Droplet Activation Research Articles

Fogs: Physical Basis, Characteristic Properties, and Impacts on the Environment and Human Health

This work presents a selective overview of natural fogs in terms of fog types, forms and states of occurrence, physical, micro-physical, chemical and dynamic properties, basic characterizing parameters, etc. In focus are related achievements and contributions reported mainly during the last decade and a half, as a result of both laboratory studies and field observations. Processes of homogeneous and heterogeneous nucleation are analyzed in the aspects of condensation, nuclei diversity and specifics, as related to the activation, growth and deposition of fog droplets. The effect is highlighted of the water vapor’s partial pressure on the surface tension of the liquid water–air interface and the freezing point of the water droplets. Some problems and aspects of fog modeling, parameterization, and forecasting are outlined and discussed on the examples of newly developed relevant 1D/3D theoretical models. Important issues of fog impacts on the air quality, ecosystems, water basins, societal life, and human health are also addressed and discussed, particularly in cases of anthropogenically modified (chemical, radioactive, etc.) fogs. In view of reducing the possible negative effects of fogs, conclusions are drawn concerning the new demands and challenges to fog characterization imposed by the changing natural and social environment and the needs for new data on and approaches to more adequate observations of fog-related events.

Cloud Activation Potentials for Atmospheric α-Pinene and β-Caryophyllene Ozonolysis Products.

The formation of atmospheric cloud droplets due to secondary organic aerosol (SOA) particles is important for quantifying the Earth’s radiative balance under future, possibly warmer, climates, yet is only poorly understood. While cloud activation may be parametrized using the surface tension depression that coincides with surfactant partitioning to the gas–droplet interface, the extent to which cloud activation is influenced by both the chemical structure and reactivity of the individual molecules comprising this surfactant pool is largely unknown. We report herein considerable differences in the surface tension depression of aqueous pendant droplets that contain synthetically prepared ozonolysis products derived from α-pinene and β-caryophyllene, the most abundant of the monoterpenes and sesquiterpenes, respectively, that are emitted over the planet’s vast forest ecosystems. Oxidation products derived from β-caryophyllene were found to exhibit significantly higher surface activity than those prepared from α-pinene, with the critical supersaturation required for cloud droplet activation reduced by 50% for β-caryophyllene aldehyde at 1 mM. These considerable reductions in the critical supersaturation were found to coincide with free energies of adsorption that exceed ∼25 kJ/mol, or just one hydrogen bond equivalent, depending on the ammonium sulfate and oxidation product concentration in the solution. Additional experiments showed that aldehyde-containing oxidation products exist in equilibrium with hydrated forms in aqueous solution, which may modulate their bulk solubility and surface activity. Equilibration time scales on the order of 10–5 to 10–4 s calculated for micrometer-sized aerosol particles indicate instantaneous surface tension depression in the activation processes leading to cloud formation in the atmosphere. Our findings highlight the underlying importance of molecular structure and reactivity when considering cloud condensation activity in the presence of SOA particles.

Modeling regional air quality and climate: improving organic aerosol and aerosol activation processes in WRF/Chem version 3.7.1

Abstract. Air quality and climate influence each other through the uncertain processes of aerosol formation and cloud droplet activation. In this study, both processes are improved in the Weather, Research and Forecasting model with Chemistry (WRF/Chem) version 3.7.1. The existing Volatility Basis Set (VBS) treatments for organic aerosol (OA) formation in WRF/Chem are improved by considering the following: the secondary OA (SOA) formation from semi-volatile primary organic aerosol (POA), a semi-empirical formulation for the enthalpy of vaporization of SOA, and functionalization and fragmentation reactions for multiple generations of products from the oxidation of VOCs. Over the continental US, 2-month-long simulations (May to June 2010) are conducted and results are evaluated against surface and aircraft observations during the Nexus of Air Quality and Climate Change (CalNex) campaign. Among all the configurations considered, the best performance is found for the simulation with the 2005 Carbon Bond mechanism (CB05) and the VBS SOA module with semivolatile POA treatment, 25 % fragmentation, and the emissions of semi-volatile and intermediate volatile organic compounds being 3 times the original POA emissions. Among the three gas-phase mechanisms (CB05, CB6, and SAPRC07) used, CB05 gives the best performance for surface ozone and PM2. 5 concentrations. Differences in SOA predictions are larger for the simulations with different VBS treatments (e.g., nonvolatile POA versus semivolatile POA) compared to the simulations with different gas-phase mechanisms. Compared to the simulation with CB05 and the default SOA module, the simulations with the VBS treatment improve cloud droplet number concentration (CDNC) predictions (normalized mean biases from −40.8 % to a range of −34.6 to −27.7 %), with large differences between CB05–CB6 and SAPRC07 due to large differences in their OH and HO2 predictions. An advanced aerosol activation parameterization based on the Fountoukis and Nenes (2005) series reduces the large negative CDNC bias associated with the default Abdul Razzak and Ghan (2000) parameterization from −35.4 % to a range of −0.8 to 7.1 %. However, it increases the errors due to overpredictions of CDNC, mainly over the northeastern US. This work indicates a need to improve other aerosol–cloud–radiation processes in the model, such as the spatial distribution of aerosol optical depth and cloud condensation nuclei, in order to further improve CDNC predictions.

Surface tension prevails over solute effect in organic-influenced cloud droplet activation.

The spontaneous growth of cloud condensation nuclei (CCN) into cloud droplets under supersaturated water vapour conditions is described by classic Köhler theory. This spontaneous activation of CCN depends on the interplay between the Raoult effect, whereby activation potential increases with decreasing water activity or increasing solute concentration, and the Kelvin effect, whereby activation potential decreases with decreasing droplet size or increases with decreasing surface tension, which is sensitive to surfactants. Surface tension lowering caused by organic surfactants, which diminishes the Kelvin effect, is expected to be negated by a concomitant reduction in the Raoult effect, driven by the displacement of surfactant molecules from the droplet bulk to the droplet-vapour interface. Here we present observational and theoretical evidence illustrating that, in ambient air, surface tension lowering can prevail over the reduction in the Raoult effect, leading to substantial increases in cloud droplet concentrations. We suggest that consideration of liquid-liquid phase separation, leading to complete or partial engulfing of a hygroscopic particle core by a hydrophobic organic-rich phase, can explain the lack of concomitant reduction of the Raoult effect, while maintaining substantial lowering of surface tension, even for partial surface coverage. Apart from the importance of particle size and composition in droplet activation, we show by observation and modelling that incorporation of phase-separation effects into activation thermodynamics can lead to a CCN number concentration that is up to ten times what is predicted by climate models, changing the properties of clouds. An adequate representation of the CCN activation process is essential to the prediction of clouds in climate models, and given the effect of clouds on the Earth's energy balance, improved prediction of aerosol-cloud-climate interactions is likely to result in improved assessments of future climate change.

Heterogeneous ice nucleation of α‐pinene SOA particles before and after ice cloud processing

AbstractThe ice nucleation ability of α‐pinene secondary organic aerosol (SOA) particles was investigated at temperatures between 253 and 205 K in the Aerosol Interaction and Dynamics in the Atmosphere cloud simulation chamber. Pristine SOA particles were nucleated and grown from pure gas precursors and then subjected to repeated expansion cooling cycles to compare their intrinsic ice nucleation ability during the first nucleation event with that observed after ice cloud processing. The unprocessed α‐pinene SOA particles were found to be inefficient ice‐nucleating particles at cirrus temperatures, with nucleation onsets (for an activated fraction of 0.1%) as high as for the homogeneous freezing of aqueous solution droplets. Ice cloud processing at temperatures below 235 K only marginally improved the particles' ice nucleation ability and did not significantly alter their morphology. In contrast, the particles' morphology and ice nucleation ability was substantially modified upon ice cloud processing in a simulated convective cloud system, where the α‐pinene SOA particles were first activated to supercooled cloud droplets and then froze homogeneously at about 235 K. As evidenced by electron microscopy, the α‐pinene SOA particles adopted a highly porous morphology during such a freeze‐drying cycle. When probing the freeze‐dried particles in succeeding expansion cooling runs in the mixed‐phase cloud regime up to 253 K, the increase in relative humidity led to a collapse of the porous structure. Heterogeneous ice formation was observed after the droplet activation of the collapsed, freeze‐dried SOA particles, presumably caused by ice remnants in the highly viscous material or the larger surface area of the particles.

Droplet Concentration and Spectral Broadening in Southeast Pacific Stratocumulus Clouds

Abstract Several airborne field experiments have been conducted to verify model descriptions of cloud droplet activation. Measurements of cloud condensation nuclei and updraft are inputs to a parcel model that predicts droplet concentration and droplet size distributions (spectra). Experiments conducted within cumulus clouds have yielded the most robust agreement between model and observation. Investigations of stratocumulus clouds are more varied, in part because of the difficulty of gauging the effects of entrainment and drizzle on droplet concentration and spectra. Airborne lidar is used here to supplement the approach used in prior studies of droplet activation in stratocumulus clouds. A model verification study was conducted using data acquired during the Southern Hemispheric VAMOS Ocean–Cloud–Aerosol–Land Study Regional Experiment. Consistency between observed and modeled droplet concentrations is achieved, but only after accounting for the effects of entrainment and drizzle on concentrations produced by droplet activation. In addition, predicted spectral dispersions are 74% of the measured dispersions following correction for instrument broadening. This result is consistent with the conjecture that differential activation (at cloud base) and internal mixing (i.e., mixing without entrainment) are important drivers of true spectral broadening.

Cloud droplet activation through oxidation of organic aerosol influenced by temperature and particle phase state

AbstractChemical aging of organic aerosol (OA) through multiphase oxidation reactions can alter their cloud condensation nuclei (CCN) activity and hygroscopicity. However, the oxidation kinetics and OA reactivity depend strongly on the particle phase state, potentially influencing the hydrophobic‐to‐hydrophilic conversion rate of carbonaceous aerosol. Here, amorphous Suwannee River fulvic acid (SRFA) aerosol particles, a surrogate humic‐like substance (HULIS) that contributes substantially to global OA mass, are oxidized by OH radicals at different temperatures and phase states. When oxidized at low temperature in a glassy solid state, the hygroscopicity of SRFA particles increased by almost a factor of two, whereas oxidation of liquid‐like SRFA particles at higher temperatures did not affect CCN activity. Low‐temperature oxidation appears to promote the formation of highly‐oxygenated particle‐bound fragmentation products with lower molar mass and greater CCN activity, underscoring the importance of chemical aging in the free troposphere and its influence on the CCN activity of OA.

Laboratory Studies of the Cloud Droplet Activation Properties and Corresponding Chemistry of Saline Playa Dust.

Playas emit large quantities of dust that can facilitate the activation of cloud droplets. Despite the potential importance of playa dusts for cloud formation, most climate models assume that all dust is nonhygroscopic; however, measurements are needed to clarify the role of dusts in aerosol-cloud interactions. Here, we report measurements of CCN activation from playa dusts and parameterize these results in terms of both κ-Köhler theory and adsorption activation theory for inclusion in atmospheric models. κ ranged from 0.002 ± 0.001 to 0.818 ± 0.094, whereas Frankel-Halsey-Hill (FHH) adsorption parameters of AFHH = 2.20 ± 0.60 and BFHH = 1.24 ± 0.14 described the water uptake properties of the dusts. Measurements made using aerosol time-of-flight mass spectrometry (ATOFMS) revealed the presence of halite, sodium sulfates, and sodium carbonates that were strongly correlated with κ underscoring the role that mineralogy, including salts, plays in water uptake by dust. Predictions of κ made using bulk chemical techniques generally showed good agreement with measured values. However, several samples were poorly predicted suggesting that chemical heterogeneities as a function of size or chemically distinct particle surfaces can determine the hygroscopicity of playa dusts. Our results further demonstrate the importance of dust in aerosol-cloud interactions.

Chemical Composition and Properties of the Liquid-Vapor Interface of Aqueous C1 to C4 Monofunctional Acid and Alcohol Solutions.

The liquid-vapor interface is playing an important role in aerosol and cloud chemistry in cloud droplet activation by aerosol particles and potentially also in ice nucleation. We have employed the surface sensitive and chemically selective X-ray photoelectron spectroscopy (XPS) technique to examine the liquid-vapor interface for mixtures of water and small alcohols or small carboxylic acids (C1 to C4), abundant chemicals in the atmosphere in concentration ranges relevant for cloud chemistry or aerosol particles at the point of activation into a cloud droplet. A linear correlation was found between the headgroup carbon 1s core-level signal intensity and the surface excess derived from literature surface tension data with the offset being explained by the bulk contribution to the photoemission signal. The relative interfacial enhancement of the carboxylic acids over the carboxylates at the same bulk concentration was found to be highest (nearly 20) for propionic acid/propionate and still about 5 for formic acid/formate, also in fair agreement with surface tension measurements. This provides direct spectroscopic evidence for high carboxylic acid concentrations at aqueous solution-air interfaces that may be responsible for acid catalyzed chemistry under moderately acidic conditions with respect to their bulk aqueous phase acidity constant. By assessing the ratio of aliphatic to headgroup C 1s signal intensities XPS also provides information about the orientation of the molecules. The results indicate an increasing orientation of alcohols and neutral acids toward the surface normal as a function of chain length, along with increasing importance of lateral hydrophobic interactions at higher surface coverage. In turn, the carboxylate ions exhibit stronger orientation toward the surface normal than the corresponding neutral acids, likely caused by the stronger hydration of the charged headgroup.

Hygroscopic growth and cloud droplet activation of xanthan gum as a proxy for marine hydrogels

AbstractKnowledge of the physical characteristics and chemical composition of marine organic aerosols is needed for the quantification of their effects on cloud microphysical processes and solar radiative transfer. Here we use xanthan gum (XG)—a bacterial biopolymer—as a proxy for marine hydrogels. Measurements were performed for pure XG particles and mixtures of XG with sodium chloride, calcium nitrate, and calcium carbonate. The aerosol hygroscopicity parameter (κ) is derived from hygroscopic growth factor measurements (κgf) at variable water activity (aw) and from cloud condensation nuclei activation efficiency (κccn). The Zdanovskii, Stokes, and Robinson (ZSR) hygroscopicity parameter derived for multicomponent systems (κmix, sol) is used to compare measurements of κgf and κccn. Pure XG shows close agreement of κgf (at aw = 0.9) and κccn of 0.09 and 0.10, respectively. Adding salts to the system results in deviations of κgf (at aw = 0.9) from κccn. The measured κgf and ZSR‐derived hygroscopicity parameter (κmix, sol) values for different solutions show close agreement at aw > 0.9, while κgf is lower in comparison to κmix, sol at aw < 0.9. The differences between predicted κmix, sol and measured κgf and κccn values are explained by the effects of hydration and presence of salt ions on the structure of the polymer networks. Results from this study imply that at supersaturations of 0.1 and 0.5%, the presence of 30% sea salt by mass can reduce the activation diameter of pure primary marine organic aerosols from 257 to 156 nm and from 87 to 53 nm, respectively.

In-cloud measurements highlight the role of aerosol hygroscopicity in cloud droplet formation

Abstract. The relationship between aerosol hygroscopicity and cloud droplet activation was studied at the Puijo measurement station in Kuopio, Finland, during the autumn 2014. The hygroscopic growth of 80, 120 and 150 nm particles was measured at 90 % relative humidity with a hygroscopic tandem differential mobility analyzer. Typically, the growth factor (GF) distributions appeared bimodal with clearly distinguishable peaks around 1.0–1.1 and 1.4–1.6. However, the relative contribution of the two modes appeared highly variable reflecting the probable presence of fresh anthropogenic particle emissions. The hygroscopicity-dependent activation properties were estimated in a case study comprising four separate cloud events with varying characteristics. At 120 and 150 nm, the activation efficiencies within the low- and high-GF modes varied between 0–34 and 57–83 %, respectively, indicating that the less hygroscopic particles remained mostly non-activated, whereas the more hygroscopic mode was predominantly scavenged into cloud droplets. By modifying the measured GF distributions, it was estimated how the cloud droplet concentrations would change if all the particles belonged to the more hygroscopic group. According to κ-Köhler simulations, the cloud droplet concentrations increased up to 70 % when the possible feedback effects on effective peak supersaturation (between 0.16 and 0.29 %) were assumed negligible. This is an indirect but clear illustration of the sensitivity of cloud formation to aerosol chemical composition.

Aerosol indirect effects on glaciated clouds. Part I: Model description

Various improvements were made to a state‐of‐the‐art aerosol–cloud model and comparison of the model results with observations from field campaigns was performed. The strength of this aerosol–cloud model is in its ability to explicitly resolve all the known modes of heterogeneous cloud droplet activation and ice crystal nucleation. The model links cloud particle activation with the aerosol loading and chemistry of seven different aerosol species. These improvements to the model resulted in more accurate prediction especially of droplet and ice crystal number concentrations in the upper troposphere and enabled the model to directly sift the aerosol indirect effects based on the chemistry and concentration of the aerosols. In addition, continental and maritime cases were simulated for the purpose of validating the aerosol–cloud model and for investigating the critical microphysical and dynamical mechanisms of aerosol indirect effects from anthropogenic solute and solid aerosols, focusing mainly on glaciated clouds. The simulations showed that increased solute aerosols reduced cloud particle sizes by about 5 μm and inhibited warm rain processes. Cloud fractions and their optical thicknesses were increased quite substantially in both cases. Although liquid mixing ratios were boosted, there was however a substantial reduction of ice mixing ratios in the upper troposphere owing to the increase in snow production aloft. These results are detailed in the subsequent parts of this study.

Meteorological and aerosol effects on marine cloud microphysical properties

AbstractMeteorology and microphysics affect cloud formation, cloud droplet distributions, and shortwave reflectance. The Eastern Pacific Emitted Aerosol Cloud Experiment and the Stratocumulus Observations of Los‐Angeles Emissions Derived Aerosol‐Droplets studies provided measurements in six case studies of cloud thermodynamic properties, initial particle number distribution and composition, and cloud drop distribution. In this study, we use simulations from a chemical and microphysical aerosol‐cloud parcel (ACP) model with explicit kinetic drop activation to reproduce observed cloud droplet distributions of the case studies. Four cases had subadiabatic lapse rates, resulting in fewer activated droplets, lower liquid water content, and higher cloud base height than an adiabatic lapse rate. A weighted ensemble of simulations that reflect measured variation in updraft velocity and cloud base height was used to reproduce observed droplet distributions. Simulations show that organic hygroscopicity in internally mixed cases causes small effects on cloud reflectivity (CR) (<0.01), except for cargo ship and smoke plumes, which increased CR by 0.02 and 0.07, respectively, owing to their high organic mass fraction. Organic hygroscopicity had larger effects on droplet concentrations for cases with higher aerosol concentrations near the critical diameter (namely, polluted cases with a modal peak near 0.1 µm). Differences in simulated droplet spectral widths (k) caused larger differences in CR than organic hygroscopicity in cases with organic mass fractions of 60% or less for the cases shown. Finally, simulations from a numerical parameterization of cloud droplet activation suitable for general circulation models compared well with the ACP model, except under high organic mass fraction.

Anionic, Cationic, and Nonionic Surfactants in Atmospheric Aerosols from the Baltic Coast at Askö, Sweden: Implications for Cloud Droplet Activation.

Recent analyses of atmospheric aerosols from different regions have demonstrated the ubiquitous presence of strong surfactants and evidenced surface tension values, σ, below 40 mN m(-1), suspected to enhance the cloud-forming potential of these aerosols. In this work, this approach was further improved and combined with absolute concentration measurements of aerosol surfactants by colorimetric titration. This analysis was applied to PM2.5 aerosols collected at the Baltic station of Askö, Sweden, from July to October 2010. Strong surfactants were found in all the sampled aerosols, with σ = (32-40) ± 1 mN m(-1) and concentrations of at least 27 ± 6 mM or 104 ± 21 pmol m(-3). The absolute surface tension curves and critical micelle concentrations (CMC) determined for these aerosol surfactants show that (1) surfactants are concentrated enough in atmospheric particles to strongly depress the surface tension until activation, and (2) the surface tension does not follow the Szyszkowski equation during activation but is nearly constant and minimal, which provides new insights on cloud droplet activation. In addition, both the CMCs determined and the correlation (R(2) ∼ 0.7) between aerosol surfactant concentrations and chlorophyll-a seawater concentrations suggest a marine and biological origin for these compounds.

Canopy‐atmosphere interactions under foggy condition—Size‐resolved fog droplet fluxes and their implications

AbstractMicrophysical processes of fog and their spatial and temporal pattern are a challenge to study under natural conditions. This work focuses on the development of bidirectional fluxes of fog droplets above a forest canopy in northeastern Taiwan. Bidirectional fluxes occurred regularly, start from the smallest droplet class (<2.66 µm diameter), and subsequently extend to larger droplets up to 7.41 µm diameter. The development of the bidirectional fluxes with positive (upward) fluxes of smaller droplets and downward fluxes of larger fluxes is associated with a temperature gradient and with the activation of fog droplets according to the Köhler theory. Small fog droplets develop close to the canopy as result of evapotranspiration and subsequent condensation. The rapid growth of small fog droplets and the accelerated growth of activated droplets, a process which is more likely to occur at higher levels of the fog layer, lead to a sink of small droplets and a source of larger droplets within the fog. This is in accordance with the observation that positive droplet number fluxes of small fog droplets outnumber the negative fluxes from the larger fog droplets. For liquid water, the net flux is negative.

Cloud condensation nuclei activity, droplet growth kinetics, and hygroscopicity of biogenic and anthropogenic secondary organic aerosol (SOA)

Abstract. Interaction of biogenic volatile organic compounds (VOCs) with Anthropogenic VOC (AVOC) affects the physicochemical properties of secondary organic aerosol (SOA). We investigated cloud droplet activation (CCN activity), droplet growth kinetics, and hygroscopicity of mixed anthropogenic and biogenic SOA (ABSOA) compared to pure biogenic SOA (BSOA) and pure anthropogenic SOA (ASOA). Selected monoterpenes and aromatics were used as representative precursors of BSOA and ASOA, respectively.We found that BSOA, ASOA, and ABSOA had similar CCN activity despite the higher oxygen to carbon ratio (O/C) of ASOA compared to BSOA and ABSOA. For individual reaction systems, CCN activity increased with the degree of oxidation. Yet, when considering all different types of SOA together, the hygroscopicity parameter, κCCN, did not correlate with O/C. Droplet growth kinetics of BSOA, ASOA, and ABSOA were comparable to that of (NH4)2SO4, which indicates that there was no delay in the water uptake for these SOA in supersaturated conditions.In contrast to CCN activity, the hygroscopicity parameter from a hygroscopic tandem differential mobility analyzer (HTDMA) measurement, κHTDMA, of ASOA was distinctively higher (0.09–0.10) than that of BSOA (0.03–0.06), which was attributed to the higher degree of oxidation of ASOA. The ASOA components in mixed ABSOA enhanced aerosol hygroscopicity. Changing the ASOA fraction by adding biogenic VOC (BVOC) to ASOA or vice versa (AVOC to BSOA) changed the hygroscopicity of aerosol, in line with the change in the degree of oxidation of aerosol. However, the hygroscopicity of ABSOA cannot be described by a simple linear combination of pure BSOA and ASOA systems. This indicates that additional processes, possibly oligomerization, affected the hygroscopicity.Closure analysis of CCN and HTDMA data showed κHTDMA was lower than κCCN by 30–70 %. Better closure was achieved for ASOA compared to BSOA. This discrepancy can be attributed to several reasons. ASOA seemed to have higher solubility in subsaturated conditions and/or higher surface tension at the activation point than that of BSOA.

Study of Droplet Activation in Thin Clouds Using Ground-Based Raman Lidar and Ancillary Remote Sensors

A methodology for the study of cloud droplet activation based on the measurements performed with ground-based multi-wavelength Raman lidars and ancillary remote sensors collected at CNR-IMAA observatory, Potenza, South Italy, is presented. The study is focused on the observation of thin warm clouds. Thin clouds are often also optically thin: this allows the cloud top detection and the full profiling of cloud layers using ground-based Raman lidar. Moreover, broken clouds are inspected to take advantage of their discontinuous structure in order to study the variability of optical properties and water vapor content in the transition from cloudy regions to cloudless regions close to the cloud boundaries. A statistical study of this variability leads to identify threshold values for the optical properties, enabling the discrimination between clouds and cloudless regions. These values can be used to evaluate and improve parameterizations of droplet activation within numerical models. A statistical study of the co-located Doppler radar moments allows to retrieve droplet size and vertical velocities close to the cloud base. First evidences of a correlation between droplet vertical velocities measured at the cloud base and the aerosol effective radius observed in the cloud-free regions of the broken clouds are found.

Immersion Freezing of Kaolinite: Scaling with Particle Surface Area

Abstract This study presents an analysis showing that the freezing probability of kaolinite particles from Fluka scales exponentially with particle surface area for different atmospherically relevant particle sizes. Immersion freezing experiments were performed at the Leipzig Aerosol Cloud Interaction Simulator (LACIS). Size-selected kaolinite particles with mobility diameters of 300, 700, and 1000 nm were analyzed with one particle per droplet. First, it is demonstrated that immersion freezing is independent of the droplet volume. Using the mobility analyzer technique for size selection involves the presence of multiply charged particles in the quasi-monodisperse aerosol, which are larger than singly charged particles. The fractions of these were determined using cloud droplet activation measurements. The development of a multiple charge correction method has proven to be essential for deriving ice fractions and other quantities for measurements in which the here-applied method of size selection is used. When accounting for multiply charged particles (electric charge itself does not matter), both a time-independent and a time-dependent description of the freezing process can reproduce the measurements over the range of examined particle sizes. Hence, either a temperature-dependent surface site density or a single contact angle distribution was sufficient to parameterize the freezing behavior. From a comparison with earlier studies using kaolinite samples from the same provider, it is concluded that the neglect of multiply charged particles and, to a lesser extent, the effect of time can cause a significant overestimation of the ice nucleation site density of one order of magnitude, which translates into a temperature bias of 5–6 K.

Dynamic Percolation and Droplet Growth Behavior in Porous Electrodes of Polymer Electrolyte Fuel Cells

The percolating flow of liquid water in the gas-diffusion layer (GDL) of polymer electrolyte fuel cells (PEFCs) was studied ex situ using a simple water-injection experiment. Water was injected into the top of the sample so the droplet was free to detach from the bottom, allowing for uninterrupted study of the dynamic cycle of droplet appearance, growth, and detachment. Although droplets emerged from a single point on the GDL, the measured pressure response in the water phase was clearly not equivalent to a single needle. The behavior of the system was explained by the simultaneous filling and inflating of many menisci, resulting in extended periods with no droplet activity at the GDL surface, followed by the sudden eruption of a droplet at the breakthrough site as all interfaces deflated and their stored water was directed toward the droplet. A simple numerical model was presented that could qualitatively explain the observed behavior. Tests were performed on GDLs, with and without microporous layers (MPLs), and all observed behavior could be interpreted in terms of the proposed model. MPLs shifted the behavior to a more needlelike behavior which was consistent with the MPL reducing the number of invading liquid clusters in the system.

Dual-frequency acoustic droplet vaporization detection for medical imaging.

Liquid-filled perfluorocarbon droplets emit a unique acoustic signature when vaporized into gas-filled microbubbles using ultrasound. Here, we conducted a pilot study in a tissue-mimicking flow phantom to explore the spatial aspects of droplet vaporization and investigate the effects of applied pressure and droplet concentration on image contrast and axial and lateral resolution. Control microbubble contrast agents were used for comparison. A confocal dual-frequency transducer was used to transmit at 8 MHz and passively receive at 1 MHz. Droplet signals were of significantly higher energy than microbubble signals. This resulted in improved signal separation and high contrast-to-tissue ratios (CTR). Specifically, with a peak negative pressure (PNP) of 450 kPa applied at the focus, the CTR of B-mode images was 18.3 dB for droplets and -0.4 for microbubbles. The lateral resolution was dictated by the size of the droplet activation area, with lower pressures resulting in smaller activation areas and improved lateral resolution (0.67 mm at 450 kPa). The axial resolution in droplet images was dictated by the size of the initial droplet and was independent of the properties of the transmit pulse (3.86 mm at 450 kPa). In post-processing, time-domain averaging (TDA) improved droplet and microbubble signal separation at high pressures (640 kPa and 700 kPa). Taken together, these results indicate that it is possible to generate high-sensitivity, high-contrast images of vaporization events. In the future, this has the potential to be applied in combination with droplet-mediated therapy to track treatment outcomes or as a standalone diagnostic system to monitor the physical properties of the surrounding environment.