous phase transition and instead involves a range of complex dissolution and water condensation dynamics.

Toward an Understanding of Uric Acid Particle Dissolution: Surface and Bulk-Driven Water Activity.

Uric acid particles contribute to kidney stones, and natural processes for the elimination of stones depend on solute-solvent interactions. The process of uric acid dissolution has previously been understood via the lens of solubility; however, for pure and mixed salt solutions, these approaches do not provide a comprehensive picture of nanoscale particle solution thermodynamics. Unlike solubility measurements, water activity measurements provide us with information about the chemical potential responsible for the migration of water molecules driving the dissolution of particles. In this work, we used in situ experimental tools to estimate water activity values for pure uric acid aqueous droplets at different stages of droplet growth. The process of cloud formation, i.e., water condensation on a solute particle resulting in aqueous droplet formation, was leveraged to compare the water affinity for nanosized uric acid particles with a well-studied inorganic salt, sodium chloride. Specifically, we investigated microscopic uric acid particles (nanoparticles <300 nm, amorphous and super micron particles >5 µm, crystalline) and the mechanism of water uptake. The growth of droplet volume (Growth Factor, GF) for uric acid particles is experimentally observed for supermicrometer crystalline particles (>1 µm) at subsaturated humidity conditions (<100% RH). In addition, the water activity of submicrometer-size uric acid particles is estimated under subsaturated and supersaturated humidity conditions. These measurements provide us with information about the volume growth of droplets as water condenses in particles exposed to different humidity conditions. Our observations under subsaturated humidity conditions show that the uric acid particles have limited volume growth (<1% change per volume and <10% change per volume for crystalline and amorphous measurement, respectively). From the experimental data, the affinity of uric acid solute with water as a solvent is quantified in terms of water activity.

Solubility Considerations for Cloud Condensation Nuclei (CCN) Activity Analysis of Pure and Mixed Black Carbon Species.

Black carbon (BC) is an aerosol that is released into the atmosphere due to the incomplete burning of biomass and can affect the climate directly or indirectly. BC commonly mixes with other primary or secondary aerosols to undergo aging, thereby changing its radiative properties and cloud condensation nuclei (CCN) activity. The composition of aged BC species in the atmosphere is difficult to measure with high confidence, so their associated CCN activity can be uncertain. In this work, the CCN activity analysis of BC was performed using laboratory measurements of proxy aged BC species. Vulcan XC72R carbon black was used as the representative of BC, and three structural isomers of benzenedicarboxylic acid─phthalic acid (PTA), isophthalic acid (IPTA), and terephthalic acid (TPTA)─were mixed with BC to generate three different proxies of aged BC species. Most studies related to CCN activity analysis of BC aerosols use the traditional Köhler theory or an adsorption theory (such as the Frenkel-Halsey-Hill adsorption theory). PTA, IPTA, and TPTA fall in the sparingly water-soluble range and therefore do not fully obey either of the aforementioned theories. Consequently, a novel hybrid activity model (HAM) was used for the CCN activity analysis of the BC mixtures studied in this work. HAM combines the features of adsorption theory via the adsorption isotherm with the features of Köhler theory by incorporating solubility partitioning. The results in this work showed that HAM improves the representation of CCN activity of pure and mixed BC aerosol species with high certainty, evident from generally better goodness of fit, R2 > 0.9. This work implies that the hygroscopicity parameterization based on HAM captures the size-dependent variability in the CCN activity of the pure and aged BC species.

Electric Field-Induced Water Condensation Visualized by Vapor-Phase Transmission Electron Microscopy.

Understanding the nanoscale water condensation dynamics in strong electric fields is important for improving the atmospheric modeling of cloud dynamics and emerging technologies utilizing electric fields for direct air moisture capture. Here, we use vapor-phase transmission electron microscopy (VPTEM) to directly image nanoscale condensation dynamics of sessile water droplets in electric fields. VPTEM imaging of saturated water vapor stimulated condensation of sessile water nanodroplets that grew to a size of ∼500 nm before evaporating over a time scale of a minute. Simulations showed that electron beam charging of the silicon nitride microfluidic channel windows generated electric fields of ∼108 V/m, which depressed the water vapor pressure and effected rapid nucleation of nanosized liquid water droplets. A mass balance model showed that droplet growth was consistent with electric field-induced condensation, while droplet evaporation was consistent with radiolysis-induced evaporation via conversion of water to hydrogen gas. The model quantified several electron beam-sample interactions and vapor transport properties, showed that electron beam heating was insignificant, and demonstrated that literature values significantly underestimated radiolytic hydrogen production and overestimated water vapor diffusivity. This work demonstrates a method for investigating water condensation in strong electric fields and under supersaturated conditions, which is relevant to vapor-liquid equilibrium in the troposphere. While this work identifies several electron beam-sample interactions that impact condensation dynamics, quantification of these phenomena here is expected to enable delineating these artifacts from the physics of interest and accounting for them when imaging more complex vapor-liquid equilibrium phenomena with VPTEM.

Relative efficacy of masks and respirators as source control for viral aerosol shedding from people infected with SARS-CoV-2: a controlled human exhaled breath aerosol experimental study.

BACKGROUND: Tight-fitting masks and respirators, in manikin studies, improved aerosol source control compared to loose-fitting masks. Whether this translates to humans is not known. METHODS: We compared efficacy of masks (cloth and surgical) and respirators (KN95 and N95) as source control for SARS-CoV-2 viral load in exhaled breath of volunteers with COVID-19 using a controlled human experimental study. Volunteers (N = 44, 43% female) provided paired unmasked and masked breath samples allowing computation of source-control factors. FINDINGS: All masks and respirators significantly reduced exhaled viral load, without fit tests or training. A duckbill N95 reduced exhaled viral load by 98% (95% CI: 97%-99%), and significantly outperformed a KN95 (p < 0.001) as well as cloth and surgical masks. Cloth masks outperformed a surgical mask (p = 0.027) and the tested KN95 (p = 0.014). INTERPRETATION: These results suggest that N95 respirators could be the standard of care in nursing homes and healthcare settings when respiratory viral infections are prevalent in the community and healthcare-associated transmission risk is elevated. FUNDING: Defense Advanced Research Projects Agency, National Institute of Allergy and Infectious Diseases, Centers for Disease Control and Prevention, the Bill & Melinda Gates Foundation, and The Flu Lab.

Hygroscopicity of nitrogen-containing organic carbon compounds: o-aminophenol and p-aminophenol.

Nitrogen-containing Organic Carbon (NOC) is a major constituent of atmospheric aerosols and they have received significant attention in the atmospheric science community. While extensive research and advancements have been made regarding their emission sources, concentrations, and their secondary formation in the atmosphere, little is known about their water uptake efficiencies and their subsequent role in climate, air quality, and visibility. In this study, we investigated the water uptake of two sparingly soluble aromatic NOCs: o-aminophenol (oAP) and p-aminophenol (pAP) under subsaturated and supersaturated conditions using a Hygroscopicity Tandem Differential Mobility Analyzer (H-TDMA) and a Cloud Condensation Nuclei Counter (CCNC), respectively. Our results show that oAP and pAP are slightly hygroscopic with comparable hygroscopicities to various studied organic aerosols. The supersaturated single hygroscopicity parameter (κCCN) was measured and reported to be 0.18 ± 0.05 for oAP and 0.04 ± 0.02 for pAP, indicating that oAP is more hygroscopic than pAP despite them having the same molecular formulae. The observed disparity in hygroscopicity is attributed to the difference in functional group locations, interactions with gas phase water molecules, and the reported bulk water solubilities of the NOC. Under subsaturated conditions, both oAP and pAP aerosols showed size dependent water uptake. Both species demonstrated growth at smaller dry particle sizes, and shrinkage at larger dry particle sizes. The measured growth factor (Gf) range, at RH = 85%, for oAP was 1.60-0.74 and for pAP was 1.53-0.74 with increasing particle size. The growth and shrinkage dichotomy is attributed to morphological particle differences verified by TEM images of small and large particles. Subsequently, aerosol physicochemical properties must be considered to properly predict the droplet growth of NOC aerosols in the atmosphere.

Size, Shape, and Phase of Nanoscale Uric Acid Particles.

Uric acid particles are formed due to hyperuricemia, and previous works have focused on understanding the surface forces, crystallization, and growth of micron- and supermicron-sized particles. However, little to no work has furthered our understanding about uric acid nanonuclei that precipitate during the initial stages of kidney stone formation. In this work, we generate nanosized uric acid particles by evaporating saturated solution droplets of uric acid. Furthermore, we quantify the effects of drying rate on the morphology of uric acid nanonuclei. An aerosol droplet drying method generates uric acid nanoparticles in the size range of 20-200 nm from aqueous droplets (1-6 µm). Results show that uric acid nanonuclei are non-spherical with a shape factor value in the range of 1.1-1.4. The shape factor values change with drying rate and indicate that the nanoparticle morphology is greatly affected by drying kinetics. The nanonuclei are amorphous but can grow to form crystalline micron-sized particles. Indeed, a pre-crystallization phase was observed for heterogeneous nucleation of uric acid particles in the size range of a few hundred nanometers. Our findings show that the morphology of uric acid nanonuclei is significantly different from that of crystalline supermicron-sized particles. These new findings imply that the dissolution characteristics, surface properties, elimination, and medical treatment of uric acid nanonuclei formed during the initial stages of nucleation must be reconsidered.

Reactivity of aminophenols in forming nitrogen-containing brown carbon from iron-catalyzed reactions.

Nitrogen-containing organic carbon (NOC) in atmospheric particles is an important class of brown carbon (BrC). Redox active NOC like aminophenols received little attention in their ability to form BrC. Here we show that iron can catalyze dark oxidative oligomerization of o- and p-aminophenols under simulated aerosol and cloud conditions (pH 1-7, and ionic strength 0.01-1 M). Homogeneous aqueous phase reactions were conducted using soluble Fe(III), where particle growth/agglomeration were monitored using dynamic light scattering. Mass yield experiments of insoluble soot-like dark brown to black particles were as high as 40%. Hygroscopicity growth factors (κ) of these insoluble products under sub- and super-saturated conditions ranged from 0.4-0.6, higher than that of levoglucosan, a prominent proxy for biomass burning organic aerosol (BBOA). Soluble products analyzed using chromatography and mass spectrometry revealed the formation of ring coupling products of o- and p-aminophenols and their primary oxidation products. Heterogeneous reactions of aminophenol were also conducted using Arizona Test Dust (AZTD) under simulated aging conditions, and showed clear changes to optical properties, morphology, mixing state, and chemical composition. These results highlight the important role of iron redox chemistry in BrC formation under atmospherically relevant conditions.

Hygroscopicity and cloud condensation nucleation activities of hydroxyalkylsulfonates.

Hydroxyalkylsulfonates may contribute significantly to atmospheric particles; however, their hygroscopic properties and cloud condensation nuclei (CCN) activities remain unknown. In this study, three complementary techniques were utilized to examine the hygroscopicity of sodium hydroxymethanesulfonate (NaHMS), sodium 2-hydroxyethylsulfonate (NaHES), and ammonium 2-hydroxyethylsulfonate (NH4HES) under subsaturated and supersaturated environments. The mass changes in the three hydroxyalkylsulfonates at different relative humidities at 25 °C were examined by a vapor sorption analyzer, and the mass growth factors were measured to be 3.25 ± 0.01 for NaHMS, 3.32 ± 0.02 for NaHES, and 3.34 ± 0.04 for NH4HES at 90% RH. Their hygroscopic growth was investigated by a humidity tandem differential mobility analyzer, and hygroscopic growth factors were 1.78 ± 0.02 for NaHMS, 1.71 ± 0.02 for NaHES, and 1.68 ± 0.03 for NH4HES at 90% RH. Furthermore, the CCN activities of NaHMS, NaHES, and NH4HES were explored, and their single hygroscopicity parameters (κccn) were measured to be 0.649 ± 0.097 for NaHMS, 0.559 ± 0.069 for NaHES, and 0.434 ± 0.073 for NH4HES. In addition, the hygroscopic growth and CCN activities of binary mixtures of ammonium sulfate with one of the three hydroxyalkylsulfonates were also examined.