Complexity of Measuring and Representing the Hygroscopicity of Mixed Component Aerosol

The validation of approaches to predict the hygroscopicity of complex mixtures of organic components in aerosol is important for understanding the hygroscopic response of organic aerosol in the atmosphere. We report new measurements of the hygroscopicity of mixtures of dicarboxylic acids and amino acids using a comparative kinetic electrodynamic balance (CK-EDB) approach, inferring the equilibrium water content of the aerosol from close to a saturation relative humidity (100%) down to 80%. We show that the solution densities and refractive indices of the mixtures can be estimated with an accuracy of better than ±2% using the molar refractive index mixing rule and densities and refractive indices for the individual binary organic–aqueous solutions. Further, we show that the often-used mass-, volume-, and mole-weighted mixing rules to estimate the hygroscopicity parameter κ can overestimate the hygroscopic parameter by a factor of as much as 3, highlighting the need to understand the specific nonideal interactions that may arise synergistically in mixtures and cannot be represented by simple models. Indeed, in some extreme cases the hygroscopicity of a multicomponent mixture can be very close to that for the least hygroscopic component. For mixtures of similar components for which no additional synergistic interactions need be considered, the hygroscopicity of the mixed component aerosol can be estimated with high accuracy from the hygroscopic response of the binary aqueous–organic aerosol. In conclusion, we suggest that the hygroscopicity of multicomponent organic aerosol can be highly nonadditive and that simple correlations of hygroscopicity with composition may often misrepresent the level of complexity essential to interpreting aerosol hygroscopicity

Hygroscopic properties of aminium sulfate aerosols

Alkylaminium sulfates originate from the neutralisation reaction between short-chained amines and sulfuric acid and have been detected in atmospheric aerosol particles. Their physicochemical behaviour is less well characterised than their inorganic equivalent, ammonium sulfate, even though they play a role in atmospheric processes such as the nucleation and growth of new particles and cloud droplet formation. In this work, a comparative evaporation kinetics experimental technique using a cylindrical electrodynamic balance is applied to determine the hygroscopic properties of six short-chained alkylaminium sulfates, specifically mono-, di-, and tri-methylaminium sulfate and mono-, di-, and tri-ethyl aminium sulfate. This approach allows for the retrieval of a water-activity-dependent growth curve in less than 10 s, avoiding the uncertainties that can arise from the volatilisation of semi-volatile components. Measurements are made on particles > 5 µm in radius, avoiding the need to correct equilibrium measurements for droplet-surface curvature with assumed values of the droplet-surface tension. Variations in equilibrium solution droplet composition with varying water activity are reported over the range 0.5 to > 0.98, along with accurate parameterisations of solution density and refractive index. The uncertainties in water activities associated with the hygroscopicity measurements are typically  0.9 and  ∼  ±1 % below 0.9, with maximum uncertainties in diameter growth factors of ±0.7 %. Comparison with previously reported measurements show deviation across the entire water activity range

Hygroscopic properties of aminium sulfate aerosols

Alkylaminium sulfates originate from the neutralisation reaction between short-chained amines and sulfuric acid and have been detected in atmospheric aerosol particles. Their physicochemical behaviour is less well characterised than their inorganic equivalent, ammonium sulfate, even though they play a role in atmospheric processes such as the nucleation and growth of new particles and cloud droplet formation. In this work, a comparative evaporation kinetics experimental technique using a cylindrical electrodynamic balance is applied to determine the hygroscopic properties of six short-chained alkylaminium sulfates, specifically mono-, di-, and tri-methylaminium sulfate and mono-, di-, and tri-ethyl aminium sulfate. This approach allows for the retrieval of a water-activity-dependent growth curve in less than 10 s, avoiding the uncertainties that can arise from the volatilisation of semi-volatile components. Measurements are made on particles > 5 µm in radius, avoiding the need to correct equilibrium measurements for droplet-surface curvature with assumed values of the droplet-surface tension. Variations in equilibrium solution droplet composition with varying water activity are reported over the range 0.5 to > 0.98, along with accurate parameterisations of solution density and refractive index. The uncertainties in water activities associated with the hygroscopicity measurements are typically  0.9 and  ∼  ±1 % below 0.9, with maximum uncertainties in diameter growth factors of ±0.7 %. Comparison with previously reported measurements show deviation across the entire water activity range

Influence of organic compound functionality on aerosol hygroscopicity:dicarboxylic acids, alkyl-substituents, sugars and amino acids

Hygroscopicity data for 36 organic compounds, including amino acids, organic acids, alcohols and sugars, are determined using a comparative kinetics electrodynamic balance (CK-EDB). The CK-EDB applies an electric field to trap-charged aqueous droplets in a chamber with controlled temperature and relative humidity (RH). The dual micro dispenser set-up allows for sequential trapping of probe and sample droplets for accurate determination of droplet water activities from 0.45 to > 0.99. Here, we validate and benchmark the CK-EDB for the homologous series of straight-chain dicarboxylic acids (oxalic–pimelic) with measurements in better agreement with Universal Quasichemical Functional Group Activity Coefficients (UNIFAC) predictions than the original data used to parametrise UNIFAC. Furthermore, a series of increasingly complex organic compounds, with subtle changes to molecular structure and branching, are used to rigorously assess the accuracy of predictions by UNIFAC, which does not explicitly account for molecular structure. We show that the changes in hygroscopicity that result from increased branching and chain length are poorly represented by UNIFAC, with UNIFAC under-predicting hygroscopicity. Similarly, amino acid hygroscopicity is under-predicted by UNIFAC predictions, a consequence of the original data used in the parametrisation of the molecular subgroups. New hygroscopicity data are also reported for a selection of alcohols and sugars and they show variable levels of agreement with predictions

Comparison of Approaches for Measuring and Predicting the Viscosity of Ternary Component Aerosol Particles

Measurements of the water activity-dependent viscosity of aerosol particles from two techniques are compared, specifically from the coalescence of two droplets in holographic optical tweezers (HOT) and poke-and-flow experiments on particles deposited onto a glass substrate. These new data are also compared with the fitting of dimer coagulation, isolation, and coalescence (DCIC) measurements. The aerosol system considered in this work are ternary mixtures of sucrose-citric acid-water and sucrose-NaNO3-water, at varying solute mass ratios. Results from HOT and poke-and-flow are in excellent agreement over their overlapping range of applicability (∼103–107 Pa s); fitted curves from DCIC data show variable agreement with the other two techniques because of the sensitivity of the applied modeling framework to the representation of water content in the particles. Further, two modeling approaches for the predictions of the water activity-dependent viscosity of these ternary systems are evaluated. We show that it is possible to represent their viscosity with relatively simple mixing rules applied to the subcooled viscosity values of each component or to the viscosity of the corresponding binary mixtures

Optimization of process models for determining volatility distribution and viscosity of organic aerosols from isothermal particle evaporation data

The composition of organic aerosol under different ambient conditions as well as their phase state have been a subject of intense study in recent years. One way to study particle properties is to measure the particle size shrinkage in a diluted environment at isothermal conditions. From these measurements it is possible to separate the fraction of low-volatility compounds from high-volatility compounds. In this work, we analyse and evaluate a method for obtaining particle composition and viscosity from measurements using process models coupled with input optimization algorithms. Two optimization methods, the Monte Carlo genetic algorithm and Bayesian inference, are used together with process models describing the dynamics of particle evaporation. The process model optimization scheme in inferring particle composition in a volatility-basis-set sense and composition-dependent particle viscosity is tested with artificially generated data sets and real experimental data. Optimizing model input so that the output matches these data yields a good match for the estimated quantities. Both optimization methods give equally good results when they are used to estimate particle composition to artificially test data. The timescale of the experiments and the initial particle size are found to be important in defining the range of values that can be identified for the properties from the optimization

Accurate Measurements of Aerosol Hygroscopic Growth over a Wide Range in Relative Humidity

Using a comparative evaporation kinetics approach, we describe a new and accurate method for determining the equilibrium hygroscopic growth of aerosol droplets. The time-evolving size of an aqueous droplet, as it evaporates to a steady size and composition that is in equilibrium with the gas phase relative humidity, is used to determine the time-dependent mass flux of water, yielding information on the vapor pressure of water above the droplet surface at every instant in time. Accurate characterization of the gas phase relative humidity is provided from a control measurement of the evaporation profile of a droplet of know equilibrium properties, either a pure water droplet or a sodium chloride droplet. In combination, and by comparison with simulations that account for both the heat and mass transport governing the droplet evaporation kinetics, these measurements allow accurate retrieval of the equilibrium properties of the solution droplet (i.e., the variations with water activity in the mass fraction of solute, diameter growth factor, osmotic coefficient or number of water molecules per solute molecule). Hygroscopicity measurements can be made over a wide range in water activity (from >0.99 to, in principle, 0.9 and ∼±1% below 80% RH, and maximum uncertainties in diameter growth factor of ±0.7%. For all of the inorganic systems examined, the time-dependent data are consistent with large values of the mass accommodation (or evaporation) coefficient (>0.1)

A New Aerosol Flow Reactor to Study Secondary Organic Aerosol

Gas-particle equilibrium partitioning is a fundamental concept used to describe the growth and loss of secondary organic aerosol (SOA). However, recent literature has suggested that gas-particle partitioning may be kinetically limited, preventing volatilization from the aerosol phase as a result of the physical state of the aerosol (e.g. glassy, viscous). Experimental measurements of diffusion constants within viscous aerosol are limited and do not represent the complex chemical composition observed in SOA (i.e. multicomponent mixtures). Motivated by the need to address fundamental questions regarding the effect of the physical state and chemical composition of a particle on gas-particle partitioning, we present the design and operation of a newly built 0.3 m3 continuous flow reactor (CFR) which can be used as a tool to gain considerable insights into the composition and physical state of SOA. The CFR was used to generate SOA from the photo-oxidation of α-pinene, limonene, β-caryophyllene and toluene under different experimental conditions (i.e. relative humidity, VOC and VOC/NOx ratios). Up to 102 mg of SOA mass was collected per experiment, allowing the use of highly accurate compositional and single particle analysis techniques which are not usually accessible, due to the large quantity of organic aerosol mass required for analysis. A suite of offline analytical techniques was used to determine the chemical composition and physical state of the generated SOA, including: attenuated total reflectance infra-red spectroscopy, CHNS elemental analyser, 1H and 1H-13C nuclear magnetic resonance spectroscopy (NMR), ultra-performance liquid chromatography ultra-high resolution mass spectrometry (UHRMS), high performance liquid chromatography ion-trap mass spectrometry (HPLC-ITMS) and an electrodynamic balance (EDB). The oxygen-to-carbon (O/C) and hydrogen-to-carbon (H/C) ratios of generated SOA samples (determined using a CHNS elemental analyser) displayed good agreement with literature values and were consistent with the characteristic Van Krevelen diagram trajectory, with an observed slope of -0.41. The elemental composition of two SOA samples formed in separate replicate experiments displayed excellent reproducibility, with the O/C and H/C ratios of the SOA samples observed to be within error of the analytical instrumentation (instrument accuracy ± 0.15 % to a reference standard). The ability to use a highly accurate CHNS elemental analyser to determine the elemental composition of the SOA samples, allowed us to evaluate the accuracy of reported SOA elemental compositions using UHRMS (a commonly used technique). In all of the experiments investigated, the SOA O/C ratios obtained for each SOA sample using UHRMS were lower than the O/C ratios obtained from the CHNS analyser (the more accurate and non-selective technique). The average difference in the ∆O/C ratios ranged from 19 to 45 % depending on the SOA precursor and formation conditions. α-pinene SOA standards were generated from the collected SOA mass using semi-preparative HPLC-ITMS coupled to an automated fraction collector, followed by 1H NMR spectroscopy. Up to 35.8 ± 1.6 % (propagated error of the uncertainty in the slope of the calibrations graphs) of α-pinene SOA was quantified using this method; a considerable improvement from most previous studies. Single aerosol droplets were generated from the collected SOA samples and trapped within an EDB at different temperatures and relative humidities to investigate the dynamic changes in their physiochemical properties. The volatilisation of organic components from toluene and β-caryophyllene SOA particles at 0 % relative humidity was found to be kinetically limited, owing to particle viscosity. The unconventional use of a newly-built CFR combined with comprehensive offline chemical characterisation and single particle measurements, offers a unique approach to further our understanding of the relationship/s between SOA formation conditions, chemical composition and physiochemical properties