Measurements of Thermodynamic and Optical Properties of Selected Aqueous Organic and Organic–Inorganic Mixtures of Atmospheric Relevance

Lienhard, Daniel M.; Bones, David L.; Zuend, Andreas; Krieger, Ulrich K.; Reid, Jonathan P.; Peter, Thomas

doi:10.1021/jp3055872

Cited by 68 publications

(96 citation statements)

References 98 publications

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“…The levitated particle is illuminated by a HeNe laser (633 nm), an LED (560 to 610 nm) and a narrow bandwidth tunable diode laser (765 to 781 nm) which allow tracking of changes in composition and size by analyzing resonances in the Mie scattering spectra (Lienhard et al, 2014;Steimer et al, 2015). Mass and radius growth factors as well as density and refractive index of the particles can be derived from these measurements over the entire concentration range after allowing sufficient time for equilibration (Lienhard et al, 2012a;Steimer et al, 2015) (examples are given in Appendix A3). Note that the mass fraction of solute can be directly inferred from the mass growth factor, without knowledge of the molar mass of the solute.…”

Section: Methodsmentioning

confidence: 99%

“…The thermodynamic and optical properties needed for the model calculations are taken from Lienhard et al (2012a) for raffinose, levoglucosan and the levoglucosan mixture with NH 4 HSO 4 . For the water activity parameterization of raffinose, which is not given by Lienhard et al (2012a), we use a w = x w exp((1 − x w ) 2 (−7.359 + 1.805(1 − x w ))).…”

Section: A3 Thermodynamic and Optical Propertiesmentioning

confidence: 99%

“…For the water activity parameterization of raffinose, which is not given by Lienhard et al (2012a), we use a w = x w exp((1 − x w ) 2 (−7.359 + 1.805(1 − x w ))).…”

Section: A3 Thermodynamic and Optical Propertiesmentioning

confidence: 99%

See 2 more Smart Citations

Viscous organic aerosol particles in the upper troposphere: diffusivity-controlled water uptake and ice nucleation?

Lienhard

Huisman

Krieger³

et al. 2015

Atmos. Chem. Phys.

118

190

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Abstract. New measurements of water diffusion in secondary organic aerosol (SOA) material produced by oxidation of α-pinene and in a number of organic/inorganic model mixtures (3-methylbutane-1,2,3-tricarboxylic acid (3-MBTCA), levoglucosan, levoglucosan/NH 4 HSO 4 , raffinose) are presented. These indicate that water diffusion coefficients are determined by several properties of the aerosol substance and cannot be inferred from the glass transition temperature or bouncing properties. Our results suggest that water diffusion in SOA particles is faster than often assumed and imposes no significant kinetic limitation on water uptake and release at temperatures above 220 K. The fast diffusion of water suggests that heterogeneous ice nucleation on a glassy core is very unlikely in these systems. At temperatures below 220 K, model simulations of SOA particles suggest that heterogeneous ice nucleation may occur in the immersion mode on glassy cores which remain embedded in a liquid shell when experiencing fast updraft velocities. The particles absorb significant quantities of water during these updrafts which plasticize their outer layers such that these layers equilibrate readily with the gas phase humidity before the homogeneous ice nucleation threshold is reached. Glass formation is thus unlikely to restrict homogeneous ice nucleation. Only under most extreme conditions near the very high tropical tropopause may the homogeneous ice nucleation rate coefficient be reduced as a consequence of slow condensed-phase water diffusion. Since the differences between the behavior limited or non limited by diffusion are small even at the very high tropical tropopause, condensed-phase water diffusivity is unlikely to have significant consequences on the direct climatic effects of SOA particles under tropospheric conditions.

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Section: Methodsmentioning

confidence: 99%

Section: A3 Thermodynamic and Optical Propertiesmentioning

confidence: 99%

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Viscous organic aerosol particles in the upper troposphere: diffusivity-controlled water uptake and ice nucleation?

Lienhard

Huisman

Krieger³

et al. 2015

Atmos. Chem. Phys.

118

190

View full text Add to dashboard Cite

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“…Heterogeneous nucleation of ice on glassy aerosol particles well below water saturation may lead to less, but larger, ice crystals which have a greater sedimentation velocity; this may be particularly important in the very cold and dry topical tropopause region where clouds play a key role in water transport into the stratosphere (Murray et al, 2010b). Reduced diffusion coefficients result in delayed interactions with the gas phase and may impact a particle's optical properties through its ability to take up water (Tong et al, 2011;Bones et al, 2012;Murray et al, 2012). Upon increasing RH, water uptake by amorphous solids occurs at the surface of a particle, proceeding to the interior of the particle only when the outer layer has softened and the rate of diffusion increased Zobrist et al, 2011).…”

Section: H C Price Et Al: Quantifying Water Diffusion In High-viscmentioning

confidence: 99%

Quantifying water diffusion in high-viscosity and glassy aqueous solutions using a Raman isotope tracer method

et al. 2014

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Abstract. Recent research suggests that under certain temperature and relative humidity conditions atmospheric aerosol may be present in the form of a glassy solid. In order to understand the impacts that this may have on aerosolcloud interactions and atmospheric chemistry, knowledge of water diffusion within such aerosol particles is required. Here, a method is described in which Raman spectroscopy is used to observe D 2 O diffusion in high-viscosity aqueous solutions, enabling a quantitative assessment of water diffusion coefficients, D water , as a function of relative humidity. Results for sucrose solutions compare well with literature data at 23.5 ± 0.3 • C, and demonstrate that water diffusion is slow (D water ∼ 5 × 10 −17 m 2 s −1 ), but not arrested, just below the glass transition at a water activity of 0.2. Room temperature water diffusion coefficients are also presented for aqueous levoglucosan and an aqueous mixture of raffinose, dicarboxylic acids and ammonium sulphate: at low humidity, diffusion is retarded but still occurs on millisecond to second timescales in atmospherically relevant-sized particles. The effect of gel formation on diffusion in magnesium sulfate solutions is shown to be markedly different from the gradual decrease in diffusion coefficients of highly viscous liquids. We show that using the Stokes-Einstein equation to determine diffusion timescales from viscosity leads to values which are more than 5 orders of magnitude too big, which emphasises the need to make measurements of diffusion coefficients. In addition, comparison of bounce fraction data for levoglucosan with measured diffusion data reveals that even when particles bounce the diffusion timescales for water are a fraction of a second for a 100 nm particle. This suggests a high bounce fraction does not necessarily indicate retarded water diffusion.

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“…Such models include the Extended Aerosol Inorganic Model (E-AIM) (Clegg et al, 1998;Clegg and Seinfeld, 2006; available online: http://www.aim.env.uea.ac.uk/ aim/aim.php), the Aerosol Diameter Dependent Equilibrium Model (ADDEM) (Topping et al, 2005), the universal quasichemical functional group activity coefficients (UNIFAC) method (Fredenslund et al, 1975;Hansen et al, 1991), and Clegg and Wexler (2011a). b Lienhard et al (2012). c Tuckermann and Cammenga (2004) at 293 K. d Jedelsky et al (2000).…”

Section: Introductionmentioning

confidence: 99%

Hygroscopicity of organic surrogate compounds from biomass burning and their effect on the efflorescence of ammonium sulfate in mixed aerosol particles

et al. 2018

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Abstract. Hygroscopic growth factors of organic surrogate compounds representing biomass burning and mixed organic-inorganic aerosol particles exhibit variability during dehydration experiments depending on their chemical composition, which we observed using a hygroscopicity tandem differential mobility analyzer (HTDMA). We observed that levoglucosan and humic acid aerosol particles release water upon dehumidification in the range from 90 to 5 % relative humidity (RH). However, 4-Hydroxybenzoic acid aerosol particles remain in the solid state upon dehumidification and exhibit a small shrinking in size at higher RH compared to the dry size. For example, the measured growth factor of 4-hyroxybenzoic acid aerosol particles is ∼ 0.96 at 90 % RH. The measurements were accompanied by RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model and Extended Aerosol Inorganics Model (E-AIM), the Zdanovskii-Stokes-Robinson (ZSR) relation, and a fitted hygroscopicity expression. We observed several effects of organic components on the hygroscopicity behavior of mixtures containing ammonium sulfate (AS) in relation to the different mass fractions of organic compounds: (1) a shift of efflorescence relative humidity (ERH) of ammonium sulfate to higher RH due to the presence of 25 wt % levoglucosan in the mixture. (2) There is a distinct efflorescence transition at 25 % RH for mixtures consisting of 25 wt % of 4-hydroxybenzoic acid compared to the ERH at 35 % for organic-free AS particles.(3) There is indication for a liquid-to-solid phase transition of 4-hydroxybenzoic acid in the mixed particles during dehydration. (4) A humic acid component shows no significant effect on the efflorescence of AS in mixed aerosol particles. In addition, consideration of a composition-dependent degree of dissolution of crystallization AS (solid-liquid equilibrium) in the AIOMFAC and E-AIM models leads to a relatively good agreement between models and observed growth factors, as well as ERH of AS in the mixed system. The use of the ZSR relation leads to good agreement with measured diameter growth factors of aerosol particles containing humic acid and ammonium sulfate. Lastly, two distinct mixtures of organic surrogate compounds, including levoglucosan, 4-hydroxybenzoic acid, and humic acid, were used to represent the average water-soluble organic carbon (WSOC) fractions observed during the wet and dry seasons in the central Amazon Basin. A comparison of the organic fraction's hygroscopicity parameter for the simple mixtures, e.g., κ ≈ 0.12 to 0.15 for the wet-season mixture in the 90 to 40 % RH range, shows good agreement with field data for the wet season in the Amazon Basin (WSOC κ ≈ 0.14 ± 0.06 at 90 % RH). This suggests that laboratory-generated mixtures containing organic surrogate compounds and ammonium sulfate can be used to mimic, in a simplified manner, the chemical composition of ambient aerosols from the Amazon Basin for the purpose of RH-de...

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Measurements of Thermodynamic and Optical Properties of Selected Aqueous Organic and Organic–Inorganic Mixtures of Atmospheric Relevance

Cited by 68 publications

References 98 publications

Viscous organic aerosol particles in the upper troposphere: diffusivity-controlled water uptake and ice nucleation?

Viscous organic aerosol particles in the upper troposphere: diffusivity-controlled water uptake and ice nucleation?

Quantifying water diffusion in high-viscosity and glassy aqueous solutions using a Raman isotope tracer method

Hygroscopicity of organic surrogate compounds from biomass burning and their effect on the efflorescence of ammonium sulfate in mixed aerosol particles

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