Improvement of the Zdanovskii−Stokes−Robinson Model for Mixtures Containing Solutes of Different Charge Types

Clegg, Simon L.; Seinfeld, John H.

doi:10.1021/jp030827q

Cited by 90 publications

(86 citation statements)

References 26 publications

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“…The onset of deliquescence occurred at much lower relative humidity (∼ 30 %) than predicted by the E-AIM (eutonic point at ∼ 63 % RH, Clegg et al, 2006) and reported from earlier bulk measurements (∼ 71 %, Brooks et al, 2002), indicating an amorphous state of MA as discussed below. The observed hygroscopic growth of fully deliquesced particles (RH > 75 %) is in good agreement with predictions based on the E-AIM (Clegg and Seinfeld, 2006) and on the E-ZSR model (Clegg et al, 2004).…”

Section: Malonic Acidsupporting

confidence: 85%

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

et al. 2013

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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 κ m which can be deconvoluted into a dilute hygroscopicity parameter (κ 0 m ) 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 κ m -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 & efflorescence regime at low-humidity where substances are just partly dissolved and exist also in a non-dissolved phase, (II) a gradual deliquescence & 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 κ m 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 κ 0 m 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 me...

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Section: Malonic Acidsupporting

confidence: 85%

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

et al. 2013

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“…The discrepancy reveals over-prediction by the model of water uptake in supersaturated environments . The water content of AS-MA system was also estimated based on the Zdanovskii-Stokes-Robinson (ZSR) relationship (Stokes and Robinson 1966;Clegg and Seinfeld 2004). The ZSR estimations are included in the figure for comparison with the E-AIM model.…”

Section: Hygroscopicitymentioning

confidence: 99%

Water Content and Phase Transitions in Particles of Inorganic and Organic Species and their Mixtures Using Micro-Raman Spectroscopy

Yeung

Chan

2010

Aerosol Science and Technology

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Hygroscopicity and phase transitions were measured with deposited particles of ammonium sulfate (AS), ammonium nitrate (AN), malonic acid (MA), glutaric acid (GA), glyoxylic acid (GlyA), as well as two mixed particle systems AS-MA and AS-GA using micro-Raman spectroscopy. Hygroscopicity was presented in terms of water-to-solute mass ratios, which were obtained from the integrated area ratios of the Raman water band to a distinct solute peak. Deliquescence and crystallization were confirmed by abrupt changes in the Raman peak positions and the full-widthhalf-heights of distinct solute peaks. The results for AS, AN, MA, and GA agreed well with literature reports and model predictions. For GlyA, we detected the Raman water band at near 0% RH, indicating that the spectral technique is sensitive for hygroscopic measurements at very low RH. Additional spectral feature at ∼0% RH was also observed. In the case of more complicated ASdicarboxylic acid mixed systems, the partial phase transitions of the organic components were identified using the intensity ratios of aqueous to solid C=O peaks. AS-MA particles did not completely crystallize and gradual water uptake with increasing RH from 3% was observed. Moreover, it was found that AS-GA particles showed step-wise crystallization in which the AS fraction crystallized prior to the GA fraction. The measured water content and complete DRH of both mixed systems were consistent with the published values. The results show the utility of micro-Raman spectroscopic analysis in studying hygroscopicity and phase characterizations of the chemical species in mixed particles.

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“…Due to its simplicity and frequent application (Cruz and Pandis, 2000;Dick et al, 2000;Chan, 2002a, 2002b;Prenni et al, 2003;Wise et al, 2003;Clegg et al, 2003;Clegg and Seinfeld, 2004Khlystov et al, 2005;Rissler et al, 2005;Aklilu et al, 2006;Svenningsson et al, 2006;Varutbangkul et al, 2006;Gysel et al, 2007;Sjogren et al, 2007;Dinar et al, 2008), the Zdanovskii-Stokes Robinson (ZSR) (Zdanovskii, 1948;Stokes and Robinson, 1966) mixing rule is employed to predict hygroscopic growth factors. This procedure of estimating hygroscopic growth based on specified composition is based on the assumption that water uptake by each individual component of a particle is independent and additive.…”

Section: Estimated Subsaturated Hygroscopic Growth Factors For the Ormentioning

confidence: 99%

Comprehensive airborne characterization of aerosol from a major bovine source

et al. 2008

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Abstract. We report an extensive airborne characterization of aerosol downwind of a massive bovine source in the San Joaquin Valley (California) on two flights during July 2007. The Center for Interdisciplinary Remotely-Piloted Aircraft Studies (CIRPAS) Twin Otter probed chemical composition, particle size distribution, mixing state, sub-and supersaturated water uptake behavior, light scattering properties, and the interrelationship between these parameters and meteorology. Total PM 1.0 levels and concentrations of organics, nitrate, and ammonium were enhanced in the plume from the source as compared to the background aerosol. Organics dominated the plume aerosol mass (∼56-64%), followed either by sulfate or nitrate, and then ammonium. Particulate amines were detected in the plume aerosol by a particleinto-liquid sampler (PILS) and via mass spectral markers in the Aerodyne C-ToF-AMS. Amines were found to be a significant atmospheric base even in the presence of ammonia; particulate amine concentrations are estimated as at least 14-23% of that of ammonium in the plume. Enhanced sub-and supersaturated water uptake and reduced refractive indices were coincident with lower organic mass fractions, higher nitrate mass fractions, and the detection of amines. The likelihood of suppressed droplet growth owing to kinetic limitations from hydrophobic organic material is explored. After removing effects associated with size distribution and mixing state, the normalized activated fraction of cloud condensation nuclei (CCN) increased as a function of the subsaturated Correspondence to: J. H. Seinfeld (seinfeld@caltech.edu) hygroscopic growth factor, with the highest activated fractions being consistent with relatively lower organic mass fractions and higher nitrate mass fractions. Subsaturated hygroscopic growth factors for the organic fraction of the aerosol are estimated based on employing the ZdanovskiiStokes Robinson (ZSR) mixing rule. Representative values for a parameterization treating particle water uptake in both the sub-and supersaturated regimes are reported for incorporation into atmospheric models.

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Improvement of the Zdanovskii−Stokes−Robinson Model for Mixtures Containing Solutes of Different Charge Types

Cited by 90 publications

References 26 publications

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

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

Water Content and Phase Transitions in Particles of Inorganic and Organic Species and their Mixtures Using Micro-Raman Spectroscopy

Comprehensive airborne characterization of aerosol from a major bovine source

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