scholarly journals Amorphous and crystalline aerosol particles interacting with water vapor: conceptual framework and experimental evidence for restructuring, phase transitions and kinetic limitations

2009 ◽  
Vol 9 (24) ◽  
pp. 9491-9522 ◽  
Author(s):  
E. Mikhailov ◽  
S. Vlasenko ◽  
S. T. Martin ◽  
T. Koop ◽  
U. Pöschl
Keyword(s):  
Phase Transitions ◽  
Water Vapor ◽  
Relative Humidity ◽  
Atmospheric Aerosols ◽  
Aerosol Particles ◽  
Organic Substances ◽  
Hygroscopic Growth ◽  
Amorphous Phases ◽  
Semi Solid ◽  
Hydration And Dehydration

Abstract. Interactions with water are crucial for the properties, transformation and climate effects of atmospheric aerosols. Here we present a conceptual framework for the interaction of amorphous aerosol particles with water vapor, outlining characteristic features and differences in comparison to crystalline particles. We used a hygroscopicity tandem differential mobility analyzer (H-TDMA) to characterize the hydration and dehydration of crystalline ammonium sulfate, amorphous oxalic acid and amorphous levoglucosan particles (diameter ~100 nm, relative humidity 5–95% at 298 K). The experimental data and accompanying Köhler model calculations provide new insights into particle microstructure, surface adsorption, bulk absorption, phase transitions and hygroscopic growth. The results of these and related investigations lead to the following conclusions: (1) Many organic substances, including carboxylic acids, carbohydrates and proteins, tend to form amorphous rather than crystalline phases upon drying of aqueous solution droplets. Depending on viscosity and microstructure, the amorphous phases can be classified as glasses, rubbers, gels or viscous liquids. (2) Amorphous organic substances tend to absorb water vapor and undergo gradual deliquescence and hygroscopic growth at lower relative humidity than their crystalline counterparts. (3) In the course of hydration and dehydration, certain organic substances can form rubber- or gel-like structures (supramolecular networks) and undergo transitions between swollen and collapsed network structures. (4) Organic gels or (semi-)solid amorphous shells (glassy, rubbery, ultra-viscous) with low molecular diffusivity can kinetically limit the uptake and release of water and may influence the hygroscopic growth and activation of aerosol particles as cloud condensation nuclei (CCN) and ice nuclei (IN). Moreover, (semi-)solid amorphous phases may influence the uptake of gaseous photo-oxidants and the chemical transformation and aging of atmospheric aerosols. (5) The shape and porosity of amorphous and crystalline particles formed upon dehydration of aqueous solution droplets depend on chemical composition and drying conditions. The apparent volume void fractions of particles with highly porous structures can range up to ~50% or more (xerogels, aerogels). (6) For efficient description of water uptake and phase transitions of aerosol particles, we propose not to limit the terms deliquescence and efflorescence to equilibrium phase transitions of crystalline substances. Instead we propose generalized definitions according to which amorphous and crystalline components can undergo gradual or prompt, partial or full deliquescence or efflorescence. We suggest that (semi-)solid amorphous phases may be important not only in the upper atmosphere as suggested in recent studies of glass formation at low temperatures. Depending on relative humidity, (semi-)solid phases and moisture-induced glass transitions may also play a role in gas-particle interactions at ambient temperatures in the lower atmosphere.

scholarly journals Amorphous and crystalline aerosol particles interacting with water vapor – Part 1: Microstructure, phase transitions, hygroscopic growth and kinetic limitations

2009 ◽  
Vol 9 (2) ◽  
pp. 7333-7412 ◽  
Author(s):  
E. Mikhailov ◽  
S. Vlasenko ◽  
S. T. Martin ◽  
T. Koop ◽  
U. Pöschl
Keyword(s):  
Aqueous Solution ◽  
Phase Transitions ◽  
Water Vapor ◽  
Aerosol Particles ◽  
Residual Water ◽  
Organic Substances ◽  
Hygroscopic Growth ◽  
Model Calculations ◽  
Void Fractions ◽  
Semi Solid

Abstract. Interactions with water are crucial for the properties, transformation and climate effects of atmospheric aerosols. Here we outline characteristic features and differences in the interaction of amorphous and crystalline aerosol particles with water vapor. Using a hygroscopicity tandem differential mobility analyzer (H-TDMA), we performed hydration, dehydration and cyclic hydration&amp;dehydration experiments with aerosol particles composed of levoglucosan, oxalic acid and ammonium sulfate (diameters ~100–200 nm, relative uncertainties <0.4%, relative humidities <5% to 95% at 298 K). The measurements and accompanying Köhler model calculations provide new insights into particle microstructure, surface adsorption, bulk absorption, phase transitions and hygroscopic growth. The results of these and related investigations lead to the following main conclusions: 1. Many organic substances (including carboxylic acids, carbohydrates and proteins) tend to form amorphous rather than crystalline phases upon drying of aqueous solution droplets. Depending on viscosity and microstructure, the amorphous phases can be classified as glasses, rubbers, gels or viscous liquids. 2. Amorphous organic substances tend to absorb water vapor and undergo gradual deliquescence and hygroscopic growth at much lower relative humidity than their crystalline counterparts. 3. In the course of hydration and dehydration, certain organic substances can form rubber- or gel-like structures (supra-molecular networks) and undergo stepwise transitions between swollen and collapsed network structures. 4. Organic gels or (semi-)solid amorphous shells (glassy, rubbery, ultra-viscous) with low molecular diffusivity can kinetically limit the uptake and release of water by submicron aerosol particles on (multi-)second time scales, which may influence the hygroscopic growth and activation of aerosol particles as cloud condensation nuclei (CCN) and ice nuclei (IN). 5. The shape and porosity of amorphous and crystalline particles formed upon dehydration of aqueous solution droplets depend on chemical composition and drying conditions. The apparent volume void fractions of particles with highly porous structures can range up to ~50% or more (xerogels, aerogels). Void fractions as well as residual water in dried aerosol particles that are not water-free (due to kinetic limitations of drying or stable hydrate formation) should be taken into account in Köhler model calculations of hygroscopic growth and CCN activation. 6. For efficient description of water uptake and phase transitions of amorphous and crystalline organic and inorganic aerosol particles and particle components, we propose not to limit the terms deliquescence and efflorescence to equilibrium phase transitions of crystalline substances interacting with water vapor. Instead we propose the following generalized definitions: Deliquescence is the transformation of a (semi-)solid substance into a liquid aqueous solution, whereby water is absorbed from the gas phase ("liquefaction upon humidification/hydration"). Efflorescence is the transformation of a substance from a liquid aqueous solution into a (semi-)solid phase, whereby water is evaporated ("solidification upon drying/dehydration"). According to these definitions, individual components as well as entire aerosol particles can undergo gradual or prompt, partial or full deliquescence or efflorescence.

Hygroscopic Growth of Multicomponent Aerosol Particles Influenced by Several Cycles of Relative Humidity

2008 ◽  
Vol 112 (11) ◽  
pp. 2378-2385 ◽  
Author(s):  
Thomas Rosenoern ◽  
Julie C. Schlenker ◽  
Scot T. Martin
Keyword(s):  
Relative Humidity ◽  
Aerosol Particles ◽  
Hygroscopic Growth

scholarly journals Effects of relative humidity on aerosol light scattering in the Arctic

2010 ◽  
Vol 10 (8) ◽  
pp. 3875-3890 ◽  
Author(s):  
P. Zieger ◽  
R. Fierz-Schmidhauser ◽  
M. Gysel ◽  
J. Ström ◽  
S. Henne ◽  
...  
Keyword(s):  
Standard Deviation ◽  
Light Scattering ◽  
Relative Humidity ◽  
Aerosol Particles ◽  
Aerosol Size Distribution ◽  
Hygroscopic Growth ◽  
Scattering Coefficients ◽  
Dry Conditions ◽  
Hygroscopic Particles

Abstract. Aerosol particles experience hygroscopic growth in the ambient atmosphere. Their optical properties – especially the aerosol light scattering – are therefore strongly dependent on the ambient relative humidity (RH). In-situ light scattering measurements of long-term observations are usually performed under dry conditions (RH>30–40%). The knowledge of this RH effect is of eminent importance for climate forcing calculations or for the comparison of remote sensing with in-situ measurements. This study combines measurements and model calculations to describe the RH effect on aerosol light scattering for the first time for aerosol particles present in summer and fall in the high Arctic. For this purpose, a field campaign was carried out from July to October 2008 at the Zeppelin station in Ny-Ålesund, Svalbard. The aerosol light scattering coefficient σsp(λ) was measured at three distinct wavelengths (λ=450, 550, and 700 nm) at dry and at various, predefined RH conditions between 20% and 95% with a recently developed humidified nephelometer (WetNeph) and with a second nephelometer measuring at dry conditions with an average RH<10% (DryNeph). In addition, the aerosol size distribution and the aerosol absorption coefficient were measured. The scattering enhancement factor f(RH, λ) is the key parameter to describe the RH effect on σsp(λ) and is defined as the RH dependent σsp(RH, λ) divided by the corresponding dry σsp(RHdry, λ). During our campaign the average f(RH=85%, λ=550 nm) was 3.24±0.63 (mean ± standard deviation), and no clear wavelength dependence of f(RH, λ) was observed. This means that the ambient scattering coefficients at RH=85% were on average about three times higher than the dry measured in-situ scattering coefficients. The RH dependency of the recorded f(RH, λ) can be well described by an empirical one-parameter equation. We used a simplified method to retrieve an apparent hygroscopic growth factor g(RH), defined as the aerosol particle diameter at a certain RH divided by the dry diameter, using the WetNeph, the DryNeph, the aerosol size distribution measurements and Mie theory. With this approach we found, on average, g(RH=85%) values to be 1.61±0.12 (mean±standard deviation). No clear seasonal shift of f(RH, λ) was observed during the 3-month period, while aerosol properties (size and chemical composition) clearly changed with time. While the beginning of the campaign was mainly characterized by smaller and less hygroscopic particles, the end was dominated by larger and more hygroscopic particles. This suggests that compensating effects of hygroscopicity and size determined the temporal stability of f(RH, λ). During sea salt influenced periods, distinct deliquescence transitions were observed. At the end we present a method on how to transfer the dry in-situ measured aerosol scattering coefficients to ambient values for the aerosol measured during summer and fall at this location.

scholarly journals Effect of mixing structure on the water uptake of mixtures of ammonium sulfate and phthalic acid particles

2021 ◽  
Vol 21 (3) ◽  
pp. 2179-2190
Author(s):  
Weigang Wang ◽  
Ting Lei ◽  
Andreas Zuend ◽  
Hang Su ◽  
Yafang Cheng ◽  
...  
Keyword(s):  
Growth Factor ◽  
Relative Humidity ◽  
Water Uptake ◽  
Phthalic Acid ◽  
Aerosol Particles ◽  
Core Shell ◽  
Hygroscopic Growth ◽  
The Core ◽  
Mass Fractions ◽  
Mixing States

Abstract. Aerosol mixing state regulates the interactions between water molecules and particles and thus controls aerosol activation and hygroscopic growth, which thereby influences visibility degradation, cloud formation, and its radiative forcing. There are, however, few current studies on the mixing structure effects on aerosol hygroscopicity. Here, we investigated the hygroscopicity of ammonium sulfate / phthalic acid (AS / PA) aerosol particles with different mass fractions of PA in different mixing states in terms of initial particle generation. Firstly, the effect of PA coatings on the hygroscopic behavior of the core-shell-generated mixtures of AS with PA was studied using a coating hygroscopicity tandem differential mobility analyzer (coating HTDMA). The slow increase in the hygroscopic growth factor of core-shell-generated particles is observed with increasing thickness of the coating PA prior to the deliquescence relative humidity (DRH) of AS. At relative humidity (RH) above 80 %, a decrease in the hygroscopic growth factor of particles occurs as the thickness of the PA shell increases, which indicates that the increase of PA mass fractions leads to a reduction of the overall core-shell-generated particle hygroscopicity. In addition, the use of the Zdanovskii–Stokes–Robinson (ZSR) relation leads to the underestimation of the measured growth factors of core-shell-generated particles without consideration of the morphological effect of core-shell-generated particles, especially at higher RH. Secondly, in the case of the AS / PA initially well-mixed particles, a shift of the DRH of AS (∼80 %, Tang and Munkelwitz, 1994) to lower RH is observed due to the presence of PA in the initially well-mixed particles. The predicted hygroscopic growth factor using the ZSR relation is consistent with the measured hygroscopic growth factor of the initially well-mixed particles. Moreover, we compared and discussed the influence of mixing states on the water uptake of AS / PA aerosol particles. It is found that the hygroscopic growth factor of the core-shell-generated particles is slightly higher than that of the initially well-mixed particles with the same mass fractions of PA at RH above 80 %. The observation of AS / PA particles may contribute to a growing field of knowledge regarding the influence of coating properties and mixing structure on water uptake.

scholarly journals Interaction of aerosol particles composed of protein and saltswith water vapor: hygroscopic growth and microstructural rearrangement

2004 ◽  
Vol 4 (2) ◽  
pp. 323-350 ◽  
Author(s):  
E. Mikhailov ◽  
S. Vlasenko ◽  
R. Niessner ◽  
U. Pöschl
Keyword(s):  
Water Vapor ◽  
Mass Fraction ◽  
Osmotic Coefficient ◽  
Aerosol Particles ◽  
Dry Mass ◽  
Virial Equation ◽  
Inorganic Salts ◽  
Equivalent Diameter ◽  
Hygroscopic Growth ◽  
Kohler Theory

Abstract. The interaction of aerosol particles composed of the protein bovine serum albumin (BSA) and the inorganic salts sodium chloride and ammonium nitrate with water vapor has been investigated by hygroscopicity tandem differential mobility analyzer (H-TDMA) experiments complemented by transmission electron microscopy (TEM) and Köhler theory calculations (100-300nm particle size range, 298K, 960hPa). BSA was chosen as a well-defined model substance for proteins and other macromolecular compounds, which constitute a large fraction of the water-soluble organic component of air particulate matter. Pure BSA particles exhibited deliquescence and efflorescence transitions at 35% relative humidity () and a hygroscopic diameter increase by up to 10% at 95% in good agreement with model calculations based on a simple parameterisation of the osmotic coefficient. Pure NaCl particles were converted from near-cubic to near-spherical shape upon interaction with water vapor at relative humidities below the deliquescence threshold (partial surface dissolution and recrystallisation), and the diameters of pure NH4NO3 particles decreased by up to 10% due to chemical decomposition and evaporation. Mixed NaCl-BSA and NH4NO3-BSA particles interacting with water vapor exhibited mobility equivalent diameter reductions of up to 20%, depending on particle generation, conditioning, size, and chemical composition (BSA dry mass fraction 10-90%). These observations can be explained by formation of porous agglomerates (envelope void fractions up to 50%) due to ion-protein interactions and electric charge effects on the one hand, and by compaction of the agglomerate structure due to capillary condensation effects on the other. The size of NH4NO3-BSA particles was apparently also influenced by volatilisation of NH4NO3, but not as much as for pure salt particles, i.e. the protein inhibited the decomposition of NH4NO3 or the evaporation of the decomposition products NH3 and HNO3. The efflorescence threshold of NaCl-BSA particles decreased with increasing BSA dry mass fraction, i.e. the protein inhibited the formation of salt crystals and enhanced the stability of supersaturated solution droplets. The H-TDMA and TEM results indicate that the protein was enriched at the surface of the mixed particles and formed an envelope, which inhibits the access of water vapor to the particle core and leads to kinetic limitations of hygroscopic growth, phase transitions, and microstructural rearrangement processes. The Köhler theory calculations performed with different types of models demonstrate that the hygroscopic growth of particles composed of inorganic salts and proteins can be efficiently described with a simple volume additivity approach, provided that the correct dry solute mass equivalent diameter and composition are known. A parameterisation for the osmotic coefficient of macromolecular substances has been derived from an osmotic pressure virial equation. For its application only the density and molar mass of the substance have to be known or estimated, and it is fully compatible with traditional volume additivity models for salt mixtures.

scholarly journals Hygroscopic properties of aerosol particles at high relative humidity and their diurnal variations in the North China Plain

2011 ◽  
Vol 11 (7) ◽  
pp. 3479-3494 ◽  
Author(s):  
P. F. Liu ◽  
C. S. Zhao ◽  
T. Göbel ◽  
E. Hallbauer ◽  
A. Nowak ◽  
...  
Keyword(s):  
Relative Humidity ◽  
North China Plain ◽  
North China ◽  
Aerosol Particles ◽  
Diurnal Variations ◽  
Hygroscopic Growth ◽  
Carbonaceous Particles ◽  
The North ◽  
Hygroscopic Properties ◽  
The North China Plain

Abstract. The hygroscopic properties of submicron aerosol particles were determined at a suburban site (Wuqing) in the North China Plain among a cluster of cities during the period 17 July to 12 August, 2009. A High Humidity Tandem Differential Mobility Analyser (HH-TDMA) instrument was applied to measure the hygroscopic growth factor (GF) at 90%, 95% and 98.5% relative humidity (RH) for particles with dry diameters between 50 and 250 nm. The probability distribution of GF (GF-PDF) averaged over the period shows a distinct bimodal pattern, namely, a dominant more-hygroscopic (MH) group and a smaller nearly-hydrophobic (NH) group. The MH group particles were highly hygroscopic, and their GF was relatively constant during the period with average values of 1.54 ± 0.02, 1.81 ± 0.04 and 2.45 ± 0.07 at 90%, 95% and 98.5% RH (D0 = 100 nm), respectively. The NH group particles grew very slightly when exposed to high RH, with GF values of 1.08 ± 0.02, 1.13 ± 0.06 and 1.24 ± 0.13 respectively at 90%, 95% and 98.5% RH (D0 = 100 nm). The hygroscopic growth behaviours at different RHs were well represented by a single-parameter Köhler model. Thus, the calculation of GF as a function of RH and dry diameter could be facilitated by an empirical parameterization of κ as function of dry diameter. A strong diurnal pattern in number fraction of different hygroscopic groups was observed. The average number fraction of NH particles during the day was about 8%, while during the nighttime fractions up to 20% were reached. Correspondingly, the state of mixing in terms of water uptake varied significantly during a day. Simulations using a particle-resolved aerosol box model (PartMC-MOSAIC) suggest that the diurnal variations of aerosol hygroscopicity and mixing state were mainly caused by the evolution of the atmospheric mixing layer. The shallow nocturnal boundary layer during the night facilitated the accumulation of freshly emitted carbonaceous particles (mainly hydrophobic) near the surface while in the morning turbulence entrained the more aged and more hygroscopic particles from aloft and diluted the NH particles near the surface resulting in a decrease in the fraction of NH particles.

scholarly journals Effects of relative humidity on aerosol light scattering in the Arctic

2010 ◽  
Vol 10 (2) ◽  
pp. 3659-3698 ◽  
Author(s):  
P. Zieger ◽  
R. Fierz-Schmidhauser ◽  
M. Gysel ◽  
J. Ström ◽  
S. Henne ◽  
...  
Keyword(s):  
Standard Deviation ◽  
Light Scattering ◽  
Relative Humidity ◽  
Aerosol Particles ◽  
Aerosol Size Distribution ◽  
Hygroscopic Growth ◽  
Scattering Coefficients ◽  
Dry Conditions ◽  
Hygroscopic Particles

Abstract. Aerosol particles experience hygroscopic growth in the ambient atmosphere. Their optical properties – especially the aerosol light scattering – are therefore strongly dependent on the ambient relative humidity (RH). In-situ light scattering measurements of long-term observations are usually performed under dry conditions (RH<30–40%). The knowledge of this RH effect is of eminent importance for climate forcing calculations or for the comparison of remote sensing with in-situ measurements. This study combines measurements and model calculations to describe the RH effect on aerosol light scattering for the first time of aerosol particles present in summer and fall at the high Arctic. For this purpose, a field campaign was carried out from July to October 2008 at the Zeppelin station in Ny-Ålesund, Svalbard. The aerosol light scattering coefficient σsp(λ) was measured at three distinct wavelengths (λ=450, 550, and 700 nm) at dry and at various, predefined RH conditions between 20% and 95% with a recently developed humidified nephelometer (WetNeph) and with a second nephelometer measuring at dry conditions (DryNeph). In addition, the aerosol size distribution and the aerosol absorption coefficient were measured. The scattering enhancement factor f(RH,λ) is the key parameter to describe the RH effect on σsp(λ) and is defined as the RH dependent σsp(RH,λ) divided by the corresponding dry σsp(RHdry,λ). During our campaign the average f(RH=85%, λ=550 nm) was 3.24±0.63 (mean ± standard deviation), and no clear wavelength dependence of f(RH,λ) was observed. This means that the ambient scattering coefficients at RH=85% were on average about three times higher than the dry measured in-situ scattering coefficients. The RH dependency of the recorded f(RH,λ) can be well described by an empirical one-parameter equation. We used a simplified method to retrieve an apparent hygroscopic growth factor g, defined as the aerosol particle diameter at a certain RH divided by the dry diameter, using the WetNeph, the DryNeph, the aerosol size distribution measurements and Mie theory. With this approach we found on average for g values of 1.61±0.12 (mean ± standard deviation). No clear seasonal shift of f(RH,λ) was observed during the 3-month period, while aerosol properties (size and chemical composition) clearly changed with time. While the beginning of the campaign was mainly characterized by smaller and less hygroscopic particles, the end was dominated by larger and more hygroscopic particles. This suggests that compensating effects of hygroscopicity and size determined the temporal stability of f(RH,λ). During sea salt influenced periods, distinct deliquescence transitions were observed. At the end we give a method on how to transfer the dry in-situ measured aerosol scattering coefficients to ambient values for the aerosol measured during summer and fall at this location.

scholarly journals Assessing relative humidity dependent photoacoustics to retrieve mass accommodation coefficients of single optically trapped aerosol particles

2019 ◽  
Vol 21 (9) ◽  
pp. 4721-4731 ◽  
Author(s):  
Matus E. Diveky ◽  
Sandra Roy ◽  
Johannes W. Cremer ◽  
Grégory David ◽  
Ruth Signorell
Keyword(s):  
Relative Humidity ◽  
Atmospheric Aerosols ◽  
Photoacoustic Spectroscopy ◽  
Aerosol Particles ◽  
Accommodation Coefficients ◽  
Humidity Dependence ◽  
Optically Trapped ◽  
Evaporation Kinetics ◽  
Absorption Measurements

Photoacoustic spectroscopy is a standout technique widely used for absorption measurements of atmospheric aerosols. Here we investigate the relative humidity dependence of photoacoustics and its implication for evaporation kinetics.

scholarly journals Interaction of aerosol particles composed of protein and salts with water vapor: hygroscopic growth and microstructural rearrangement

2003 ◽  
Vol 3 (5) ◽  
pp. 4755-4832 ◽  
Author(s):  
E. Mikhailov ◽  
S. Vlasenko ◽  
R. Niessner ◽  
U. Pöschl
Keyword(s):  
Water Vapor ◽  
Mass Fraction ◽  
Osmotic Coefficient ◽  
Aerosol Particles ◽  
Dry Mass ◽  
Water Soluble ◽  
Equivalent Diameter ◽  
Hygroscopic Growth ◽  
Air Particulate ◽  
Kohler Theory

Abstract. The interaction of aerosol particles in the 100–200 nm size range composed of the protein bovine serum albumin (BSA) and the inorganic salts sodium chloride and ammonium nitrate with water vapor at ambient temperature and pressure (25°C, 1 atm) has been investigated by hygroscopicity tandem differential mobility analyzer (H-TDMA) experiments complemented by transmission electron microscopy (TEM) and Köhler theory calculations. BSA was chosen as a well-defined model substance for proteins and other macromolecular compounds, which constitute a large fraction of the water-soluble organic component of air particulate matter. Pure BSA particles exhibited deliquescence and efflorescence transitions at ~35% relative humidity (RH) and a hygroscopic diameter increase by up to ~10% at 95% RH in good agreement with model calculations based on a simple parameterisation of the osmotic coefficient. Pure NaCl particles were converted from near-cubic to near-spherical or polyhedral shape upon interaction with water vapor at relative humidities below the deliquescence threshold (partial surface dissolution and recrystallisation), and the diameters of pure NH4NO3 particles decreased by up to 10% due to chemical decomposition and evaporation. Mixed NaCl-BSA and NH4NO3-BSA particles interacting with water vapor exhibited mobility equivalent diameter reductions of up to 20%, depending on particle generation, conditioning, size, and chemical composition (BSA dry mass fraction 10–90%). These observations can be explained by formation of porous agglomerates (envelope void fractions up to 50%) due to ion-protein interactions and electric charge effects on the one hand, and by compaction of the agglomerate structure due to capillary condensation effects on the other. The size of NH4NO3-BSA particles was apparently also influenced by volatilisation of NH4NO3, but not as much as for pure salt particles, i.e. the protein inhibited the decomposition of NH4NO3 or the evaporation of the decomposition products NH3 and HNO3. The efflorescence threshold of NaCl-BSA particles decreased with increasing BSA dry mass fraction, i.e. the protein inhibited the formation of salt crystals and enhanced the stability of supersaturated solution droplets. The H-TDMA and TEM results indicate that the protein was enriched at the surface of the mixed particles and formed an envelope, which inhibits the access of water vapor to the particle core and leads to kinetic limitations of hygroscopic growth, phase transitions, and microstructural rearrangement processes. Besides these surface and kinetic effects, proteins and comparable organic macromolecules may also influence the thermodynamic properties of the aqueous bulk solution (solubilities, vapor pressures, and chemical equilibria, e.g. for the decomposition and evaporation of NH4NO3. The observed effects should be taken into account in the analysis of data from laboratory experiments and field measurements and in the modelling of aerosol processes involving water vapor and particles with complex composition. They can strongly influence experimental results, and depending on ambient conditions they may also play a significant role in the atmosphere (deliquescence, efflorescence, and CCN activation of particles). In fact, irregular hygroscopic growth curves similar to the ones observed in this study have recently been reported from H-TDMA experiments with water-soluble organics extracted from real air particulate matter and with humic-like substances. The Köhler theory calculations performed with different models demonstrate that the hygroscopic growth of particles composed of inorganic salts and proteins can be efficiently described with a simple volume additivity approach, provided that the correct dry solute mass equivalent diameter and composition are known. A simple parameterisation of the osmotic coefficient has been derived from an osmotic pressure virial equation and appears to be well-suited for proteins and comparable substances. It is fully compatible with traditional volume additivity models for salt mixtures, and for its application only the density and molar mass of the substance have to be known or estimated.

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