Multiphase reactivity of polycyclic aromatic hydrocarbons is driven by phase separation and diffusion limitations

Zhou, Shouming; Hwang, Brian; Lakey, Pascale S. J.; Zuend, Andreas; Abbatt, Jonathan P. D.; Shiraiwa, Manabu

doi:10.1073/pnas.1902517116

Cited by 112 publications

(136 citation statements)

References 58 publications

Supporting

Mentioning

121

Contrasting

Order By: Relevance

“…210 Also, although BaP is fully soluble in cooking oil, its oxygenated ozonolysis reaction products phase separate from the reactants and cooking oil, forming a more viscous reaction medium. 212 By preventing the BaP from reacting with incoming ozone molecules, residual BaP is le on the surface even though all the BaP would have reacted away had the solution remained well mixed. Such complex interactions need to be fully understood to arrive at a quantitative description of multiphase reactivity on indoor surfaces and aerosol particles.…”

Section: (C) Multiphase Reactionsmentioning

confidence: 99%

The atmospheric chemistry of indoor environments

Abbatt

Wang

2020

Environ. Sci.: Processes Impacts

Self Cite

133

161

View full text Add to dashboard Cite

show abstract

Section: (C) Multiphase Reactionsmentioning

confidence: 99%

The atmospheric chemistry of indoor environments

Abbatt

Wang

2020

Environ. Sci.: Processes Impacts

Self Cite

133

161

View full text Add to dashboard Cite

show abstract

“…Oxidation reactions within a particle or diffusion of reactants to the particle surface are also slowed, leading to the extended preservation of organic species within aerosol phases that would otherwise undergo photodegradation (Zelenyuk et al, 2017). Reduced evaporation and shielding from oxidation may increase the residence time or organic species, giving these particles and their constituents an advantage in undergoing long-range transport (Schum et al, 2018;Zhou et al, 2019) and in turn, contributing to transboundary pollution (Shrivastava et al, 2017).…”

Section: Introductionmentioning

confidence: 99%

A predictive group-contribution model for the viscosity of aqueous organic aerosol

Gervasi¹,

Topping²,

Zuend³

2019

Preprint

Self Cite

View full text Add to dashboard Cite

Abstract. The viscosity of primary and secondary organic aerosol (SOA) has important implications for the processing of aqueous organic aerosol phases in the atmosphere, their involvement in climate forcing, and transboundary pollution. Here we introduce a new thermodynamics-based group-contribution model, which is capable of accurately predicting the dynamic viscosity of a mixture over several orders of magnitude (~&#8201;10&#8722;3 to >&#8201;1012&#8201;Pa&#8201;s) as a function of temperature and mixture composition, accounting for the effect of relative humidity on aerosol water content. The mixture viscosity modelling framework builds on the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic&#8211;Organic Mixtures Functional groups Activity Coefficients) for predictions of liquid mixture non-ideality, including liquid&#8211;liquid phase separation, and the calorimetric glass transition temperature model by DeRieux et al. (2018) for pure-component viscosity values of organic components. Comparing this new model with simplified modelling approaches reveals that the group-contribution method is the most accurate in predicting mixture viscosity, although accurate pure-component viscosity predictions (and associated experimental data) are key and one of the main sources of uncertainties in current models, including the model presented here. Nonetheless, we find excellent agreement between the viscosity predictions and measurements for systems in which mixture constituents have a molar mass below 350&#8201;g&#8201;mol&#8722;1. As such, we demonstrate the validity of the model in quantifying mixture viscosity for aqueous binary mixtures (glycerol, citric acid, sucrose, and trehalose), aqueous multicomponent mixtures (citric acid&#8201;+&#8201;sucrose and a mixture of nine dicarboxylic acids), and aqueous SOA surrogate mixtures derived from the oxidation of &#945;-pinene, toluene, or isoprene. We also use the model to assess the expected change in SOA particle viscosity during idealized adiabatic air parcel transport from the surface to higher altitudes within the troposphere. This work demonstrates the capability and flexibility of our model in predicting the viscosity for organic mixtures of varying degrees of complexity and its applicability for modelling SOA viscosity over a wide range of temperatures and relative humidities.

show abstract

“…A large body of research demonstrates that heterogeneous chemistry in aerosols needs to be taken into account as it affects the growth of inorganic aerosol (e.g., [3,[60][61][62][63][64]) and SOA [65][66][67] in urban and remote regions. In addition, organic chemistry both in the gas and aerosol phases can produce hydrophobic and hydrophilic compounds and result in heterogeneous aerosol composition (multiphase morphologies) [37,[68][69][70][71].…”

Section: Introductionmentioning

confidence: 99%

Current State of Atmospheric Aerosol Thermodynamics and Mass Transfer Modeling: A Review

Semeniuk

Dastoor

2020

Atmosphere

View full text Add to dashboard Cite

A useful aerosol model must be able to adequately resolve the chemical complexity and phase state of the wide particle size range arising from the many different secondary aerosol growth processes to assess their environmental and health impacts. Over the past two decades, significant advances in understanding of gas-aerosol partitioning have occurred, particularly with respect to the role of organic compounds, yet aerosol representations have changed little in air quality and climate models since the late 1990s and early 2000s. The gas-aerosol partitioning models which are still commonly used in air quality models are separate inorganics-only thermodynamics and secondary organic aerosol (SOA) formation based on absorptive partitioning theory with an assumption of well-mixed liquid-like particles that continuously maintain equilibrium with the gas phase. These widely used approaches in air quality models for secondary aerosol composition and growth based on separated inorganic and organic processes are inadequate. This review summarizes some of the important developments during the past two decades in understanding of gas aerosol mass transfer processes. Substantial increases in computer performance in the last decade justify increasing the process detail in aerosol models. Organics play a central role during post-nucleation growth into the accumulation mode and change the hygroscopic properties of sulfate aerosol. At present, combined inorganic-organic aerosol thermodynamics models are too computationally expensive to be used online in 3-D simulations without high levels of aggregation of organics into a small number of functional surrogates. However, there has been progress in simplified modeling of liquid-liquid phase separation (LLPS) and distinct chemical regimes within organic-rich and inorganic-rich phases. Additional limitations of commonly used thermodynamics models are related to lack of surface tension data for various aerosol compositions in the small size limit, and lack of a comprehensive representation of surface interaction terms such as disjoining pressure in the Gibbs free energy which become significant in the small size limit and which affect both chemical composition and particle growth. As a result, there are significant errors in modeling of hygroscopic growth and phase transitions for particles in the nucleation and Aitken modes. There is also increasing evidence of reduced bulk diffusivity in viscous organic particles and, therefore, traditional secondary organic aerosol models, which are typically based on the assumption of instantaneous equilibrium gas-particle partitioning and neglect the kinetic effects, are no longer tenable.

show abstract

Multiphase reactivity of polycyclic aromatic hydrocarbons is driven by phase separation and diffusion limitations

Cited by 112 publications

References 58 publications

The atmospheric chemistry of indoor environments

The atmospheric chemistry of indoor environments

A predictive group-contribution model for the viscosity of aqueous organic aerosol

Current State of Atmospheric Aerosol Thermodynamics and Mass Transfer Modeling: A Review

Contact Info

Product

Resources

About