Predictions of the glass transition temperature and viscosity of organic aerosols from volatility distributions

Liu, Ying; Day, Douglas A.; Stark, Harald; Jimenez, José L.; Shiraiwa, Manabu

doi:10.5194/acp-20-8103-2020

Cited by 68 publications

(132 citation statements)

References 125 publications

(247 reference statements)

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“…7) of toluene-derived SOA when compared with the other two types of SOA may enhance the hygroscopicity of the particle (Lambe et al, 2011b;Liu et al, 2018;Zhao et al, 2016) and thus may reduce the deposition IN ability of BC particles. On the other hand, Hinks et al (2018) shows that toluene-derived SOA also contains a significant amount of oligomers under dry laboratory conditions, similar to what we conducted in the PAM chamber in this study, potentially reducing the hygroscopicity and altering the phase state of the SOA to be semi-solid or solid (Li et al, 2020;Zhang et al, 2018b), under which the SOA can still nucleate ice (Zhang et al, 2019c). Overall, these two competing factors make our toluene SOA coating IN onset move towards but not fully in the homogeneous freezing regime, agreeing with the results of Kulkarni et al (2016).…”

Section: Ice Nucleation On Bc Coated With Soa Materialssupporting

confidence: 79%

The effects of morphology, mobility size and SOA material coating on the ice nucleation activity of black carbon in the cirrus regime

Zhang¹,

Zhang²,

Wolf³

et al. 2020

Preprint

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Abstract. There is evidence that black carbon (BC) particles may affect cirrus formation and hence global climate by acting as potential ice nucleating particles (INPs) in the troposphere. Nevertheless, the ice nucleation (IN) ability of bare BC and BC coated with secondary organic aerosol (SOA) material remains uncertain. We have systematically examined the IN ability of 100–400 nm size-selected BC particles with different morphologies and different SOA coatings representative of anthropogenic (toluene and n-dodecane) and biogenic (β-caryophyllene) sources in the cirrus regime (−46 to −38 °C). Several aerosolized BC proxies were selected to represent different particle morphologies and oxidation levels. Atmospheric aging was further replicated with exposure of SOA-coated BC to OH. The results demonstrate that the 400 nm hydrophobic BC types nucleate ice only at or near the homogeneous freezing threshold (−42 to −46 ˚C). Deposition IN, as opposed to purely homogeneous freezing, was observed to occur for some BC types between 100–200 nm within the investigated temperature range. More fractal BC particles did not consistently act as superior deposition INPs over more spherical ones. SOA coating generated by oxidizing β-caryophyllene with O3 did not seem to affect BC IN ability. However, SOA coatings generated from OH oxidation of various organic species did exhibit higher IN onset supersaturation ratio with respect to ice (SSi) compared with bare BC particles, with toluene SOA coating showing an increase of SSi by 0.1–0.15 while still below the homogeneous threshold. n-dodecane and β-caryophyllene-derived SOA only froze in the homogeneous regime. We attribute the inhibition of IN ability to the filling of the pores on the BC surface by the SOA material coating. OH exposure levels of all SOA coating experiments, from an equivalent atmospheric 10 days to 90 days, did not render significant differences in IN potential. Our study suggests that BC particles with large sizes and/or oxidized surfaces generally exhibit better IN ability, and that the organic coating materials can inhibit ice formation.

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Section: Ice Nucleation On Bc Coated With Soa Materialssupporting

confidence: 79%

The effects of morphology, mobility size and SOA material coating on the ice nucleation activity of black carbon in the cirrus regime

Zhang¹,

Zhang²,

Wolf³

et al. 2020

Preprint

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“…However, the effects of molecular structure and functional groups on glass transition temperature (T g ), a parameter determining a phase transition between amorphous solid and semisolid states, are not considered in those studies. Recently, the close relation between volatility and viscosity have been proved (Zhang et al, 2019;Champion et al, 2019), and parameterizations are developed to predict viscosity based on O/C and volatility at 11 global sites (Li et al, 2020). However, the simulation of the phase state and viscosity of OA in NCP during wintertime have not yet been made, impeding our understanding of the phase states of OA and its potential impacts.…”

Section: ;mentioning

confidence: 99%

“…A detailed description of predicting the glass transition temperature, viscosity and some parameters of OA is given in Li et al (2020). Briefly, T g,i for each volatility bin is predicted based on volatility and O/C (A-A method) using Eq.…”

Section: Predictions Of the Glass Transition Temperature And Viscositymentioning

confidence: 99%

Organic aerosol volatility and viscosity in North China Plain: Contrast between summer and winter

Xu¹,

Chen²,

Qiu³

et al. 2020

Preprint

Self Cite

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Abstract. Volatility and viscosity have substantial impacts on gas-particle partitioning, formation and evolution of aerosol, and hence the predictions of aerosol related air quality and climate effects. Here aerosol volatility and viscosity at a rural site (Gucheng) and an urban site (Beijing) in North China Plain (NCP) in summer and winter were investigated by using a thermodenuder coupled with high resolution aerosol mass spectrometer. The effective saturation concentration (C*) of organic aerosol (OA) in summer was smaller than that in winter (0.55 μg m−3 vs. 0.71–0.75 μg m−3), indicating that OA in winter in NCP is more volatile due to enhanced primary emissions from coal combustion and biomass burning. The volatility distributions varied largely different among different OA factors. In particular, we found that hydrocarbon-like OA (HOA) contained more non-volatile compounds compared to coal combustion related OA. The more oxidized oxygenated OA (MO-OOA) showed overall lower volatility than less oxidized OOA (LO-OOA) in both summer and winter, yet the volatility of MO-OOA was found to be relative humidity (RH) dependent showing more volatile properties at higher RH. Our results demonstrated the different composition and chemical formation pathways of MO-OOA under different RH levels. The glass transition temperature (Tg) and viscosity of OA in summer and winter are estimated using the recently developed parameterization formula. Our results showed that the Tg of OA in summer in Beijing (291.5 K) was higher than that in winter (289.7–290.0 K), while it varied greatly among different OA factors. The viscosity suggested that OA existed mainly as solid in winter in Beijing, but as semi-solids in Beijing in summer and Gucheng in winter. These results have important implications that kinetically limited gas-particle partitioning may need to be considered when simulating secondary OA formation in NCP.

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“…Freshly emitted BC particles are typically hydrophobic, fractal, nanoscale (< 200 nm) aggregates with branched or chain-like structures (e.g., Kinsey et al, 2010;Beyersdorf et al, 2014;Liati et al, 2014;Vander Wal et al, 2014;Lobo et al, 2015;Moore et al, 2017). BC aggregate surface area is determined by the primary particle sizes, the number of primary particles, and the way primary particles are connected (Kittelson, 1998).…”

Section: Introductionmentioning

confidence: 99%

The effects of morphology, mobility size, and secondary organic aerosol (SOA) material coating on the ice nucleation activity of black carbon in the cirrus regime

Zhang

Wolf

et al. 2020

Atmos. Chem. Phys.

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Abstract. There is evidence that black carbon (BC) particles may affect cirrus formation and, hence, global climate by acting as potential ice nucleating particles (INPs) in the troposphere. Nevertheless, the ice nucleation (IN) ability of bare BC and BC coated with secondary organic aerosol (SOA) material remains uncertain. We have systematically examined the IN ability of 100–400 nm size-selected BC particles with different morphologies and different SOA coatings representative of anthropogenic (toluene and n-dodecane) and biogenic (β-caryophyllene) sources in the cirrus regime (−46 to −38 ∘C). Several BC proxies were selected to represent different particle morphologies and oxidation levels. Atmospheric aging was further replicated with the exposure of SOA-coated BC to OH. The results demonstrate that the 400 nm hydrophobic BC types nucleate ice only at or near the homogeneous freezing threshold. Ice formation at cirrus temperatures below homogeneous freezing thresholds, as opposed to purely homogeneous freezing, was observed to occur for some BC types between 100 and 200 nm within the investigated temperature range. More fractal BC particles did not consistently act as superior INPs over more spherical ones. SOA coating generated by oxidizing β-caryophyllene with O3 did not seem to affect BC IN ability, probably due to an SOA-phase state transition. However, SOA coatings generated from OH oxidation of various organic species did exhibit higher IN-onset supersaturation ratio with respect to ice (SSi), compared with bare BC particles, with the toluene-SOA coating showing an increase in SSi of 0.1–0.15 while still below the homogeneous freezing threshold. Slightly oxidized toluene SOA coating seemed to have a stronger deactivation effect on BC IN ability than highly oxidized toluene SOA, which might be caused by oligomer formation and the phase state transition of toluene SOA under different oxidation levels. n-dodecane and β-caryophyllene-derived SOA-coated BC only froze in the homogeneous regime. We attribute the inhibition of IN ability to the filling of the pores on the BC surface by the SOA material coating. OH exposure levels of n-dodecane and β-caryophyllene SOA coating experiments, from an equivalent atmospheric exposure time from 10 to 90 d, did not render significant differences in the IN potential. Our study of selected BC types and sizes suggests that increases in diameter, compactness, and/or surface oxidation of BC particles lead to more efficient IN via the pore condensation freezing (PCF) pathway, and that coatings of common SOA materials can inhibit the formation of ice.

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Predictions of the glass transition temperature and viscosity of organic aerosols from volatility distributions

Cited by 68 publications

References 125 publications

The effects of morphology, mobility size and SOA material coating on the ice nucleation activity of black carbon in the cirrus regime

The effects of morphology, mobility size and SOA material coating on the ice nucleation activity of black carbon in the cirrus regime

Organic aerosol volatility and viscosity in North China Plain: Contrast between summer and winter

The effects of morphology, mobility size, and secondary organic aerosol (SOA) material coating on the ice nucleation activity of black carbon in the cirrus regime

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