Hygroscopic Growth Measurements Research Articles

Water activity and surface tension of aqueous ammonium sulfate and D-glucose aerosol nanoparticles

Abstract. Water activity (aw) and interfacial energy or surface tension (σ) are key thermodynamic parameters to describe the hygroscopic growth of atmospheric aerosol particles and their ability to serve as cloud condensation nuclei (CCN), thus influencing the hydrological cycle and climate. Due to size effects and complex mixing states, however, these parameters are not well constrained for nanoparticles composed of organic and inorganic compounds in aqueous solution. In this study, we determined aw and σ by differential Köhler analysis (DKA) of hygroscopic growth measurement data for aerosol particles smaller than 100 nm composed of aqueous ammonium sulfate (AS), D-glucose (Gl), and their mixtures. High-precision measurements of hygroscopic growth were performed at relative humidities (denoted RH) ranging from 2.0 % to 99.6 % with a high-humidity tandem differential mobility analyzer (HHTDMA) in three complementary modes of operation: hydration, dehydration, and restructuring. The restructuring mode (hydration followed by dehydration) enabled the transformation of initially irregular particles into compact globules and the determination of mass equivalent diameters. The HHTDMA-derived growth factors complemented by DKA allows for determination of water activity and surface tension from dilute to highly supersaturated aqueous solutions that are not accessible with other methods. Thus, for mixed AS / Gl nanoparticles with mass ratios of 4:1 and 1:1, the upper limit of solute mass fraction (Xs) was 0.92 and 0.98, respectively. For pure AS and Gl, the DKA-derived aw is in good agreement with electrodynamic balance and bulk measurement data. For AS particles, our aw data also agree well with the Extended Aerosol Inorganics Model (E-AIM III) over the entire concentration range. In contrast, the UNIFAC model as a part of AIOMFAC (Zuend et al., 2011) was found to overestimate aw in aqueous Gl particles, which can be attributed to unaccounted intermolecular interactions. For mixed AS and Gl nanoparticles, we observed a non-monotonic concentration dependence of the surface tension that does not follow the predictions by modeling approaches constructed for mixed inorganic/organic systems. Thus, AS / Gl particles with a 1:1 mass ratio exhibited a strong decrease of σ with increasing solute mass fraction, a minimum value of 56.5 mN m−1 at Xs≈0.5, and a reverse trend of increasing σ at higher concentrations. We suggest that D-glucose molecules surrounded by ammonium sulfate ions tend to associate, forming non-polar aggregates, which lowers the surface tension at the air–droplet interface. We analyzed the uncertainty in the DKA-derived water activity and surface tension, related to the instrumental errors as well as to the morphology of the nanoparticles and their phase state. Our studies have shown that under optimal modes of operation of HHTDMA for moderate aqueous concentrations, the uncertainty in aw and σ does not exceed 0.2 %–0.4 % and 3 %–4 %, respectively, but it increases by an order of magnitude in the case of highly concentrated nanodroplet solutions.

Tutorial: Electrodynamic balance methods for single particle levitation and the physicochemical analysis of aerosol

Single particle levitation methods are a powerful subset of aerosol instrumentation that allow a wide range of particle properties and processes to be explored. One of the most common forms of single particle levitation uses electric fields and is generally referred to as an electrodynamic balance (EDB). There are many different kinds of EDB's that have been designed with different applications in mind, and a corresponding array of analytical tools have been developed to characterize particles held in these traps. In this tutorial, we review the design and development of the EDB and discuss a range of analytical methods, including electrostatic analysis, light scattering, spectroscopy, and imaging, that allow for measurements of hygroscopic growth, volatility, surface tension and viscosity, diffusion, and phase and morphology. We go on to review recent advanced analytical methods using mass spectrometry to probe particle composition. This review is intended to provide readers with the basic knowledge to set up an EDB platform, design measurement protocols based on the available analytical tools, and run experiments to probe the fundamental properties of aerosol particles relevant to their role in the atmosphere, impacts on clouds and climate, effects on air quality, role in health and disease, and applications in industrial processes.

Atmospheric nanoparticles hygroscopic growth measurement by a combined surface plasmon resonance microscope and hygroscopic tandem differential mobility analyzer

Abstract. The hygroscopic growth of atmospheric aerosols plays an important role in regional radiation, cloud formation, and hence climate. Aerosol hygroscopic growth is often characterized by hygroscopic tandem differential mobility analyzers (HTDMAs), and Xie et al. (2020) recently demonstrated that hygroscopic growth measurements of a single particle are possible using a surface plasmon resonance microscope-azimuthal rotation illumination (SPRM-ARI). The hygroscopic properties of ambient aerosols are not uniform and often exhibit large relative humidity (RH) and size variabilities due to different chemical compositions and mixing states. To better understand the contribution of different aerosol components and establish a link between the apparent hygroscopic properties of single particles and bulk aerosols, we conduct combined hygroscopic growth measurements using a SPRM-ARI and an HTDMA as a case study to prove the concept (experimental information: 100–200 nm, during noontime on 28 September 2021 and 22 March 2022 in Hefei, China). According to the distinct hygroscopic growth behavior from single-particle probing using a SPRM-ARI, the individual particles can be classified into three categories defined as non-hygroscopic (NH), less hygroscopic (LH), and more hygroscopic (MH). The mean growth factor (GF) of the three categories can be utilized to reproduce the GF distribution obtained from the HTDMA measurement. The chemical compositions of individual particles from the three categories are identified to be organic carbon (OC), soot (mainly elemental carbon), fly ash, and secondary aerosols (mainly OC and sulfate), using scanning electron microscopy (SEM) with an energy-dispersive spectrometer (EDS). The coupled SPRM–HTDMA measurement suggests a size-dependent variation of aerosol chemical components, i.e., an increase of OC fraction with increasing particle sizes, which agrees reasonably well with the chemical compositions from collected aerosol samples. This likely links the hygroscopic properties of individual particles to their bulk hygroscopic growth and chemical composition.

Rapid measurement of RH-dependent aerosol hygroscopic growth using a humidity-controlled fast integrated mobility spectrometer (HFIMS)

Abstract. The ability of aerosol particles to uptake water (hygroscopic growth) is an important determinant of aerosol optical properties and radiative effects. Aerosol hygroscopic growth is traditionally measured by humidified tandem differential mobility analyzers (HTDMA), in which size-selected dry particles are exposed to elevated relative humidity (RH), and the size distribution of humidified particles is subsequently measured using a scanning mobility particle sizer. As a scanning mobility particle sizer can measure only one particle size at a time, HTDMA measurements are time consuming, and ambient measurements are often limited to a single RH level. Pinterich et al. (2017b) showed that fast measurements of aerosol hygroscopic growth are possible using a humidity-controlled fast integrated mobility spectrometer (HFIMS). In HFIMS, the size distribution of humidified particles is rapidly captured by a water-based fast integrated mobility spectrometer (WFIMS), leading to a factor of ∼10 increase in measurement time resolution. In this study we present a prototype HFIMS that extends fast hygroscopic growth measurements to a wide range of atmospherically relevant RH values, allowing for more comprehensive characterizations of aerosol hygroscopic growth. A dual-channel humidifier consisting of two humidity conditioners in parallel is employed such that aerosol RH can be quickly stepped among different RH levels by sampling from alternating conditioners. The measurement sequence is also optimized to minimize the transition time between different particle sizes. The HFIMS is capable of measuring aerosol hygroscopic growth of six particle diameters under five RH levels ranging from 20 % to 85 % (30 separate measurements) every 25 min. The performance of this HFIMS is characterized and validated using laboratory-generated ammonium sulfate aerosol standards. Measurements of ambient aerosols are shown to demonstrate the capability of HFIMS to capture the rapid evolution of aerosol hygroscopic growth and its dependence on both size and RH.

Measurements of atmospheric aerosol hygroscopic growth based on multi-channel Raman-Mie lidar

In this study, an effective method with a multi-channel Raman-Mie lidar has been proposed to detect the hygroscopic growth of atmospheric aerosol in the boundary layer, and the effect of aerosol hygroscopic growth on the optical and microphysical properties of aerosol particles is studied. The vertical relative humidity profile is obtained by combining calibrated water vapor mixing ratio and temperature profiles from Raman-Mie lidar. Two cases were selected in Hefei to analyze the aerosol hygroscopic growth. Case studies show that the increase of the backscatter coefficient of aerosol is consistent with the increase of relative humidity, and the decrease of Ångstrom exponent indicates the increasing aerosol particle size due to the hygroscopic growth process. The Kasten model is used to fit the aerosol hygroscopic enhancement factor, and the b value from the Kasten parameterization for Case II is much larger than that for Case I, which shows the stronger hygroscopicity in Case II. The results indicate that the multi-channel Raman-Mie lidar has potential in the measurements of the hygroscopic growth of aerosols.

Nano-hygroscopicity tandem differential mobility analyzer (nano-HTDMA) for investigating hygroscopic properties of sub-10 nm aerosol nanoparticles

Abstract. Interactions between water and nanoparticles are relevant for atmospheric multiphase processes, physical chemistry, and materials science. Current knowledge of the hygroscopic and related physicochemical properties of nanoparticles, however, is restricted by the limitations of the available measurement techniques. Here, we present the design and performance of a nano-hygroscopicity tandem differential mobility analyzer (nano-HTDMA) apparatus that enables high accuracy and precision in hygroscopic growth measurements of aerosol nanoparticles with diameters less than 10 nm. Detailed methods of calibration and validation are provided. Besides maintaining accurate and stable sheath and aerosol flow rates (±1 %), high accuracy of the differential mobility analyzer (DMA) voltage (±0.1 %) in the range of ∼0–50 V is crucial for achieving accurate sizing and small sizing offsets between the two DMAs (<1.4 %). To maintain a stable relative humidity (RH), the humidification system and the second DMA are placed in a well-insulated and air conditioner housing (±0.1 K). We also tested and discussed different ways of preventing predeliquescence in the second DMA. Our measurement results for ammonium sulfate nanoparticles are in good agreement with Biskos et al. (2006b), with no significant size effect on the deliquescence and efflorescence relative humidity (DRH and ERH, respectively) at diameters down to 6 nm. For sodium sulfate nanoparticles, however, we find a pronounced size dependence of DRH and ERH between 20 and 6 nm nanoparticles.

The Dependence of Radius on Relative Humidity and Solute Mass at High Relative Humidities Up to and Including 100%

AbstractThis manuscript presents a rigorous examination of the equilibrium radius ratio of hygroscopic aerosol particles that are solution drops of ideal and actual inorganic solutes for a range of solute masses in the relative humidity range 99–100%. Analysis is presented first for ideal solutes over a range of solute masses for different hygroscopicities, providing a theoretical framework for the subsequent analysis of actual solutes. Dimensionless quantities are used to reduce the Köhler equation to one with no free parameters and an approximate solution is presented. Next analysis is presented for three common inorganic solutes of atmospheric importance: sodium chloride, ammonium sulfate, and sulfuric acid, with a range of solute masses considered for each substance. The extent to which nonideality is important for these solutes over the ranges of relative humidities and solute masses considered is examined. A simple but accurate single‐parameter expression is presented for the equilibrium radius ratio as a function of relative humidity that contains the dependences on solute mass and composition for these solutes. The accuracy of this expression is quantified and factors that limit this accuracy are discussed. The expression is accurate to within 5% over most of the range of mass‐equivalent dry radii from 10 to 250 nm and relative humidities from below 99 up to 100%, over which the equilibrium radius ratio varies by more than a factor of 5, and it remains finite at 100% relative humidity. Finally, measurements of hygroscopic growth of aerosol particles in this relative humidity range are discussed.

A humidity-controlled fast integrated mobility spectrometer (HFIMS) for rapid measurements of particle hygroscopic growth

Abstract. We present a humidity-controlled fast integrated mobility spectrometer (HFIMS) for rapid particle hygroscopicity measurements. The HFIMS consists of a differential mobility analyzer (DMA), a relative humidity (RH) control unit and a water-based FIMS (WFIMS) coupled in series. The WFIMS (Pinterich et al., 2017) combines the fast integrated mobility spectrometer (Kulkarni and Wang, 2006a, b) with laminar flow water condensation methodologies (Hering and Stolzenburg, 2005; Spielman et al., 2017). Inside the WFIMS, particles of different electrical mobilities are spatially separated in an electric field, condensationally enlarged and imaged to provide 1 Hz measurements of size distribution spanning a factor of ∼ 3 in particle diameter, which is sufficient to cover the entire range of growth factor (GF) for atmospheric aerosol particles at 90 % RH. By replacing the second DMA of a traditional hygroscopicity tandem DMA (HTDMA) system with the WFIMS, the HFIMS greatly increases the speed of particle growth factor measurement. The performance of the HFIMS was evaluated using NaCl particles with well-known hygroscopic growth behavior and further through measurements of ambient aerosols. Results show that the HFIMS can reproduce, within 2 %, the literature values for hygroscopic growth of NaCl particles. NaCl deliquescence was observed between 76 and 77 % RH in agreement with the theoretical value of 76.5 % (Ming and Russell, 2001), and efflorescence relative humidity (43 %) was found to lie within the RH range of 41 to 56 % reported in the literature. Ambient data indicate that the HFIMS can measure the hygroscopic growth of five standard dry particle sizes ranging from 35 to 165 nm within less than 3 min, which makes it about 1 order of magnitude faster than traditional HTDMA systems.

Seven years of aerosol scattering hygroscopic growth measurements from SGP: Factors influencing water uptake

AbstractLong‐term measurements of changes in the aerosol scattering coefficient hygroscopic growth at the U.S. Department of Energy Southern Great Plains site provide information on the seasonal as well as size and chemical dependence of aerosol water uptake. Annual average sub‐10 μm fRH values (the ratio of aerosol scattering at 85%/40% relative humidity (RH)) were 1.78 and 1.99 for the gamma and kappa fit algorithms, respectively. The study found higher growth rates in the winter and spring seasons that correlated with a high aerosol nitrate mass fraction. fRH exhibited strong, but differing, correlations with the scattering Ångström exponent and backscatter fraction, two optical size‐dependent parameters. The aerosol organic mass fraction had a strong influence on fRH. Increases in the organic mass fraction and absorption Ångström exponent coincided with a decrease in fRH. Similarly, fRH declined with decreases in the aerosol single scatter albedo. Uncertainty analysis of the fit algorithms revealed high uncertainty at low scattering coefficients and increased uncertainty at high RH and fit parameters values.

Discontinuities in hygroscopic growth below and above water saturation for laboratory surrogates of oligomers in organic atmospheric aerosols

Abstract. Discontinuities in apparent hygroscopicity below and above water saturation have been observed for organic and mixed organic–inorganic aerosol particles in both laboratory studies and in the ambient atmosphere. However, uncertainty remains regarding the factors that contribute to observations of low hygroscopic growth below water saturation but enhanced cloud condensation nuclei (CCN) activity for a given aerosol population. Utilizing laboratory surrogates for oligomers in atmospheric aerosols, we explore the extent to which such discontinuities are influenced by organic component molecular mass and viscosity, non-ideal thermodynamic interactions between aerosol components, and the combination of these factors. Measurements of hygroscopic growth under subsaturated conditions and the CCN activity of aerosols comprised of polyethylene glycol (PEG) with average molecular masses ranging from 200 to 10 000 g mol−1 and mixtures of PEG with ammonium sulfate (AS) were conducted. Experimental results are compared to calculations of hygroscopic growth at thermodynamic equilibrium conducted with the Aerosol Inorganic Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model, and the potential influence of kinetic limitations on observed water uptake was further explored through estimations of water diffusivity in the PEG oligomers. Particle-phase behavior, including the prevalence of liquid–liquid phase separation (LLPS), was also modeled with AIOMFAC. Under subsaturated relative humidity (RH) conditions, we observed little variability in hygroscopic growth across PEG systems with different molecular masses; however, an increase in CCN activity with increasing PEG molecular mass was observed. This effect is most pronounced for PEG–AS mixtures, and, in fact, an enhancement in CCN activity was observed for the PEG10000–AS mixture as compared to pure AS, as evidenced by a 15 % reduction in critical activation diameter at a supersaturation of 0.8 %. We also observed a marked increase in apparent hygroscopicity for mixtures of higher molecular mass PEG and AS under supersaturated conditions as compared to subsaturated hygroscopic growth. AIOMFAC-based predictions and estimations of water diffusivity in PEG suggest that such discontinuities in apparent hygroscopicity above and below water saturation can be attributed, at least in part, to differences in the sensitivity of water uptake behavior to surface tension effects. There is no evidence that kinetic limitations to water uptake due to the presence of viscous aerosol components influenced hygroscopic growth. For the systems that display an enhancement in apparent hygroscopicity above water saturation, LLPS is predicted to persist to high RH. This indicates a miscibility gap and is likely to influence bulk-to-surface partitioning of PEG at high RH, impacting droplet surface tension and CCN activity. This work provides insight into the factors likely to be contributing to discontinuities in aerosol water-uptake behavior below and above water saturation that have been observed previously in the ambient atmosphere.

Accurate Measurements of Aerosol Hygroscopic Growth over a Wide Range in Relative Humidity

Using a comparative evaporation kinetics approach, we describe a new and accurate method for determining the equilibrium hygroscopic growth of aerosol droplets. The time-evolving size of an aqueous droplet, as it evaporates to a steady size and composition that is in equilibrium with the gas phase relative humidity, is used to determine the time-dependent mass flux of water, yielding information on the vapor pressure of water above the droplet surface at every instant in time. Accurate characterization of the gas phase relative humidity is provided from a control measurement of the evaporation profile of a droplet of know equilibrium properties, either a pure water droplet or a sodium chloride droplet. In combination, and by comparison with simulations that account for both the heat and mass transport governing the droplet evaporation kinetics, these measurements allow accurate retrieval of the equilibrium properties of the solution droplet (i.e., the variations with water activity in the mass fraction of solute, diameter growth factor, osmotic coefficient or number of water molecules per solute molecule). Hygroscopicity measurements can be made over a wide range in water activity (from >0.99 to, in principle, <0.05) on time scales of <10 s for droplets containing involatile or volatile solutes. The approach is benchmarked for binary and ternary inorganic solution aerosols with typical uncertainties in water activity of <±0.2% at water activities >0.9 and ∼±1% below 80% RH, and maximum uncertainties in diameter growth factor of ±0.7%. For all of the inorganic systems examined, the time-dependent data are consistent with large values of the mass accommodation (or evaporation) coefficient (>0.1).

Chemical composition, microstructure, and hygroscopic properties of aerosol particles at the Zotino Tall Tower Observatory (ZOTTO), Siberia, during a summer campaign

Abstract. In this study we describe the hygroscopic properties of accumulation- and coarse-mode aerosol particles sampled at the Zotino Tall Tower Observatory (ZOTTO) in central Siberia (61° N, 89° E) from 16 to 21 June 2013. The hygroscopic growth measurements were supplemented with chemical analyses of the samples, including inorganic ions and organic/elemental carbon. In addition, the microstructure and chemical compositions of aerosol particles were analyzed by x-ray micro-spectroscopy (STXM-NEXAFS) and transmission electron microscopy (TEM). A mass closure analysis indicates that organic carbon accounted for 61 and 38 % of particulate matter (PM) in the accumulation mode and coarse mode, respectively. The water-soluble fraction of organic matter was estimated to be 52 and 8 % of PM in these modes. Sulfate, predominantly in the form of ammoniated sulfate, was the dominant inorganic component in both size modes: ~ 34 % in the accumulation mode vs. ~ 47 % in the coarse mode. The hygroscopic growth measurements were conducted with a filter-based differential hygroscopicity analyzer (FDHA) over the range of 5–99.4 % RH in the hydration and dehydration operation modes. The FDHA study indicates that both accumulation and coarse modes exhibit pronounced water uptake approximately at the same relative humidity (RH), starting at ~ 70 %, while efflorescence occurred at different humidities, i.e., at ~ 35 % RH for submicron particles vs. ~ 50 % RH for supermicron particles. This ~ 15 % RH difference was attributed to higher content of organic material in the submicron particles, which suppresses water release in the dehydration experiments. The kappa mass interaction model (KIM) was applied to characterize and parameterize non-ideal solution behavior and concentration-dependent water uptake by atmospheric aerosol samples in the 5–99.4 % RH range. Based on KIM, the volume-based hygroscopicity parameter, κv, was calculated. The κv,ws value related to the water-soluble (ws) fraction was estimated to be ~ 0.15 for the accumulation mode and ~ 0.36 for the coarse mode, respectively. The obtained κv,ws for the accumulation mode is in good agreement with earlier data reported for remote sites in the Amazon rain forest (κv &amp;amp;approx; 0.15) and a Colorado mountain forest (κv &amp;amp;approx; 0.16 ). We used the Zdanovskii–Stokes–Robinson (ZSR) mixing rule to predict the chemical composition dependent hygroscopicity, κv,p. The obtained κv,p values overestimate the experimental FDHA-KIM-derived κv,ws by factors of 1.8 and 1.5 for the accumulation and coarse modes, respectively. This divergence can be explained by incomplete dissolution of the hygroscopic inorganic compounds resulting from kinetic limitations due to a sparingly soluble organic coating. The TEM and STXM-NEXAFS results indicate that aged submicron (&gt; 300 nm) and supermicron aerosol particles possess core–shell structures with an inorganic core, and are enriched in organic carbon at the mixed particle surface. The direct FDHA kinetic studies provide a bulk diffusion coefficient of water of ~ 10−12 cm2 s−1 indicating a semi-solid state of the organic-rich phase leading to kinetic limitations of water uptake and release during hydration and dehydration cycles. Overall, the present ZOTTO data set, obtained in the growing season, has revealed a strong influence of organic carbon on the hygroscopic properties of the ambient aerosols. The sparingly soluble organic coating controls hygroscopic growth, phase transitions, and microstructural rearrangement processes. The observed kinetic limitations can strongly influence the outcome of experiments performed on multi-second timescales, such as the commonly applied HTDMA (Hygroscopicity Tandem Differential Mobility Analyzer) and CCNC (Cloud Condensation Nuclei Counter) measurements.

Relating particle hygroscopicity and CCN activity to chemical composition during the HCCT-2010 field campaign

Abstract. Particle hygroscopic growth at 90% RH (relative humidity), cloud condensation nuclei (CCN) activity, and size-resolved chemical composition were concurrently measured in the Thüringer Wald mid-level mountain range in central Germany in the fall of 2010. The median hygroscopicity parameter values, κ, of 50, 75, 100, 150, 200, and 250 nm particles derived from hygroscopicity measurements are respectively 0.14, 0.14, 0.17, 0.21, 0.24, and 0.28 during the sampling period. The closure between HTDMA (Hygroscopicity Tandem Differential Mobility Analyzers)-measured (κHTDMA) and chemical composition-derived (κchem) hygroscopicity parameters was performed based on the Zdanovskii–Stokes–Robinson (ZSR) mixing rule. Using size-averaged chemical composition, the κ values are substantially overpredicted (30 and 40% for 150 and 100 nm particles). Introducing size-resolved chemical composition substantially improved closure. We found that the evaporation of NH4NO3, which may happen in a HTDMA system, could lead to a discrepancy in predicted and measured particle hygroscopic growth. The hygroscopic parameter of the organic fraction, κorg, is positively correlated with the O : C ratio (κorg = 0.19 × (O : C) − 0.03). Such correlation is helpful to define the κorg value in the closure study. κ derived from CCN measurement was around 30% (varied with particle diameters) higher than that determined from particle hygroscopic growth measurements (here, hydrophilic mode is considered only). This difference might be explained by the surface tension effects, solution non-ideality, gas-particle partitioning of semivolatile compounds, and the partial solubility of constituents or non-dissolved particle matter. Therefore, extrapolating from HTDMA data to properties at the point of activation should be done with great care. Finally, closure study between CCNc (cloud condensation nucleus counter)-measured (κCCN) and chemical composition (κCCN, chem) was performed using CCNc-derived κ values for individual components. The results show that the κCCN can be well predicted using particle size-resolved chemical composition and the ZSR mixing rule.

Mass-based hygroscopicity parameter interaction model and measurement of atmospheric aerosol water uptake

Abstract. In this study we derive and apply a mass-based hygroscopicity parameter interaction model for efficient description of concentration-dependent water uptake by atmospheric aerosol particles with complex chemical composition. The model approach builds on the single hygroscopicity parameter model of Petters and Kreidenweis (2007). We introduce an observable mass-based hygroscopicity parameter κm which can be deconvoluted into a dilute hygroscopicity parameter (κm0) and additional self- and cross-interaction parameters describing non-ideal solution behavior and concentration dependencies of single- and multi-component systems. For reference aerosol samples of sodium chloride and ammonium sulfate, the κm-interaction model (KIM) captures the experimentally observed concentration and humidity dependence of the hygroscopicity parameter and is in good agreement with an accurate reference model based on the Pitzer ion-interaction approach (Aerosol Inorganic Model, AIM). Experimental results for pure organic particles (malonic acid, levoglucosan) and for mixed organic-inorganic particles (malonic acid – ammonium sulfate) are also well reproduced by KIM, taking into account apparent or equilibrium solubilities for stepwise or gradual deliquescence and efflorescence transitions. The mixed organic-inorganic particles as well as atmospheric aerosol samples exhibit three distinctly different regimes of hygroscopicity: (I) a quasi-eutonic deliquescence &amp;amp; efflorescence regime at low-humidity where substances are just partly dissolved and exist also in a non-dissolved phase, (II) a gradual deliquescence &amp;amp; efflorescence regime at intermediate humidity where different solutes undergo gradual dissolution or solidification in the aqueous phase; and (III) a dilute regime at high humidity where the solutes are fully dissolved approaching their dilute hygroscopicity. For atmospheric aerosol samples collected from boreal rural air and from pristine tropical rainforest air (secondary organic aerosol) we present first mass-based measurements of water uptake over a wide range of relative humidity (1–99.4%) obtained with a new filter-based differential hygroscopicity analyzer (FDHA) technique. For these samples the concentration dependence of κm can be described by a simple KIM model equation based on observable mass growth factors and a total of only six fit parameters summarizing the combined effects of the dilute hygroscopicity parameters, self- and cross-interaction parameters, and solubilities of all involved chemical components. One of the fit parameters represents κm0 and can be used to predict critical dry diameters for the activation of cloud condensation nuclei (CCN) as a function of water vapor supersaturation according to Köhler theory. For sodium chloride and ammonium sulfate reference particles as well as for pristine rainforest aerosols consisting mostly of secondary organic matter, we obtained good agreement between the KIM predictions and measurement data of CCN activation. The application of KIM and mass-based measurement techniques shall help to bridge gaps in the current understanding of water uptake by atmospheric aerosols: (1) the gap between hygroscopicity parameters determined by hygroscopic growth measurements under sub-saturated conditions and by CCN activation measurements at water vapor supersaturation, and (2) the gap between the results of simplified single parameter models widely used in atmospheric or climate science and the results of complex multi-parameter ion- and molecule-interaction models frequently used in physical chemistry and solution thermodynamics (e.g., AIM, E-AIM, ADDEM, UNIFAC, AIOMFAC).

Characterization of Solvent-Extractable Organics in Urban Aerosols Based on Mass Spectrum Analysis and Hygroscopic Growth Measurement

To characterize atmospheric particulate organics with respect to polarity, aerosol samples collected on filters in the urban area of Nagoya, Japan, in 2009 were extracted using water, methanol, and ethyl acetate. The extracts were atomized and analyzed using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a hygroscopicity tandem differential mobility analyzer. The atmospheric concentrations of the extracted organics were determined using phthalic acid as a reference material. Comparison of the organic carbon concentrations measured using a carbon analyzer and the HR-ToF-AMS suggests that organics extracted with water (WSOM) and ethyl acetate (EASOM) or those extracted with methanol (MSOM) comprise the greater part of total organics. The oxygen-carbon ratios (O/C) of the extracted organics varied: 0.51-0.75 (WSOM), 0.37-0.48 (MSOM), and 0.27-0.33 (EASOM). In the ion-group analysis, WSOM, MSOM, and EASOM were clearly characterized by the different fractions of the CH and CO(2) groups. On the basis of the hygroscopic growth measurements of the extracts, κ of organics at 90% relative humidity (κ(org)) were estimated. Positive correlation of κ(org) with O/C (r 0.70) was found for MSOM and EASOM, but no clear correlation was found for WSOM.

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.

Size‐segregated measurements of cloud condensation nucleus activity and hygroscopic growth for aerosols at Cape Hedo, Japan, in spring 2008

Size‐segregated measurements of cloud condensation nucleus (CCN) activity and hygroscopic growth were performed simultaneously for sulfate‐rich aerosols at Cape Hedo, Okinawa, Japan, in spring 2008. The CCN fractions as functions of particle size at water vapor supersaturations of 0.44%, 0.25%, and 0.10% had nearly stepwise increases, and the diameters for 50% activation of its maximum (dact) were close to that of (NH4)2SO4. The size‐resolved hygroscopic growth factor g measured using a hygroscopicity tandem differential mobility analyzer at 85% relative humidity (RH) mainly showed unimodal and highly hygroscopic characteristics. The observed characteristics as well as aerosol mass spectrometer data suggest the dominance of internally mixed ammoniated sulfate‐rich particles. A clear negative correlation between dact and median g (gmedian) was observed for Aitken‐mode particles, and backward air mass trajectories indicate lower dact and higher g of the aerosols from China and the Pacific and the opposite tendency for those from Korea and Japan. The size dependence of gmedian suggests that less hygroscopic carbonaceous components were more enriched in Aitken‐mode particles and therefore affect the CCN activity and hygroscopicity. The CCN activation diameters were predicted on the basis of gmedian using a core‐shell model. The modeled activation diameters reasonably agreed with measured dact, suggesting that the surface tension lowering effect due to organics and the enhancement of bulk hygroscopicity at high RH due to sparingly soluble or polymeric compounds were small. The results suggest that CCN activity of sulfate‐rich aerosol particles is predicted well in regional and global aerosol models without incorporating these effects.

Examination of laboratory‐generated coated soot particles: An overview of the LACIS Experiment in November (LExNo) campaign

In the suite of laboratory measurements described here and in companion articles we deal with the hygroscopic growth and activation behavior of coated soot particles synthesized to mimic those of an atmospheric aerosol originating from biomass combustion. The investigations were performed during the measurement campaign LACIS Experiment in November (LExNo) which took place at the Leipzig Aerosol Cloud Interaction Simulator (LACIS). The specific goals of this campaign were (1) to perform a critical supersaturation measurement intercomparison using data sets from three different cloud condensation nucleus (CCN) instruments (two static thermal gradient type, one stream‐wise thermal gradient type) and LACIS, (2) to examine particle hygroscopic growth (hydrated particle size as function of relative humidity) for particle characteristics such as aerosol mass spectrometer (AMS) measured soluble mass and particle morphology, and (3) to relate critical supersaturations derived from both measurements of soluble mass and high‐humidity tandem differential mobility analyzer (HH‐TDMA) determined growth factors to critical supersaturations measured by means of the CCN instruments. This paper provides information on the particle synthesis techniques used during LExNo, an overview concerning the particle characterization measurements performed, and, by proving relations between measured composition, hygroscopic growth, and activation data, lay the foundations for the detailed investigations described in the companion studies. In the context of the present paper, excellent agreement of the critical supersaturations measured with three different CCN instruments and LACIS was observed. Furthermore, clear relations between coating masses determined with AMS and both hygroscopic growth factors at 98% RH and measured critical supersaturations could be seen. Also, a strong correlation between measured hygroscopic growth (growth factors at 98%) and measured critical supersaturation for all of the differently coated soot particles (coating substances being levoglucosan and/or ammonium (hydrogen) sulfate) was found. This is clearly indicative of the possibility of predicting the critical supersaturation of coated soot particles based on hygroscopic growth measurements using Köhler theory.

Widening the gap between measurement and modelling of secondary organic aerosol properties?

Abstract. The link between measured sub-saturated hygroscopicity and cloud activation potential of secondary organic aerosol particles produced by the chamber photo-oxidation of α-pinene in the presence or absence of ammonium sulphate seed aerosol was investigated using two models of varying complexity. A simple single hygroscopicity parameter model and a more complex model (incorporating surface effects) were used to assess the detail required to predict the cloud condensation nucleus (CCN) activity from the sub-saturated water uptake. Sub-saturated water uptake measured by three hygroscopicity tandem differential mobility analyser (HTDMA) instruments was used to determine the water activity for use in the models. The predicted CCN activity was compared to the measured CCN activation potential using a continuous flow CCN counter. Reconciliation using the more complex model formulation with measured cloud activation could be achieved widely different assumed surface tension behavior of the growing droplet; this was entirely determined by the instrument used as the source of water activity data. This unreliable derivation of the water activity as a function of solute concentration from sub-saturated hygroscopicity data indicates a limitation in the use of such data in predicting cloud condensation nucleus behavior of particles with a significant organic fraction. Similarly, the ability of the simpler single parameter model to predict cloud activation behaviour was dependent on the instrument used to measure sub-saturated hygroscopicity and the relative humidity used to provide the model input. However, agreement was observed for inorganic salt solution particles, which were measured by all instruments in agreement with theory. The difference in HTDMA data from validated and extensively used instruments means that it cannot be stated with certainty the detail required to predict the CCN activity from sub-saturated hygroscopicity. In order to narrow the gap between measurements of hygroscopic growth and CCN activity the processes involved must be understood and the instrumentation extensively quality assured. It is impossible to say from the results presented here due to the differences in HTDMA data whether: i) Surface tension suppression occurs ii) Bulk to surface partitioning is important iii) The water activity coefficient changes significantly as a function of the solute concentration.

Cloud condensation nucleation activity of biomass burning aerosol

We examine the hygroscopic properties of particles freshly emitted from laboratory biomass burning experiments conducted during the second Fire Lab At Missoula Experiment (FLAME‐II). Values of the hygroscopicity parameter, kappa, were derived from both hygroscopic growth measurements and size‐resolved (30–300 nm in diameter) cloud condensation nuclei (CCN) measurements for smokes emitted by the open combustion of 24 biomass fuels from the United States and Asia. To analyze the complex cloud condensation nuclei response curves we propose a new inversion scheme that corrects for multiple charge effects without the necessity of prior assumptions about the chemical composition and mixing state of the particles. Kappa varied between 0.02 (weakly hygroscopic) and 0.8 (highly hygroscopic). For individual smokes, kappa was a function of particle size, with 250 nm particles being generally weakly hygroscopic and sub‐100 nm particles being more hygroscopic. At any given size the emissions were often externally mixed, showing more and less hygroscopic growth modes and bimodal CCN activation spectra. Comparisons between growth factor‐derived and CCN‐derived hygroscopicities were consistent when taking this heterogeneity into account. A conceptual model of biomass burning emissions suggests that most particles are CCN active at the point of emission and do not require conversion in the atmosphere to more hygroscopic compositions before they can participate in cloud formation and undergo wet deposition.