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.

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 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 Cloud condensation nuclei in pristine tropical rainforest air of Amazonia: size-resolved measurements and modeling of atmospheric aerosol composition and CCN activity

2009 ◽  
Vol 9 (19) ◽  
pp. 7551-7575 ◽  
Author(s):  
S. S. Gunthe ◽  
S. M. King ◽  
D. Rose ◽  
Q. Chen ◽  
P. Roldin ◽  
...  
Keyword(s):  
Water Vapor ◽  
Size Distribution ◽  
Atmospheric Aerosol ◽  
Particle Number ◽  
Tropical Rainforest ◽  
Cloud Condensation Nuclei ◽  
Aerosol Particles ◽  
Model Calculations ◽  
Measurement Results ◽  
Aitken Mode

Abstract. Atmospheric aerosol particles serving as cloud condensation nuclei (CCN) are key elements of the hydrological cycle and climate. We have measured and characterized CCN at water vapor supersaturations in the range of S=0.10–0.82% in pristine tropical rainforest air during the AMAZE-08 campaign in central Amazonia. The effective hygroscopicity parameters describing the influence of chemical composition on the CCN activity of aerosol particles varied in the range of κ≈0.1–0.4 (0.16±0.06 arithmetic mean and standard deviation). The overall median value of κ≈0.15 was by a factor of two lower than the values typically observed for continental aerosols in other regions of the world. Aitken mode particles were less hygroscopic than accumulation mode particles (κ≈0.1 at D≈50 nm; κ≈0.2 at D≈200 nm), which is in agreement with earlier hygroscopicity tandem differential mobility analyzer (H-TDMA) studies. The CCN measurement results are consistent with aerosol mass spectrometry (AMS) data, showing that the organic mass fraction (forg) was on average as high as ~90% in the Aitken mode (D≤100 nm) and decreased with increasing particle diameter in the accumulation mode (~80% at D≈200 nm). The κ values exhibited a negative linear correlation with forg (R2=0.81), and extrapolation yielded the following effective hygroscopicity parameters for organic and inorganic particle components: κorg≈0.1 which can be regarded as the effective hygroscopicity of biogenic secondary organic aerosol (SOA) and κinorg≈0.6 which is characteristic for ammonium sulfate and related salts. Both the size dependence and the temporal variability of effective particle hygroscopicity could be parameterized as a function of AMS-based organic and inorganic mass fractions (κp=κorg×forg +κinorg×finorg). The CCN number concentrations predicted with κp were in fair agreement with the measurement results (~20% average deviation). The median CCN number concentrations at S=0.1–0.82% ranged from NCCN,0.10≈35 cm−3 to NCCN,0.82≈160 cm−3, the median concentration of aerosol particles larger than 30 nm was NCN,30≈200 cm−3, and the corresponding integral CCN efficiencies were in the range of NCCN,0.10/NCN,30≈0.1 to NCCN,0.82/NCN,30≈0.8. Although the number concentrations and hygroscopicity parameters were much lower in pristine rainforest air, the integral CCN efficiencies observed were similar to those in highly polluted megacity air. Moreover, model calculations of NCCN,S assuming an approximate global average value of κ≈0.3 for continental aerosols led to systematic overpredictions, but the average deviations exceeded ~50% only at low water vapor supersaturation (0.1%) and low particle number concentrations (≤100 cm−3). Model calculations assuming a constant aerosol size distribution led to higher average deviations at all investigated levels of supersaturation: ~60% for the campaign average distribution and ~1600% for a generic remote continental size distribution. These findings confirm earlier studies suggesting that aerosol particle number and size are the major predictors for the variability of the CCN concentration in continental boundary layer air, followed by particle composition and hygroscopicity as relatively minor modulators. Depending on the required and applicable level of detail, the information and parameterizations presented in this paper should enable efficient description of the CCN properties of pristine tropical rainforest aerosols of Amazonia in detailed process models as well as in large-scale atmospheric and climate models.

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.

scholarly journals Sulfobetaine Cryogels for Preferential Adsorption of Methyl Orange from Mixed Dye Solutions

Polymers ◽  
2021 ◽  
Vol 13 (2) ◽  
pp. 208
Author(s):  
Ramona B. J. Ihlenburg ◽  
Anne-Catherine Lehnen ◽  
Joachim Koetz ◽  
Andreas Taubert
Keyword(s):  
Aqueous Solution ◽  
Methylene Blue ◽  
Methyl Orange ◽  
Dye Removal ◽  
Selective Adsorption ◽  
Water Soluble ◽  
Organic Substances ◽  
Preferential Adsorption ◽  
Dimethyl Ammonium ◽  
Dye Solutions

New cryogels for selective dye removal from aqueous solution were prepared by free radical polymerization from the highly water-soluble crosslinker N,N,N’,N’-tetramethyl-N,N’-bis(2-ethylmethacrylate)-propyl-1,3-diammonium dibromide and the sulfobetaine monomer 2-(N-3-sulfopropyl-N,N-dimethyl ammonium)ethyl methacrylate. The resulting white and opaque cryogels have micrometer sized pores with a smaller substructure. They adsorb methyl orange (MO) but not methylene blue (MB) from aqueous solution. Mixtures of MO and MB can be separated through selective adsorption of the MO to the cryogels while the MB remains in solution. The resulting cryogels are thus candidates for the removal of hazardous organic substances, as exemplified by MO and MB, from water. Clearly, it is possible that the cryogels are also potentially interesting for removal of other compounds such as pharmaceuticals or pesticides, but this must be investigated further.

scholarly journals Calibration of LACIS as a CCN detector and its use in measuring activation and hygroscopic growth of atmospheric aerosol particles

2006 ◽  
Vol 6 (12) ◽  
pp. 4519-4527 ◽  
Author(s):  
H. Wex ◽  
A. Kiselev ◽  
M. Ziese ◽  
F. Stratmann
Keyword(s):  
Sodium Chloride ◽  
Wall Temperature ◽  
Atmospheric Aerosol ◽  
Volume Fraction ◽  
Cloud Condensation Nuclei ◽  
Aerosol Particles ◽  
Urban Aerosol ◽  
Hygroscopic Growth ◽  
Atmospheric Aerosol Particles ◽  
Droplet Activation

Abstract. A calibration for LACIS (Leipzig Aerosol Cloud Interaction Simulator) for its use as a CCN (cloud condensation nuclei) detector has been developed. For this purpose, sodium chloride and ammonium sulfate particles of known sizes were generated and their grown sizes were detected at the LACIS outlet. From these signals, the effective critical super-saturation was derived as a function of the LACIS wall temperature. With this, LACIS is calibrated for its use as a CCN detector. The applicability of LACIS for measurements of the droplet activation, and also of the hygroscopic growth of atmospheric aerosol particles was tested. The activation of the urban aerosol particles used in the measurements was found to occur at a critical super-saturation of 0.46% for particles with a dry diameter of 75 nm, and at 0.42% for 85 nm, respectively. Hygroscopic growth was measured for atmospheric aerosol particles with dry diameters of 150, 300 and 350 nm at relative humidities of 98 and 99%, and it was found that the larger dry particles contained a larger soluble volume fraction of about 0.85, compared to about 0.6 for the 150 nm particles.

scholarly journals A novel tandem differential mobility analyzer with organic vapor treatment of aerosol particles

2001 ◽  
Vol 1 (1) ◽  
pp. 51-60 ◽  
Author(s):  
J. Joutsensaari ◽  
P. Vaattovaara ◽  
M. Vesterinen ◽  
K. Hämeri ◽  
A. Laaksonen
Keyword(s):  
Water Vapor ◽  
Sodium Chloride ◽  
Citric Acid ◽  
Ammonium Sulfate ◽  
Adipic Acid ◽  
Aerosol Particles ◽  
Ethanol Vapor ◽  
Differential Mobility Analyzer ◽  
Differential Mobility ◽  
Organic Vapor

Abstract. A novel method to characterize the organic composition of aerosol particles has been developed. The method is based on organic vapor interaction with aerosol particles and it has been named an Organic Tandem Differential Mobility Analyzer (OTDMA). The OTDMA method has been tested for inorganic (sodium chloride and ammonium sulfate) and organic (citric acid and adipic acid) particles. Growth curves of the particles have been measured in ethanol vapor and as a comparison in water vapor as a function of saturation ratio. Measurements in water vapor show that sodium chloride and ammonium sulfate as well as citric acid particles grow at water saturation ratios (S) of 0.8 and above, whereas adipic acid particles do not grow at S <  0.96. For sodium chloride and ammonium sulfate particles, a deliquescence point is observed at S = 0.75 and S = 0.79, respectively. Citric acid particles grow monotonously with increasing saturation ratios already at low saturation ratios and no clear deliquescence point is found. For sodium chloride and ammonium sulfate particles, no growth can be seen in ethanol vapor at saturation ratios below 0.93. In contrast, for adipic acid particles, the deliquescence takes place at around S = 0.95 in the ethanol vapor. The recrystallization of adipic acid takes place at S < 0.4. Citric acid particles grow in ethanol vapor similarly as in water vapor; the particles grow monotonously with increasing saturation ratios and no stepwise deliquescence is observed. The results show that the working principles of the OTDMA are operational for single-component aerosols. Furthermore, the results indicate that the OTDMA method may prove useful in determining whether aerosol particles contain organic substances, especially if the OTDMA is operated in parallel with a hygroscopicity TDMA, as the growth of many substances is different in ethanol and water vapors.

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