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.

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

2001 ◽  
Vol 1 (1) ◽  
pp. 1-22 ◽  
Author(s):  
J. Joutsensaari ◽  
P. Vaattovaara ◽  
K. Hämeri ◽  
A. Laaksonen
Keyword(s):  
Water Vapor ◽  
Sodium Chloride ◽  
Citric Acid ◽  
Ammonium Sulfate ◽  
Adipic Acid ◽  
Aerosol Particles ◽  
Ethanol Vapor ◽  
Differential Mobility ◽  
Organic Vapor ◽  
Organic Composition

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 inorganic sodium chloride and ammonium sulfate particles, no growth can be seen in ethanol vapor at saturation ratios below 0.9. In contrast, for organic adipic acid particles, the deliquescence takes place at around S=0.95 in the ethanol vapor. 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 and the OTDMA method can be used to determine an organic composition of the aerosol particles. Operation of OTDMA and hygroscopicity TDMA together allows making a rough categorization of different substances found in atmospheric aerosol particles based on their growth in pure ethanol and pure water vapor.

scholarly journals A combined particle trap/HTDMA hygroscopicity study of mixed inorganic/organic aerosol particles

2008 ◽  
Vol 8 (18) ◽  
pp. 5589-5601 ◽  
Author(s):  
A. A. Zardini ◽  
S. Sjogren ◽  
C. Marcolli ◽  
U. K. Krieger ◽  
M. Gysel ◽  
...  
Keyword(s):  
Citric Acid ◽  
Growth Factor ◽  
Ammonium Sulfate ◽  
Adipic Acid ◽  
Atmospheric Aerosols ◽  
Glutaric Acid ◽  
Large Fraction ◽  
Aerosol Particles ◽  
Organic Aerosol ◽  
Water Soluble

Abstract. Atmospheric aerosols are often mixtures of inorganic and organic material. Organics can represent a large fraction of the total aerosol mass and are comprised of water-soluble and insoluble compounds. Increasing attention was paid in the last decade to the capability of mixed inorganic/organic aerosol particles to take up water (hygroscopicity). We performed hygroscopicity measurements of internally mixed particles containing ammonium sulfate and carboxylic acids (citric, glutaric, adipic acid) in parallel with an electrodynamic balance (EDB) and a hygroscopicity tandem differential mobility analyzer (HTDMA). The organic compounds were chosen to represent three distinct physical states. During hygroscopicity cycles covering hydration and dehydration measured by the EDB and the HTDMA, pure citric acid remained always liquid, adipic acid remained always solid, while glutaric acid could be either. We show that the hygroscopicity of mixtures of the above compounds is well described by the Zdanovskii-Stokes-Robinson (ZSR) relationship as long as the two-component particle is completely liquid in the ammonium sulfate/glutaric acid system; deviations up to 10% in mass growth factor (corresponding to deviations up to 3.5% in size growth factor) are observed for the ammonium sulfate/citric acid 1:1 mixture at 80% RH. We observe even more significant discrepancies compared to what is expected from bulk thermodynamics when a solid component is present. We explain this in terms of a complex morphology resulting from the crystallization process leading to veins, pores, and grain boundaries which allow for water sorption in excess of bulk thermodynamic predictions caused by the inverse Kelvin effect on concave surfaces.

scholarly journals A combined particle trap/HTDMA hygroscopicity study of mixed inorganic/organic aerosol particles

2008 ◽  
Vol 8 (2) ◽  
pp. 5235-5268 ◽  
Author(s):  
A. A. Zardini ◽  
S. Sjogren ◽  
C. Marcolli ◽  
U. K. Krieger ◽  
M. Gysel ◽  
...  
Keyword(s):  
Citric Acid ◽  
Ammonium Sulfate ◽  
Adipic Acid ◽  
Atmospheric Aerosols ◽  
Glutaric Acid ◽  
Large Fraction ◽  
Aerosol Particles ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Component Particle

Abstract. Atmospheric aerosols are often mixtures of inorganic and organic material. Organics can represent a large fraction of the total aerosol mass and are comprised of water-soluble and insoluble compounds. Increasing attention was paid in the last decade to the capability of mixed inorganic/organic aerosol particles to take up water (hygroscopicity). We performed hygroscopicity measurements of internally mixed particles containing ammonium sulfate and carboxylic acids (citric, glutaric, adipic acid) in parallel with an electrodynamic balance (EDB) and a hygroscopicity tandem differential mobility analyzer (HTDMA). The organic compounds were chosen to represent three distinct physical states. During hygroscopicity cycles covering hydration and dehydration measured by the EDB and the HTDMA, pure citric acid remained always liquid, adipic acid remained always solid, while glutaric acid could be either. We show that the hygroscopicity of mixtures of the above compounds is well described by the Zdanovskii-Stokes-Robinson (ZSR) relationship as long as the two-component particle is completely liquid in the ammonium sulfate/citric acid and in the ammonium sulfate/glutaric acid cases. However, we observe significant discrepancies compared to what is expected from bulk thermodynamics when a solid component is present. We explain this in terms of a complex morphology resulting from the crystallization process leading to veins, pores, and grain boundaries which allow for water sorption in excess of bulk thermodynamic predictions caused by the inverse Kelvin effect on concave surfaces.

scholarly journals Size Resolved Online Chemical Analysis of Nano Aerosol Particles: A Thermal Desorption Differential Mobility Analyzer Coupled to a Chemical Ionization Time Of Flight Mass Spectrometer

2018 ◽  
Author(s):  
Andrea C. Wagner ◽  
Anton Bergen ◽  
Sophia Brilke ◽  
Claudia Fuchs ◽  
Markus Ernst ◽  
...  
Keyword(s):  
Chemical Analysis ◽  
Mass Spectrometer ◽  
Thermal Desorption ◽  
Chemical Ionization ◽  
Aerosol Particles ◽  
Transmission Efficiency ◽  
Test Substance ◽  
Ionization Mass ◽  
Differential Mobility Analyzer ◽  
Differential Mobility

Abstract. A new method for size resolved chemical analysis of nucleation mode aerosol particles (size range from ~ 10 to ~ 30 nm) is presented. The Thermal Desorption Differential Mobility Analyzer (TD-DMA) uses an online, discontinuous principle. The particles are charged, a specific size is selected by differential mobility analysis and they are collected on a filament by electrostatic precipitation. Subsequently, the sampled mass is evaporated in a clean carrier gas and analyzed by a chemical ionization mass spectrometer. Gas phase measurements are performed with the same mass spectrometer during the sampling of particles. The characterization shows reproducible results, with a particle size resolution of 1.19 and the transmission efficiency for 15 nm particles being slightly above 50 %. The signal from the evaporation of a test substance can be detected starting from 0.01 ng and shows a linear response in the mass spectrometer. Instrument operation in the range of pg/m3 is demonstrated by an example measurement of 15 nm particles produced by nucleation from dimethylamine, sulfuric acid and water.

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

2013 ◽  
Vol 13 (2) ◽  
pp. 717-740 ◽  
Author(s):  
E. Mikhailov ◽  
S. Vlasenko ◽  
D. Rose ◽  
U. Pöschl
Keyword(s):  
Water Vapor ◽  
Sodium Chloride ◽  
Ammonium Sulfate ◽  
Water Uptake ◽  
Malonic Acid ◽  
Atmospheric Aerosol ◽  
Interaction Model ◽  
Inorganic Particles ◽  
Vapor Supersaturation ◽  
Good Agreement

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; efflorescence regime at low-humidity where substances are just partly dissolved and exist also in a non-dissolved phase, (II) a gradual deliquescence &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).

scholarly journals Hygroscopic growth and activation of HULIS particles: experimental data and a new iterative parameterization scheme for complex aerosol particles

2007 ◽  
Vol 7 (5) ◽  
pp. 13773-13803 ◽  
Author(s):  
M. Ziese ◽  
H. Wex ◽  
E. Nilsson ◽  
I. Salma ◽  
R. Ocskay ◽  
...  
Keyword(s):  
Experimental Data ◽  
Aerosol Particles ◽  
Water Extract ◽  
High Humidity ◽  
Hygroscopic Growth ◽  
Differential Mobility Analyzer ◽  
Growth Behaviour ◽  
Differential Mobility ◽  
Three Samples ◽  
Activation Behavior

Abstract. The hygroscopic growth and activation of two HULIS and one Aerosol-Water-Extract sample, prepared from urban-type aerosol, were investigated. All samples were extracted from filters, redissolved in water and atomized for the investigations presented here. The hygroscopic growth measurements were done using LACIS (Leipzig Aerosol Cloud Interaction Simulator) together with a HH-TDMA (High Humidity Tandem Differential Mobility Analyzer). Hygroscopic growth was determined for relative humidities up to 99.75%. The critical diameters for activation were measured using LACIS for supersaturations between 2 and 10 per mill. All three samples showed a similar hygroscopic growth behaviour, and the two HULIS samples also were similar in their activation behavior, while the Aerosol-Water-Extract turned out to be more CCN active than the HULIS samples. The experimental data was used to derive parameterizations for the hygroscopic growth and activation of HULIS particles. The concept of ρion (Wex et al., 2007a) and the Szyszkowski-equation (Szyszkowski, 1908; Facchini et al., 1999) were used for parameterizing the Raoult and the Kelvin (surface tension) terms of the Köhler equation, respectively. This concept proved to be very successful for the HULIS samples in the saturation range from relative humidities larger than 98% up to activation. However it failed for the Aerosol-Water extract.

scholarly journals Calibration and measurement uncertainties of a continuous-flow cloud condensation nuclei counter (DMT-CCNC): CCN activation of ammonium sulfate and sodium chloride aerosol particles in theory and experiment

2008 ◽  
Vol 8 (5) ◽  
pp. 1153-1179 ◽  
Author(s):  
D. Rose ◽  
S. S. Gunthe ◽  
E. Mikhailov ◽  
G. P. Frank ◽  
U. Dusek ◽  
...  
Keyword(s):  
Sodium Chloride ◽  
Ammonium Sulfate ◽  
Flow Rate ◽  
Continuous Flow ◽  
Flow Model ◽  
Cloud Condensation Nuclei ◽  
Aerosol Particles ◽  
High Accuracy ◽  
Condensation Nuclei ◽  
Model Calculations

Abstract. Experimental and theoretical uncertainties in the measurement of cloud condensation nuclei (CCN) with a continuous-flow thermal-gradient CCN counter from Droplet Measurement Technologies (DMT-CCNC) have been assessed by model calculations and calibration experiments with ammonium sulfate and sodium chloride aerosol particles in the diameter range of 20–220 nm. Experiments have been performed in the laboratory and during field measurement campaigns, covering a wide range of instrument operating conditions (650–1020 hPa pressure, 293–303 K inlet temperature, 4–34 K m−1 temperature gradient, 0.5–1.0 L min−1 flow rate). For each set of conditions, the effective water vapor supersaturation (Seff, 0.05–1.4%) was determined from the measured CCN activation spectra (dry particle activation diameters) and Köhler model calculations. High measurement precision was achieved under stable laboratory conditions, where the relative standard deviations of Seff were as low as ±1%. During field measurements, however, the relative deviations increased to about ±5%, which can be mostly attributed to variations of the CCNC column top temperature with ambient temperature. The observed dependence of Seff on temperature, pressure, and flow rate was compared to the CCNC flow model of Lance et al. (2006). At high Seff the relative deviations between flow model and experimental results were mostly less than 10%, but at Seff≤0.1% they exceeded 40%. Thus, careful experimental calibration is required for high-accuracy CCN measurements – especially at low Seff. A comprehensive comparison and uncertainty analysis of the various Köhler models and thermodynamic parameterizations commonly used in CCN studies showed that the relative deviations between different approaches are as high as 25% for (NH4)2SO4 and 12% for NaCl. The deviations were mostly caused by the different parameterizations for the activity of water in aqueous solutions of the two salts. To ensure comparability of results, we suggest that CCN studies should always report exactly which Köhler model equations and parameters were used. Provided that the Aerosol Inorganics Model (AIM) can be regarded as an accurate source of water activity data for highly dilute solutions of (NH4)2SO4 and NaCl, only Köhler models that are based on the AIM or yield similar results should be used in CCN studies involving these salts and aiming at high accuracy. Experiments with (NH4)2SO4 and NaCl aerosols showed that the conditions of particle generation and the shape and microstructure of NaCl particles are critical for their application in CCN activation experiments (relative deviations up to 18%).

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