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Title: Liquid–liquid phase separation and viscosity within secondary organic aerosol generated from diesel fuel vapors
Abstract. Information on liquid–liquid phase separation (LLPS) and viscosity (ordiffusion) within secondary organic aerosol (SOA) is needed to improvepredictions of particle size, mass, reactivity, and cloud nucleatingproperties in the atmosphere. Here we report on LLPS and viscosities withinSOA generated by the photooxidation of diesel fuel vapors. Diesel fuelcontains a wide range of volatile organic compounds, and SOA generated bythe photooxidation of diesel fuel vapors may be a good proxy for SOA fromanthropogenic emissions. In our experiments, LLPS occurred over the relativehumidity (RH) range of ∼70 % to ∼100 %,resulting in an organic-rich outer phase and a water-rich inner phase. Theseresults may have implications for predicting the cloud nucleating propertiesof anthropogenic SOA since the presence of an organic-rich outer phase athigh-RH values can lower the supersaturation with respect to water requiredfor cloud droplet formation. At ≤10 % RH, the viscosity was ≥1×108 Pa s, which corresponds to roughly the viscosity of tarpitch. At 38 %–50 % RH, the viscosity was in the range of 1×108 to 3×105 Pa s. These measured viscosities areconsistent with predictions based on oxygen to carbon elemental ratio (O:C)and molar mass as well as predictions based on the number of carbon,hydrogen, and oxygen atoms. Based on the measured viscosities and theStokes–Einstein relation, at ≤10 % RH diffusion coefficients oforganics within diesel fuel SOA is ≤5.4×10-17 cm2 s−1 and the mixing time of organics within 200 nm diesel fuel SOAparticles (τmixing) is 50 h. These small diffusion coefficientsand large mixing times may be important in laboratory experiments, where SOAis often generated and studied using low-RH conditions and on timescales ofminutes to hours. At 38 %–50 % RH, the calculated organic diffusioncoefficients are in the range of 5.4×10-17 to 1.8×10-13 cm2 s−1 and calculated τmixing values arein the range of ∼0.01 h to ∼50 h. These valuesprovide important constraints for the physicochemical properties ofanthropogenic SOA.  more » « less
Award ID(s):
1654104
PAR ID:
10142832
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ; ;
Date Published:
Journal Name:
Atmospheric Chemistry and Physics
Volume:
19
Issue:
19
ISSN:
1680-7324
Page Range / eLocation ID:
12515 to 12529
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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