Water Uptake Of Particles Research Articles

Using particle-resolved aerosol model simulations to guide the interpretations of cloud condensation nuclei experimental data

Ambient aerosol particles can undergo dynamic mixing processes as they coagulate with particles from other air masses and emission sources. Therefore, aerosols exist in a spectrum, from externally mixed to internally mixed. The mixing state of aerosols can affect their ability to uptake water (hygroscopicity) and their cloud condensation nuclei (CCN) activity, modifying their contribution to the planet’s total radiative budget. However, current water-uptake measurement methods may not be able to capture the complex mixing state. In this research, the dynamic mixing process was simulated by the particle-resolved aerosol model PartMC and also created by experiments in a laminar flow mixing tube. The mixing evolution of ammonium sulfate and sucrose binary mixtures were observed along with the changes in their water uptake properties expressed as the single hygroscopicity parameter, κ. The use of a mixing simulation in conjunction with experiments allow for better identification of the particle mixing state and the particle water uptake and show that no one kappa value can capture the complexity of mixing across the mixed particle size distribution. In other words, the PartMC simulations can be used as a guiding tool to interpret a system’s mixing state based on its experimental droplet activation spectra. This work demonstrates the importance of the integration and use of mixing models to aid in mixing state determination and hygroscopicity measurements of mixed systems.Copyright © 2023 American Association for Aerosol Research

Multiwavelength fluorescence lidar observations of smoke plumes

Abstract. A five-channel fluorescence lidar was developed for the study of atmospheric aerosol. The fluorescence spectrum induced by 355 nm laser emission is analyzed in five spectral intervals using interference filters. Central wavelengths and the widths of these five interference filters are, respectively, as follows: 438 and 29, 472 and 32, 513 and 29, 560 and 40, and 614 and 54 nm. The relative calibration of these channels has been performed using a tungsten–halogen lamp with a color temperature of 2800 K. This new lidar system was operated during summer–autumn 2022, when strong forest fires occurred in the Moscow region and generated a series of smoke plumes analyzed in this study. Our results demonstrate that, for urban aerosol, the maximal fluorescence backscattering is observed in a 472 nm channel. For the smoke, the maximum is shifted toward longer wavelengths, and the fluorescence backscattering coefficients in 472, 513 and 560 nm channels have comparable values. Thus, from the analysis of the ratios of fluorescence backscattering in available channels, we show that it is possible to identify smoke layers. The particle classification based on single-channel fluorescence capacity (ratio of the fluorescence backscattering to the elastic one) has limitations at high relative humidity (RH). The fluorescence capacity indeed decreases when water uptake of particles enhances the elastic scattering. However, the spectral variation of fluorescence backscattering does not exhibit any dependence on RH and can be therefore applied to aerosol identification.

Missed Evaporation from Atmospherically Relevant Inorganic Mixtures Confounds Experimental Aerosol Studies.

Sea salt aerosol particles are highly abundant in the atmosphere and play important roles in the global radiative balance. After influence from continental air, they are typically composed of Na+, Cl-, NH4+, and SO42- and organics. Analogous particle systems are often studied in laboratory settings by atomizing and drying particles from a solution. Here, we present evidence that such laboratory studies may be consistently biased in that they neglect losses of solutes to the gas phase. We present experimental evidence from a hygroscopic tandem differential mobility analyzer and an aerosol mass spectrometer, further supported by thermodynamic modeling. We show that, at normally prevailing laboratory aerosol mass concentrations, for mixtures of NaCl and (NH4)2SO4, a significant portion of the Cl- and NH4+ ions are lost to the gas phase, in some cases, leaving mainly Na2SO4 in the dry particles. Not considering losses of solutes to the gas phase during experimental studies will likely result in misinterpretation of the data. One example of such data is that from particle water uptake experiments. This may bias the explanatory models constructed from the data and introduce errors inte predictions made by air quality or climate models.

Constraining the Effect of Surfactants on the Hygroscopic Growth of Model Sea Spray Aerosol Particles

The cloud condensation nuclei activation of sea spray aerosol (SSA) is tightly linked to the hygroscopic properties of these particles and is defined by their physical and chemical properties. While hygroscopic sea salt in SSA strongly influences particle water uptake, the marine-derived components that make up the organic fraction of SSA constitute a complex mixture, and their effect on hygroscopic growth is unknown. To constrain the effect of organic compounds and specifically surface-active compounds that adsorb on particle interfaces, particle hygroscopic growth studies were performed on laboratory-generated model sea salt/sugar particles. For sea salt/glucose particles, ionic surfactants facilitated water uptake at low relative humidity (RH), increasing the particle growth factor (GF) by up to 7.61%, and caused a reduction in the deliquescence relative humidity (DRH), while nonionic surfactants had a minimal effect. Replacing glucose with polysaccharide laminarin in sea salt/sugar/surfactant particles caused a reduction in GF at low RHs and minimized the effect of ionic surfactants on the DRH. At RHs above the DRH, the addition of anionic or nonionic surfactants caused a decrease in GF for both sea salt/glucose and sea salt/laminarin particles. The addition of cationic surfactants, however, did not have a dampening effect on water uptake of sea salt/sugar particles and even showed a GF increase of up to 3.7% at 90% RH. An increase in the complexity of the sugar dampens the water uptake for particles containing nonionic surfactants but increases the water uptake for cationic surfactants. The cloud activation potential for 100 nm particles analyzed in this study is higher for ionic surfactants and decreases with an increase in surfactant molecular size when particle interfacial tension is considered. The surfactant effect on the hygroscopic growth and cloud activation potential of the particles containing sea salt/sugar is dependent on the surfactant ionicity and molecular size, the particle size and interfacial tension, and the interactions between inorganic salt and organic species under different RH conditions.

Modelling the gas–particle partitioning and water uptake of isoprene-derived secondary organic aerosol at high and low relative humidity

Abstract. This study presents a characterization of the hygroscopic growth behaviour and effects of different inorganic seed particles on the formation of secondary organic aerosols (SOAs) from the dark ozone-initiated oxidation of isoprene at low NOx conditions. We performed simulations of isoprene oxidation using a gas-phase chemical reaction mechanism based on the Master Chemical Mechanism (MCM) in combination with an equilibrium gas–particle partitioning model to predict the SOA concentration. The equilibrium model accounts for non-ideal mixing in liquid phases, including liquid–liquid phase separation (LLPS), and is based on the AIOMFAC (Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients) model for mixture non-ideality and the EVAPORATION (Estimation of VApour Pressure of ORganics, Accounting for Temperature, Intramolecular, and Non-additivity effects) model for pure compound vapour pressures. Measurements from the Cosmics Leaving Outdoor Droplets (CLOUD) chamber experiments, conducted at the European Organization for Nuclear Research (CERN) for isoprene ozonolysis cases, were used to aid in parameterizing the SOA yields at different atmospherically relevant temperatures, relative humidity (RH), and reacted isoprene concentrations. To represent the isoprene-ozonolysis-derived SOA, a selection of organic surrogate species is introduced in the coupled modelling system. The model predicts a single, homogeneously mixed particle phase at all relative humidity levels for SOA formation in the absence of any inorganic seed particles. In the presence of aqueous sulfuric acid or ammonium bisulfate seed particles, the model predicts LLPS to occur below ∼ 80 % RH, where the particles consist of an inorganic-rich liquid phase and an organic-rich liquid phase; however, this includes significant amounts of bisulfate and water partitioned to the organic-rich phase. The measurements show an enhancement in the SOA amounts at 85 % RH, compared to 35 % RH, for both the seed-free and seeded cases. The model predictions of RH-dependent SOA yield enhancements at 85 % RH vs. 35 % RH are 1.80 for a seed-free case, 1.52 for the case with ammonium bisulfate seed, and 1.06 for the case with sulfuric acid seed. Predicted SOA yields are enhanced in the presence of an aqueous inorganic seed, regardless of the seed type (ammonium sulfate, ammonium bisulfate, or sulfuric acid) in comparison with seed-free conditions at the same RH level. We discuss the comparison of model-predicted SOA yields with a selection of other laboratory studies on isoprene SOA formation conducted at different temperatures and for a variety of reacted isoprene concentrations. Those studies were conducted at RH levels at or below 40 % with reported SOA mass yields ranging from 0.3 % up to 9.0 %, indicating considerable variations. A robust feature of our associated gas–particle partitioning calculations covering the whole RH range is the predicted enhancement of SOA yield at high RH (> 80 %) compared to low RH (dry) conditions, which is explained by the effect of particle water uptake and its impact on the equilibrium partitioning of all components.

Measured particle water uptake enhanced by co-condensing vapours

Abstract. Co-condensation of inorganic or organic vapours on growing droplets could significantly enhance both cloud condensation nucleus (CCN) and cloud droplet number concentration, thereby influencing cloud albedo and climate. Until now, there has been very few direct observational evidence of this process. We have measured the growth of inorganic salt particles exposed to both water and organic vapours at 291.15 K in the laboratory, showing that co-condensation of the organic vapours significantly enhances water uptake of aerosols. After exposure to water and propylene glycol vapours, ammonium sulfate particles grew much more than any previously measured particles, inorganic or organic, at the same relative humidity (RH). The maximum equivalent hygroscopicity parameter, κ, was observed to reach up to 2.64, very much higher than values (0.1 < κ < 0.9) measured for atmospheric particulate matter using conventional instrumentation, which may be blind to this effect. Under a continuously replenishing organic vapour field, the particles never reached equilibrium owing to the presence of the involatile solute and were observed to continuously grow with increasing exposure time, in agreement with model simulations. Co-condensation of butylene glycol (which has similar volatility but, at aw = 0.9, a higher Sorg than propylene glycol in our system) and tri-ethylene glycol (which has lower volatility and, at aw = 0.9, lower Sorg than propylene glycol in our system) vapours was additionally measured in this study. The maximum equivalent hygroscopicity parameter, κ, reached as high as 8.48 for ammonium sulfate particles exposed to water and tri-ethylene glycol vapours at 90 % RH. This enhancement of particle water uptake through co-condensation of vapours constitutes the direct measurement of this process, which may substantially influence cloud droplet formation in the atmosphere. In addition, the model simulations for exposure to co-condensing butylene glycol and tri-ethylene glycol vapours with water show that there are factors other than Sorg which influence the co-condensation of semi-volatile organic compounds (SVOCs) that are as yet not understood.

<i>α</i>-Pinene secondary organic aerosol at low temperature: chemical composition and implications for particle viscosity

Abstract. Chemical composition, size distributions, and degree of oligomerization of secondary organic aerosol (SOA) from α-pinene (C10H16) ozonolysis were investigated for low-temperature conditions (223 K). Two types of experiments were performed using two simulation chambers at the Karlsruhe Institute of Technology: the Aerosol Preparation and Characterization (APC) chamber, and the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) chamber. Experiment type 1 simulated SOA formation at upper tropospheric conditions: SOA was generated in the AIDA chamber directly at 223 K at 61 % relative humidity (RH; experiment termed “cold humid”, CH) and for comparison at 6 % RH (experiment termed “cold dry”, CD) conditions. Experiment type 2 simulated SOA uplifting: SOA was formed in the APC chamber at room temperature (296 K) and < 1 % RH (experiment termed “warm dry”, WD) or 21 % RH (experiment termed “warm humid”, WH) conditions, and then partially transferred to the AIDA chamber kept at 223 K, and 61 % RH (WDtoCH) or 30 % RH (WHtoCH), respectively. Precursor concentrations varied between 0.7 and 2.2 ppm α-pinene, and between 2.3 and 1.8 ppm ozone for type 1 and type 2 experiments, respectively. Among other instrumentation, a chemical ionization mass spectrometer (CIMS) coupled to a filter inlet for gases and aerosols (FIGAERO), deploying I− as reagent ion, was used for SOA chemical composition analysis. For type 1 experiments with lower α-pinene concentrations and cold SOA formation temperature (223 K), smaller particles of 100–300 nm vacuum aerodynamic diameter (dva) and higher mass fractions (> 40 %) of adducts (molecules with more than 10 carbon atoms) of α-pinene oxidation products were observed. For type 2 experiments with higher α-pinene concentrations and warm SOA formation temperature (296 K), larger particles (∼ 500 nm dva) with smaller mass fractions of adducts (< 35 %) were produced. We also observed differences (up to 20 ∘C) in maximum desorption temperature (Tmax) of individual compounds desorbing from the particles deposited on the FIGAERO Teflon filter for different experiments, indicating that Tmax is not purely a function of a compound's vapor pressure or volatility, but is also influenced by diffusion limitations within the particles (particle viscosity), interactions between particles deposited on the filter (particle matrix), and/or particle mass on the filter. Highest Tmax were observed for SOA under dry conditions and with higher adduct mass fraction; lowest Tmax were observed for SOA under humid conditions and with lower adduct mass fraction. The observations indicate that particle viscosity may be influenced by intra- and inter-molecular hydrogen bonding between oligomers, and particle water uptake, even under such low-temperature conditions. Our results suggest that particle physicochemical properties such as viscosity and oligomer content mutually influence each other, and that variation in Tmax of particle desorptions may have implications for particle viscosity and particle matrix effects. The differences in particle physicochemical properties observed between our different experiments demonstrate the importance of taking experimental conditions into consideration when interpreting data from laboratory studies or using them as input in climate models.

Modeling the thermodynamics and kinetics of sulfuric acid-dimethylamine-water nanoparticle growth in the CLOUD chamber

ABSTRACTDimethylamine (DMA) has a stabilizing effect on sulfuric acid (SA) clusters, and the SA and DMA molecules and clusters likely play important roles in both aerosol particle formation and growth in the atmosphere. We use the monodisperse particle growth model for acid-base chemistry in nanoparticle growth (MABNAG) together with direct and indirect observations from the CLOUD4 and CLOUD7 experiments in the cosmics leaving outdoor droplets (CLOUD) chamber at CERN to investigate the size and composition evolution of freshly formed particles consisting of SA, DMA, and water as they grow to 20 nm in dry diameter. Hygroscopic growth factors are measured using a nano-hygroscopicity tandem differential mobility analyzer (nano-HTDMA), which combined with simulations of particle water uptake using the thermodynamic extended-aerosol inorganics model (E-AIM) constrain the chemical composition. MABNAG predicts a particle-phase ratio between DMA and SA molecules of 1.1–1.3 for a 2 nm particle and DMA gas-phase mi...

Hygroscopicity of internally mixed multi-component aerosol particles of atmospheric relevance

The hygroscopic properties of two water-soluble organic compounds (WSOCs) relevant to urban haze pollution (phthalic acid and levoglucosan) and their internally mixtures with inorganic salts (ammonium sulfate and ammonium nitrate) are investigated using a hygroscopicity tandem differential mobility analyzer (H-TDMA) system. The multi-component particles uptake water gradually in the range 5-90% relative humidity (RH). The experimental results are compared with the thermodynamic model predictions. For most mixtures, Extended Aerosol Inorganic Model (E-AIM) predictions agree well with the measured growth factors. The hygroscopic growth of mixed particles can be well described by the Zdanovskii-Stokes-Robinson (ZSR) relation as long as the mixed particles are completely liquid. ZSR calculations underestimate the water uptake of mixed particles at moderate RH due to the partial dissolution of ammonium sulfate in the organic and ammonium nitrate solution in this RH region. The phase of ammonium nitrate in the initial dry particles changes dramatically with the composition of mixtures. The presence of organics in the mixed particles can inhibit the crystallization of ammonium nitrate during the drying process and results in water uptake at low RH (RH < 60%). These results demonstrate that certain representative WSOCs can substantially influence the hygroscopicity of inorganic salts and overall water uptake of particles. (c) 2015 Elsevier Ltd. All rights reserved.

Characterization of submicron aerosols and effect on visibility during a severe haze-fog episode in Yangtze River Delta, China

Particle size, composition and optical properties were measured at a regional atmosphere background station in the Yangtze River Delta (YRD) to understand the formation and evolution of haze-fog episodes in Jan. 2013. The peak of particle number size distribution was in the size range of 80–100 nm during the measurements. PM1 mass concentration contributed 84% to the total particle mass (PM10). Based on visibility and ambient relative humidity, three types of weather conditions (i.e., clear, haze and fog) were classified in this study. The extinction coefficients of PM1 and PM10 under dry conditions were simulated by the Mie model. Under dry conditions, PM1 was found to contribute approximately 91% to the light extinction coefficient of PM10. However, the PM1 with the assumption of dry state was found to contribute approximately 85% to the ambient extinction coefficient of PM10 during clear conditions, 58% during haze conditions and approximately 41% during fog conditions. The variation of the dry PM1 contribution was related to the water uptake of particles under different relative humidity conditions.A severe haze-fog event on Jan. 14–17 was discussed in more detail as a case study. Two episodes were chosen to show that nitrate and organics dominated the aerosol component during the severe haze-fog episode and were related to secondary aerosol formation and air mass origin. Nitrate played a more dominant role than sulfate in heavy haze formation in the YRD region, which was different from the North China Plain region.

A meta-analysis of particle water uptake reconciliation studies

Abstract. Water uptake by aerosol particles controls their ability to form cloud droplets, and reconciliation between different techniques for examining cloud condensation nuclei (CCN) properties is important to our understanding of these processes and our ability to measure and predict them. Reconciliation between measurements of sub-saturated and supersaturated aerosol particle water uptake was attempted at a wide range of locations between 2007 and 2013. The agreement in derived number of CCN (NCCN or particle hygroscopicity was mixed across the projects, with some data sets showing poor agreement across all supersaturations and others agreeing within errors for at least some of the supersaturation range. The degree of reconciliation did not seem to depend on the environment in which the measurements were taken. The discrepancies can only be attributable to differences in the chemical behaviour of aerosols and gases in each instrument, leading to under- or overestimated growth factors and/or CCN counts, though poorer reconciliation at lower supersaturations can be attributed to uncertainties in the size distribution at the threshold diameter found at these supersaturations. From a single instrument, the variability in NCCN calculated using particle hygroscopicity or size distribution averaged across a project demonstrates a greater sensitivity to variation in the size distribution than chemical composition in most of the experiments. However, the discrepancies between instruments indicate a strong requirement for reliable quantification of CCN in line with an improved understanding of the physical processes involved in their measurement. Without understanding the reason for discrepancies in the measurements, it is questionable whether quantification of CCN behaviour is meaningful.

Hygroscopicity of organic compounds from biomass burning and their influence on the water uptake of mixed organic ammonium sulfate aerosols

Abstract. Hygroscopic behavior of organic compounds, including levoglucosan, 4-hydroxybenzoic acid, and humic acid, as well as their effects on the hygroscopic properties of ammonium sulfate (AS) in internally mixed particles are studied by a hygroscopicity tandem differential mobility analyzer (HTDMA). The organic compounds used represent pyrolysis products of wood that are emitted from biomass burning sources. It is found that humic acid aerosol particles only slightly take up water, starting at RH (relative humidity) above ~70%. This is contrasted by the continuous water absorption of levoglucosan aerosol particles in the range 5–90% RH. However, no hygroscopic growth is observed for 4-hydroxybenzoic acid aerosol particles. Predicted water uptake using the ideal solution theory, the AIOMFAC model and the E-AIM (with UNIFAC) model are consistent with measured hygroscopic growth factors of levoglucosan. However, the use of these models without consideration of crystalline organic phases is not appropriate to describe the hygroscopicity of organics that do not exhibit continuous water uptake, such as 4-hydroxybenzoic acid and humic acid. Mixed aerosol particles consisting of ammonium sulfate and levoglucosan, 4-hydroxybenzoic acid, or humic acid with different organic mass fractions, take up a reduced amount of water above 80% RH (above AS deliquescence) relative to pure ammonium sulfate aerosol particles of the same mass. Hygroscopic growth of mixtures of ammonium sulfate and levoglucosan with different organic mass fractions agree well with the predictions of the thermodynamic models. Use of the Zdanovskii–Stokes–Robinson (ZSR) relation and AIOMFAC model lead to good agreement with measured growth factors of mixtures of ammonium sulfate with 4-hydroxybenzoic acid assuming an insoluble organic phase. Deviations of model predictions from the HTDMA measurement are mainly due to the occurrence of a microscopical solid phase restructuring at increased humidity (morphology effects), which are not considered in the models. Hygroscopic growth factors of mixed particles containing humic acid are well reproduced by the ZSR relation. Lastly, the organic surrogate compounds represent a selection of some of the most abundant pyrolysis products of biomass burning. The hygroscopic growths of mixtures of the organic surrogate compounds with ammonium sulfate with increasing organics mass fraction representing ambient conditions from the wet to the dry seasonal period in the Amazon basin, exhibit significant water uptake prior to the deliquescence of ammonium sulfate. The measured water absorptions of mixtures of several organic surrogate compounds (including levoglucosan) with ammonium sulfate are close to those of binary mixtures of levoglucosan with ammonium sulfate, indicating that levoglucosan constitutes a major contribution to the aerosol water uptake prior to (and beyond) the deliquescence of ammonium sulfate. Hence, certain hygroscopic organic surrogate compounds can substantially affect the deliquescence point of ammonium sulfate and overall particle water uptake.

Contribution of particulate water to the measured aerosol optical properties of aged aerosol

Measurements of aged aerosol scattering in the Eastern Mediterranean at ambient and low relative humidity (RH) are combined with measurements of its size composition distribution and its aerosol water content to gain insights about its hygroscopic and optical properties. The particle water uptake above 60% RH can be explained by the water absorption by the inorganic particulate matter in this sulphate rich environment. However, the particles were supersaturated aqueous solutions at low RH and this water cannot be explained just by the water associated with their inorganic components in a metastable state. We estimate that approximately 20% of this water may be contributed by the aged organic particulate matter. A semi-empirical equation is derived allowing the estimation of the aged aerosol Volume Growth Factor (VGF) from the ratios of scattering at ambient and low RH. The predictions of the equation are in good agreement with the measurement dataset obtained during the study.

Reconciliation of measurements of hygroscopic growth and critical supersaturation of aerosol particles in central Germany

Abstract. Aerosol physical, chemical and hygroscopic properties were measured in a range of airmasses during COPS (Convective and Orographically-induced Precipitation Study) ground-based in June and July of 2007 at the Hornisgrinde mountain site in the Black Forest, Southwest Germany. Non-refractory aerosol composition was measured with an Aerosol Mass Spectrometer, simultaneous to hygroscopic growth factors at 86% relative humidity and CCN activity measurements for particles of dry (&lt;20%) diameters 27 to 217 nm, with particle water uptake exhibiting substantial variability with time and with particle size. Variability in the measurements of hygroscopic growth factor and critical supersaturation for particles of similar sizes indicates significant compositional impact on particle water affinity. Critical supersaturation prediction using a single parameter hygroscopicity approximation derived from measured HTDMA mean growth factors deviate, beyond measurement uncertainties, from critical supersaturations derived from CCN measurements. These led to differences averaging around 35% in the number of CCN (NCCN) for the most reliable measurements depending on averaging methodology, often very much larger for individual time periods. This indicates aspects of water uptake behaviour unresolved in this experiment by the single parameter representation which, depending on its origin, may have important consequences on its generalised use.

An evaluation and comparison of cloud condensation nucleus activity models: Predicting particle critical saturation from growth at subsaturation

The ability of particles to activate and form cloud droplets influences the functioning of the Earth's hydrological cycle. This work links the particle water uptake at subsaturation to the critical supersaturation ratio needed for particles to become cloud condensation nuclei (CCN). Five models using the particle hygroscopic growth at subsaturation for predicting the critical supersaturation needed for droplet activation were applied to a laboratory data set of inorganic and organic compounds and mixtures of them. The data set consisted of hygroscopicity tandem differential mobility analyzer measurements and CCN counter measurements. No chemical composition information was used when applying the models. All models tested were based on modifications of Köhler theory and gave similar results. The agreement between predicted and measured critical supersaturations was good, considering the relatively simple models used. A trend of overestimating the critical supersaturations was observed, typically by ∼15%. The best performing model gave on average only a 4% offset from experimental values; the model with the largest deviation was offset by 20%. A comparison was made between the number of soluble entities (ions or nondissociating molecules) estimated from the particle hygroscopic growth at 90% relative humidity (RH) and the number estimated from the particle critical supersaturation; a ∼35% increase was observed in the effective number of entities in solution when going from 90% RH to activation. For many types of aerosols, differences in the model approaches tested do not induce large differences in the predicted critical supersaturation. However, it is most important to follow the recommendations published with the respective models and not use them indiscriminately.

Deliquescence and efflorescence of small particles

We examine size-dependent deliquescence/efflorescence phase transformation for particles down to several nanometers in size. Thermodynamic properties of inorganic salt particles, coated with aqueous solution layers of varying thickness and surrounded by vapor, are analyzed. A thin layer criterion (TLC) is introduced to define a limiting deliquescence relative humidity (RH(D)) for small particles. This requires: (1) equality of chemical potentials between salt in an undissolved core, and thin adsorbed solution layer, and (2) equality of chemical potentials between water in the thin layer and vapor phase. The usual bulk deliquescence conditions are recovered in the limit of large dry particle size. Nanosize particles are found to deliquesce at relative humidity just below the RH(D) on crossing a nucleation barrier, located at a critical solution layer thickness. This barrier vanishes precisely at the RH(D) defined by the TLC. Concepts and methods from nucleation theory including the kinetic potential, self-consistent nucleation theory, nucleation theorems, and the Gibbs dividing surface provide theoretical foundation and point to unifying features of small particle deliquescence/efflorescence processes. These include common thermodynamic area constructions, useful for interpretation of small particle water uptake measurements, and a common free-energy surface, with constant RH cross sections describing deliquescence and efflorescence related through the nucleation theorem.

Comprehensive airborne characterization of aerosol from a major bovine source

Abstract. We report an extensive airborne characterization of aerosol downwind of a massive bovine source in the San Joaquin Valley (California) on two flights during July 2007. The Center for Interdisciplinary Remotely-Piloted Aircraft Studies (CIRPAS) Twin Otter probed chemical composition, particle size distribution, mixing state, sub- and supersaturated water uptake behavior, light scattering properties, and the interrelationship between these parameters and meteorology. Total PM1.0 levels and concentrations of organics, nitrate, and ammonium were enhanced in the plume from the source as compared to the background aerosol. Organics dominated the plume aerosol mass (~56–64%), followed either by sulfate or nitrate, and then ammonium. Particulate amines were detected in the plume aerosol by a particle-into-liquid sampler (PILS) and via mass spectral markers in the Aerodyne C-ToF-AMS. Amines were found to be a significant atmospheric base even in the presence of ammonia; particulate amine concentrations are estimated as at least 14–23% of that of ammonium in the plume. Enhanced sub- and supersaturated water uptake and reduced refractive indices were coincident with lower organic mass fractions, higher nitrate mass fractions, and the detection of amines. The likelihood of suppressed droplet growth owing to kinetic limitations from hydrophobic organic material is explored. After removing effects associated with size distribution and mixing state, the normalized activated fraction of cloud condensation nuclei (CCN) increased as a function of the subsaturated hygroscopic growth factor, with the highest activated fractions being consistent with relatively lower organic mass fractions and higher nitrate mass fractions. Subsaturated hygroscopic growth factors for the organic fraction of the aerosol are estimated based on employing the Zdanovskii-Stokes Robinson (ZSR) mixing rule. Representative values for a parameterization treating particle water uptake in both the sub- and supersaturated regimes are reported for incorporation into atmospheric models.

Aerosol optical properties and related chemical apportionment at Xinken in Pearl River Delta of China

Aerosol optical properties (AOPs) of sub- 10 μ m particles under dry conditions (relative humidity (RH) < 20 % ) were investigated at Xinken in Pearl River Delta of China from 4 October to 5 November 2004. Severe aerosol optical pollution has been found characterized by strongly light-absorbing particles. At 550 nm, the magnitude of the light scattering ( 333 ± 138 Mm - 1 ) and absorption ( 70 ± 42 Mm - 1 ), limited visual range ( 5.3 ± 2.5 km ), and low single scattering albedo ( 0.83 ± 0.05 ) show Xinken to be comparable to the most polluted urban cores rather than even a polluted rural site. Other presented AOPs include hemispheric backscattering fraction ( 11 ± 1 % ) and asymmetry parameter ( 0.67 ± 0.01 ) at 550 nm, and Ångström exponent ( a ˚ 450 / 700 = 1.6 ± 0.15 ). Systematic relationships exist among the various AOPs. Their diurnal variations cannot be solely explained with the development of atmospheric boundary layer, but also obviously influenced by local wind patterns, variation of sources, photochemistry and nighttime heterogeneous chemistry. The fractional contributions to extinction, scattering and absorption ( f ep ; sp ; ap ) due to sub-aerosol-populations and individual chemical compounds are derived by the Mie simulations. The sub- 1 μ m particles contribute more than 90% of the particle extinction ( σ ep , 550 nm ). Under dry conditions, f ep of non-sea-salt sulfate, particulate organic matter, elemental carbon (EC) and residual are about 44%, 17%, 17% and 15%, respectively. However, the water uptake of particles can contribute 50–60% to σ ep , 550 nm at RH 90%. So in the ambient atmosphere, sulfate, carbonaceous material and water all play very important roles, concerning the visibility impairment at Xinken. The respective mass extinction, scattering and absorption efficiencies ( α ep ; sp ; ap ) are mostly consistent with previously reported values for the polluted area. α ap , EC , 550 nm for sub- 1 μ m and sub- 10 μ m ranges are 9.3 ± 1.4 and 7.2 ± 1.0 m 2 g - 1 , respectively. Our results imply a higher α ap , EC for more internally mixed EC under the atmospheric conditions present at Xinken.

Aerosol thermodynamics of potassium salts, double salts, and water content near the eutectic

Water uptake by hygroscopic constituents of atmospheric particles has implications for climate and health. This article focuses on three topics related to calculating particle water uptake. First, an electrodynamic balance (EDB) is used to measure water activity for supersaturated binary KNO3 and KCl solutions. The EDB measurements for KNO3 confirm earlier predictions, while those for KCl confirm earlier measurements. Second, our earlier theory for the variation in mutual deliquescence relative humidity (MDRH) with temperature (T) is extended to double salt systems. The MDRH(T) equation for double salt systems reduces to the earlier equation under some conditions, and predictions for two systems are in reasonable agreement with solubility-based calculations. Finally, an approximate treatment of water uptake in the MDRH region (i.e., near the eutectic) is evaluated, and a new approach is developed that accounts for particle composition. The new approach represents predictions of a benchmark model well and eliminates most of the error associated with the earlier method. Although simple treatments of water uptake near the eutectic may introduce error into equilibrium calculations, their use can sometimes be justified based on inherent limitations of aerosol representations in chemistry-transport models. Results of this study can be used to improve calculations of water content in atmospheric aerosol models.

Size distribution and hygroscopic properties of aerosol particles from dry-season biomass burning in Amazonia

Abstract. Aerosol particle number size distributions and hygroscopic properties were measured at a pasture site in the southwestern Amazon region (Rondonia). The measurements were performed 11 September-14 November 2002 as part of LBA-SMOCC (Large scale Biosphere atmosphere experiment in Amazonia - SMOke aerosols, Clouds, rainfall and Climate), and cover the later part of the dry season (with heavy biomass burning), a transition period, and the onset of the wet period. Particle number size distributions were measured with a DMPS (Differential Mobility Particle Sizer, 3-850nm) and an APS (Aerodynamic Particle Sizer), extending the distributions up to 3.3 µm in diameter. An H-TDMA (Hygroscopic Tandem Differential Mobility Analyzer) measured the hygroscopic diameter growth factors (Gf) at 90% relative humidity (RH), for particles with dry diameters (dp) between 20-440 nm, and at several occasions RH scans (30-90% RH) were performed for 165nm particles. These data provide the most extensive characterization of Amazonian biomass burning aerosol, with respect to particle number size distributions and hygroscopic properties, presented until now. The evolution of the convective boundary layer over the course of the day causes a distinct diel variation in the aerosol physical properties, which was used to get information about the properties of the aerosol at higher altitudes. The number size distributions averaged over the three defined time periods showed three modes; a nucleation mode with geometrical median diameters (GMD) of ~12 nm, an Aitken mode (GMD=61-92 nm) and an accumulation mode (GMD=128-190 nm). The two larger modes were shifted towards larger GMD with increasing influence from biomass burning. The hygroscopic growth at 90% RH revealed a somewhat external mixture with two groups of particles; here denoted nearly hydrophobic (Gf~1.09 for 100 nm particles) and moderately hygroscopic (Gf~1.26). While the hygroscopic growth factors were surprisingly similar over the periods, the number fraction of particles belonging to each hygroscopic group varied more, with the dry period aerosol being more dominated by nearly hydrophobic particles. As a result the total particle water uptake rose going into the cleaner period. The fraction of moderately hygroscopic particles was consistently larger for particles in the accumulation mode compared to the Aitken mode for all periods. Scanning the H-TDMA over RH (30-90% RH) showed no deliquescence behavior. A parameterization of both Gf(RH) and Gf(dp), is given.