The formation and aging of organic aerosols (OA) proceed through multiple steps of chemical reaction and mass transport in the gas and particle phases, which is challenging for the interpretation of ...field measurements and laboratory experiments as well as accurate representation of OA evolution in atmospheric aerosol models. Based on data from over 30 000 compounds, we show that organic compounds with a wide variety of functional groups fall into molecular corridors, characterized by a tight inverse correlation between molar mass and volatility. We developed parameterizations to predict the saturation mass concentration of organic compounds containing oxygen, nitrogen, and sulfur from the elemental composition that can be measured by soft-ionization high-resolution mass spectrometry. Field measurement data from new particle formation events, biomass burning, cloud/fog processing, and indoor environments were mapped into molecular corridors to characterize the chemical nature of the observed OA components. We found that less-oxidized indoor OA are constrained to a corridor of low molar mass and high volatility, whereas highly oxygenated compounds in atmospheric water extend to high molar mass and low volatility. Among the nitrogen- and sulfur-containing compounds identified in atmospheric aerosols, amines tend to exhibit low molar mass and high volatility, whereas organonitrates and organosulfates follow high O : C corridors extending to high molar mass and low volatility. We suggest that the consideration of molar mass and molecular corridors can help to constrain volatility and particle-phase state in the modeling of OA particularly for nitrogen- and sulfur-containing compounds.
Secondary organic aerosols (SOA) account for a substantial fraction of air
particulate matter, and SOA formation is often modeled assuming rapid
establishment of gas–particle equilibrium. Here, we ...estimate the
characteristic timescale for SOA to achieve gas–particle equilibrium under
a wide range of temperatures and relative humidities using a
state-of-the-art kinetic flux model. Equilibration timescales were
calculated by varying particle phase state, size, mass loadings, and
volatility of organic compounds in open and closed systems. Model
simulations suggest that the equilibration timescale for semi-volatile
compounds is on the order of seconds or minutes for most conditions in the
planetary boundary layer, but it can be longer than 1 h if particles
adopt glassy or amorphous solid states with high glass transition
temperatures at low relative humidity. In the free troposphere with lower
temperatures, it can be longer than hours or days, even at moderate or
relatively high relative humidities due to kinetic limitations of bulk
diffusion in highly viscous particles. The timescale of partitioning of
low-volatile compounds into highly viscous particles is shorter compared to
semi-volatile compounds in the closed system, as it is largely determined by
condensation sink due to very slow re-evaporation with relatively quick
establishment of local equilibrium between the gas phase and the
near-surface bulk. The dependence of equilibration timescales on both
volatility and bulk diffusivity provides critical insights into
thermodynamic or kinetic treatments of SOA partitioning for accurate
predictions of gas- and particle-phase concentrations of semi-volatile
compounds in regional and global chemical transport models.
Secondary organic aerosol (SOA) formed from partitioning of oxidation products of anthropogenic and biogenic volatile organic compounds (VOCs) accounts for a substantial portion of atmospheric ...particulate matter. In describing SOA formation, it is generally assumed that VOC oxidation products rapidly adopt gas‐aerosol equilibrium. Here we estimate the equilibration timescale,τeq, of SOA gas‐particle partitioning using a state‐of‐the‐art kinetic flux model.τeqis found to be of order seconds to minutes for partitioning of relatively high volatility organic compounds into liquid particles, thereby adhering to equilibrium gas‐particle partitioning. However,τeqincreases to hours or days for organic aerosol associated with semi‐solid particles, low volatility, large particle size, and low mass loadings. Instantaneous equilibrium partitioning may lead to substantial overestimation of particle mass concentration and underestimation of gas‐phase concentration.
Key Points
Equilibration timescale of SOA partitioning is estimated
Kinetically limited vs. quasi‐equilibrium particle growth is discussed
Phase state has large impact on SOA partitioning kinetics
Recently, it has been proposed that organic aerosol particles in the atmosphere can exist in an amorphous semi-solid or solid (i.e. glassy) state. In this perspective, we analyse and discuss the ...formation and properties of amorphous semi-solids and glasses from organic liquids. Based on a systematic survey of a wide range of organic compounds, we present estimates for the glass forming properties of atmospheric secondary organic aerosol (SOA). In particular we investigate the dependence of the glass transition temperature T(g) upon various molecular properties such as the compounds' melting temperature, their molar mass, and their atomic oxygen-to-carbon ratios (O:C ratios). Also the effects of mixing different compounds and the effects of hygroscopic water uptake depending on ambient relative humidity are investigated. In addition to the effects of temperature, we suggest that molar mass and water content are much more important than the O:C ratio for characterizing whether an organic aerosol particle is in a liquid, semi-solid, or glassy state. Moreover, we show how the viscosity in liquid, semi-solid and glassy states affect the diffusivity of those molecules constituting the organic matrix as well as that of guest molecules such as water or oxidants, and we discuss the implications for atmospheric multi-phase processes. Finally, we assess the current state of knowledge and the level of scientific understanding, and we propose avenues for future studies to resolve existing uncertainties.
Emissions from biomass burning are a significant source of brown carbon (BrC) in the atmosphere. In this study, we investigate the molecular composition of freshly emitted biomass burning organic ...aerosol (BBOA) samples collected during test burns of sawgrass, peat, ponderosa pine, and black spruce. We demonstrate that both the BrC absorption and the chemical composition of light-absorbing compounds depend significantly on the type of biomass fuels. Common BrC chromophores in the selected BBOA samples include nitro-aromatics, polycyclic aromatic hydrocarbon derivatives, and polyphenols spanning a wide range of molecular weights, structures, and light absorption properties. A number of biofuel-specific BrC chromophores are observed, indicating that some of them may be used as source-specific markers of BrC. On average, ∼50% of the light absorption in the solvent-extractable fraction of BBOA can be attributed to a limited number of strong BrC chromophores. The absorption coefficients of BBOA are affected by solar photolysis. Specifically, under typical atmospheric conditions, the 300 nm absorbance decays with a half-life of ∼16 h. A “molecular corridor” analysis of the BBOA volatility distribution suggests that many BrC compounds in the fresh BBOA have low saturation mass concentration (<1 μg m–3) and will be retained in the particle phase under atmospherically relevant conditions.
Organic substances can adopt an amorphous solid or semisolid state, influencing the rate of heterogeneous reactions and multiphase processes in atmospheric aerosols. Here we demonstrate how molecular ...diffusion in the condensed phase affects the gas uptake and chemical transformation of semisolid organic particles. Flow tube experiments show that the ozone uptake and oxidative aging of amorphous protein is kinetically limited by bulk diffusion. The reactive gas uptake exhibits a pronounced increase with relative humidity, which can be explained by a decrease of viscosity and increase of diffusivity due to hygroscopic water uptake transforming the amorphous organic matrix from a glassy to a semisolid state (moisture-induced phase transition). The reaction rate depends on the condensed phase diffusion coefficients of both the oxidant and the organic reactant molecules, which can be described by a kinetic multilayer flux model but not by the traditional resistor model approach of multiphase chemistry. The chemical lifetime of reactive compounds in atmospheric particles can increase from seconds to days as the rate of diffusion in semisolid phases can decrease by multiple orders of magnitude in response to low temperature or low relative humidity. The findings demonstrate that the occurrence and properties of amorphous semisolid phases challenge traditional views and require advanced formalisms for the description of organic particle formation and transformation in atmospheric models of aerosol effects on air quality, public health, and climate.
Abstract
This review outlines recent advances in the investigation of the chemical properties, molecular interactions and health effects of hazardous compounds in atmospheric aerosols, in particular ...reactive oxygen species (ROS), soot, polycyclic aromatic compounds (PACs) and allergenic proteins. Epidemiological studies show correlations between air particulate matter and adverse health effects of air pollution including allergy, asthma, cardiovascular and respiratory diseases, but the causative relations and mechanisms of interaction on the molecular level are still unclear. ROS generated by photochemical and heterogeneous reactions in the atmosphere seem to play a key role in aerosol health effects and provide a direct link between atmospheric and physiological multiphase processes. Soot and PACs can trigger formation of ROS in vivo, leading to inflammation and cellular damage. PACs as well as allergenic proteins are efficiently oxygenated and nitrated upon exposure to ozone and nitrogen dioxide, which leads to an enhancement of their toxicity and allergenicity.
Secondary organic aerosols (SOA) are a large source of uncertainty in our current understanding of climate change and air pollution. The phase state of SOA is important for quantifying their effects ...on climate and air quality, but its global distribution is poorly characterized. We developed a method to estimate glass transition temperatures based on the molar mass and molecular O:C ratio of SOA components, and we used the global chemistry climate model EMAC with the organic aerosol module ORACLE to predict the phase state of atmospheric SOA. For the planetary boundary layer, global simulations indicate that SOA are mostly liquid in tropical and polar air with high relative humidity, semi-solid in the mid-latitudes and solid over dry lands. We find that in the middle and upper troposphere SOA should be mostly in a glassy solid phase state. Thus, slow diffusion of water, oxidants and organic molecules could kinetically limit gas-particle interactions of SOA in the free and upper troposphere, promote ice nucleation and facilitate long-range transport of reactive and toxic organic pollutants embedded in SOA.