Modeling the gas-particle partitioning of secondary organic aerosol: the importance of liquid-liquid phase separation

The partitioning of semivolatile organic compounds between the gas phase and aerosol particles is an important source of secondary organic aerosol (SOA). Gas-particle partitioning of organic and inorganic species is influenced by the physical state and water content of aerosols, and therefore ambient relative humidity (RH), as well as temperature and organic loading levels. We introduce a novel combination of the thermodynamic models AIOMFAC (for liquid mixture non-ideality) and EVAPORATION (for pure compound vapor pressures) with oxidation product information from the Master Chemical Mechanism (MCM) for the computation of gas-particle partitioning of organic compounds and water. The presence and impact of a liquid-liquid phase separation in the condensed phase is calculated as a function of variations in relative humidity, organic loading levels, and associated changes in aerosol composition. We show that a complex system of water, ammonium sulfate, and SOA from the ozonolysis of α-pinene exhibits liquid-liquid phase separation over a wide range of relative humidities (simulated from 30% to 99% RH). Since fully coupled phase separation and gas-particle partitioning calculations are computationally expensive, several simplified model approaches are tested with regard to computational costs and accuracy of predictions compared to the benchmark calculation. It is shown that forcing a liquid one-phase aerosol with or without consideration of non-ideal mixing bears the potential for vastly incorrect partitioning predictions. Assuming an ideal mixture leads to substantial overestimation of the particulate organic mass, by more than 100% at RH values of 80% and by more than 200% at RH values of 95%. Moreover, the simplified one-phase cases stress two key points for accurate gas-particle partitioning calculations: (1) non-ideality in the condensed phase needs to be considered and (2) liquid-liquid phase separation is a consequence of considerable deviations from ideal mixing in solutions containing inorganic ions and organics that cannot be ignored. Computationally much more efficient calculations relying on the assumption of a complete organic/electrolyte phase separation below a certain RH successfully reproduce gas-particle partitioning in systems in which the average oxygen-to-carbon (O:C) ratio is lower than ~0.6, as in the case of α-pinene SOA, and bear the potential for implementation in atmospheric chemical transport models and chemistry-climate models. A full equilibrium calculation is the method of choice for accurate offline (box model) computations, where high computational costs are acceptable. Such a calculation enables the most detailed predictions of phase compositions and provides necessary information on whether assuming a complete organic/electrolyte phase separation is a good approximation for a given aerosol system. Based on the group-contribution concept of AIOMFAC and O:C ratios as a proxy for polarity and hygroscopicity of organic mixtures, the results from the α-pinene system are also discussed from a more general point of view

Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols

Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE) affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008). This model allows the reliable computation of the liquid-liquid coexistence curve (binodal), corresponding tie-lines, the limit of stability/metastability (spinodal), and further thermodynamic properties of multicomponent systems. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH) and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility) are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six-component system simulation. For simplified partitioning parametrizations, we suggest a modified definition of the effective saturation concentration, C_j^*, by including water and other inorganics in the absorbing phase. Such a C_j^* definition reduces the RH-dependency of the gas/particle partitioning of semivolatile organics in organic-inorganic aerosols by an order of magnitude as compared to the currently accepted definition, which considers the organic species only

Water-soluble SOA from Alkene ozonolysis: composition and droplet activation kinetics inferences from analysis of CCN activity

Cloud formation characteristics of the water-soluble organic fraction (WSOC) of secondary organic aerosol (SOA) formed from the ozonolysis of alkene hydrocarbons (terpinolene, 1-methlycycloheptene and cycloheptene) are studied. Based on size-resolved measurements of CCN activity (of the pure and salted WSOC samples) we estimate the average molar volume and surface tension depression associated with the WSOC using Köhler Theory Analysis (KTA). Consistent with known speciation, the results suggest that the WSOC are composed of low molecular weight species, with an effective molar mass below 200 g mol^(−1). The water-soluble carbon is also surface-active, depressing surface tension 10–15% from that of pure water (at CCN-relevant concentrations). The inherent hygroscopicity parameter, κ, of the WSOC ranges between 0.17 and 0.25; if surface tension depression and molar volume effects are considered in κ, a remarkably constant "apparent" hygroscopicity ~0.3 emerges for all samples considered. This implies that the volume fraction of soluble material in the parent aerosol is the key composition parameter required for prediction of the SOA hygroscopicity, as shifts in molar volume across samples are compensated by changes in surface tension. Finally, using "threshold droplet growth analysis", the water-soluble organics in all samples considered do not affect CCN activation kinetics

Kinetic modeling of Secondary Organic Aerosol formation: effects of particle- and gas-phase reactions of semivolatile products

The distinguishing mechanism of formation of secondary organic aerosol (SOA) is the partitioning of semivolatile hydrocarbon oxidation products between the gas and aerosol phases. While SOA formation is typically described in terms of partitioning only, the rate of formation and ultimate yield of SOA can also depend on the kinetics of both gas- and aerosol-phase processes. We present a general equilibrium/kinetic model of SOA formation that provides a framework for evaluating the extent to which the controlling mechanisms of SOA formation can be inferred from laboratory chamber data. With this model we examine the effect on SOA formation of gas-phase oxidation of first-generation products to either more or less volatile species, of particle-phase reaction (both first- and second-order kinetics), of the rate of parent hydrocarbon oxidation, and of the extent of reaction of the parent hydrocarbon. The effect of pre-existing organic aerosol mass on SOA yield, an issue of direct relevance to the translation of laboratory data to atmospheric applications, is examined. The importance of direct chemical measurements of gas- and particle-phase species is underscored in identifying SOA formation mechanisms

Ternary nucleation of H_2SO_4, NH_3 and H_2O

A classical theory of the ternary homogeneous nucleation of sulfuric acid—ammonia—water is presented. For NH3 mixing ratios exceeding 1 ppt, the presence of ammonia enhances the binary (sulfuric acid—water) nucleation rate by several orders of magnitude. However, the limiting component for ternary nucleation—as for binary nucleation—is sulfuric acid. The sulfuric acid concentration needed for significant ternary nucleation is several orders of magnitude below that required in binary case

Aerosol hygroscopicity in the marine atmosphere: a closure study using high-time-resolution, multiple-RH DASH-SP and size-resolved C-ToF-AMS data

We have conducted the first airborne hygroscopic growth closure study to utilize data from an Aerodyne compact Time-of-Flight Aerosol Mass Spectrometer (C-ToF-AMS) coupled with size-resolved, multiple-RH, high-time-resolution hygroscopic growth factor (GF) measurements from the differential aerosol sizing and hygroscopicity spectrometer probe (DASH-SP). These data were collected off the coast of Central California during seven of the 16 flights carried out during the MASE-II field campaign in July 2007. Two of the seven flights were conducted in airmasses characterized by continental origin. These flights exhibited elevated organic volume fractions (VF_(organic)=0.56±0.19, as opposed to 0.39±0.20 for all other flights), corresponding to significantly suppressed GFs at high RH (1.61±0.14 at 92% RH, as compared with 1.91±0.07 for all other flights), more moderate GF suppression at intermediate RH (1.53±0.10 at 85%, compared with 1.58±0.08 for all other flights), and no measurable GF suppression at low RH (1.31±0.06 at 74%, compared with 1.31±0.07 for all other flights). Organic loadings were slightly elevated in above-cloud aerosols, as compared with below-cloud aerosols, and corresponded to a similar trend of significantly suppressed GF at high RH, but more moderate impacts at lower values of RH. A hygroscopic closure based on a volume-weighted mixing rule provided good agreement with DASH-SP measurements (R^2=0.78). Minimization of root mean square error between observations and predictions indicated mission-averaged organic GFs of 1.22, 1.45, and 1.48 at 74, 85, and 92% RH, respectively. These values agree with previously reported values for water-soluble organics such as dicarboxylic and multifunctional acids, and correspond to a highly oxidized, presumably water-soluble, organic fraction (mission-averaged O:C=0.92±0.33). Finally, a backward stepwise linear regression revealed that, other than RH, the most important predictor for GF is VF_(organic), indicating that a simple emperical model relating GF, RH, and the relative abundance of organic material can provide accurate predictions (R^2=0.77) of hygroscopic growth for the California coast

Impact of a large wildfire on water-soluble organic aerosol in a major urban area: the 2009 Station Fire in Los Angeles County

This study examines the nature of water-soluble organic aerosol measured in Pasadena, CA, under typical conditions and under the influence of a large wildfire (the 2009 Station Fire). During non-fire periods, water-soluble organic carbon (WSOC) variability was driven by photochemical production processes and sea breeze transport, resulting in an average diurnal cycle with a maximum at 15:00 local time (up to 4.9 μg C m^(−3)). During the Station Fire, primary production was a key formation mechanism for WSOC. High concentrations of WSOC (up to 41 μg C m^(−3)) in smoke plumes advected to the site in the morning hours were tightly correlated with nitrate and chloride, numerous aerosol mass spectrometer (AMS) organic mass spectral markers, and total non-refractory organic mass. Processed residual smoke was transported to the measurement site by the sea breeze later in the day, leading to higher afternoon WSOC levels than on non-fire days. Parameters representing higher degrees of oxidation of organics, including the ratios of the organic metrics m/z 44:m/z 57 and m/z 44:m/z 43, were elevated in those air masses. Intercomparisons of relative amounts of WSOC, organics, m/z 44, and m/z 43 show that the fraction of WSOC comprising acid-oxygenates increased as a function of photochemical aging owing to the conversion of aliphatic and non-acid oxygenated organics to more acid-like organics. The contribution of water-soluble organic species to the organic mass budget (10th–90th percentile values) ranged between 27 %–72 % and 27 %–68 % during fire and non-fire periods, respectively. The seasonal incidence of wildfires in the Los Angeles Basin greatly enhances the importance of water-soluble organics, which has implications for the radiative and hygroscopic properties of the regional aerosol

A new atmospheric aerosol phase equilibrium model (UHAERO): organic systems

In atmospheric aerosols, water and volatile inorganic and organic species are distributed between the gas and aerosol phases in accordance with thermodynamic equilibrium. Within an atmospheric particle, liquid and solid phases can exist at equilibrium. Models exist for computation of phase equilibria for inorganic/water mixtures typical of atmospheric aerosols; when organic species are present, the phase equilibrium problem is complicated by organic/water interactions as well as the potentially large number of organic species. We present here an extension of the UHAERO inorganic thermodynamic model (Amundson et al., 2006c) to organic/water systems. Phase diagrams for a number of model organic/water systems characteristic of both primary and secondary organic aerosols are computed. Also calculated are inorganic/organic/water phase diagrams that show the effect of organics on inorganic deliquescence behavior. The effect of the choice of activity coefficient model for organics on the computed phase equilibria is explored

Modeling of secondary organic aerosol yields from laboratory chamber data

Laboratory chamber data serve as the basis for constraining models of secondary organic aerosol (SOA) formation. Current models fall into three categories: empirical two-product (Odum), product-specific, and volatility basis set. The product-specific and volatility basis set models are applied here to represent laboratory data on the ozonolysis of α-pinene under dry, dark, and low-NOx conditions in the presence of ammonium sulfate seed aerosol. Using five major identified products, the model is fit to the chamber data. From the optimal fitting, SOA oxygen-to-carbon (O/C) and hydrogen-to-carbon (H/C) ratios are modeled. The discrepancy between measured H/C ratios and those based on the oxidation products used in the model fitting suggests the potential importance of particle-phase reactions. Data fitting is also carried out using the volatility basis set, wherein oxidation products are parsed into volatility bins. The product-specific model is most likely hindered by lack of explicit inclusion of particle-phase accretion compounds. While prospects for identification of the majority of SOA products for major volatile organic compounds (VOCs) classes remain promising, for the near future empirical product or volatility basis set models remain the approaches of choice

A computationally efficient inorganic atmospheric aerosol phase equilibrium model (UHAERO)

A variety of thermodynamic models have been developed to predict inorganic gas-aerosol equilibrium. To achieve computational efficiency a number of the models rely on a priori specification of the phases present in certain relative humidity regimes. Presented here is a new computational model, named UHAERO, that is both efficient and rigorously computes phase behavior without any a priori specification. The computational implementation is based on minimization of the Gibbs free energy using a primal-dual method, coupled to a Newton iteration. The mathematical details of the solution are given elsewhere. The model also computes deliquescence and crystallization behavior without any a priori specification of the relative humidities of deliquescence or crystallization. Detailed phase diagrams of the sulfate/nitrate/ammonium/water system are presented as a function of relative humidity at 298.15 K over the complete space of composition