Partitioning Of Organic Compounds Research Articles

Saturation vapor pressure characterization of selected low-volatility organic compounds using a residence time chamber

Abstract. Saturation vapor pressure (psat) is an important thermodynamic property regulating the gas-to-particle partitioning of organic compounds in the atmosphere. Low-volatility organic compounds (LVOCs), with sufficiently low psat values, primarily stay in the particle phase and contribute to aerosol formation. Obtaining accurate information on the psat of LVOCs requires volatility measurements performed at temperatures relevant to atmospheric aerosol formation. Here, we present an isothermal evaporation method using a residence time chamber to measure psat for dry single-compound nanoparticles at 295 K. Our method is able to characterize organic compounds with psat spanning from 10−8 to 10−4 Pa at 295 K. The compounds included four polyethylene glycols (PEGs: PEG6, PEG7, PEG8, and PEG9), two monocarboxylic acids (palmitic acid and stearic acid), two dicarboxylic acids (azelaic acid and sebacic acid), two alcohols (meso-erythritol and xylitol), and one ester (di-2-ethylhexyl sebacate). There was a good agreement between our measured psat values and those reported by previous volatility studies using different measurement techniques, mostly within 1 order of magnitude. Additionally, quantum-chemistry-based COSMOtherm calculations were performed to estimate the psat values of the studied compounds. COSMOtherm predicted the psat values for most of the studied compounds within 1 order of magnitude difference between the experimental and computational estimates.

Real-time measurement of phase partitioning of organic compounds using a proton-transfer-reaction time-of-flight mass spectrometer coupled to a CHARON inlet

Abstract. Understanding the gas–particle partitioning of semivolatile organic compounds (SVOCs) is of crucial importance in the accurate representation of the global budget of atmospheric organic aerosols. In this study, we quantified the gas- vs. particle-phase fractions of a large number of SVOCs in real time in an urban area of East China with the use of a CHemical Analysis of aeRosols ONline (CHARON) inlet coupled to a high-resolution proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS). We demonstrated the use of the CHARON inlet for highly efficient collection of particulate SVOCs while maintaining the intact molecular structures of these compounds. The collected month-long dataset with hourly resolution allows us to examine the gas–particle partitioning of a variety of SVOCs under ambient conditions. By comparing the measurements with model predictions using instantaneous equilibrium partitioning theory, we found that the dissociation of large parent molecules during the PTR ionization process likely introduces large uncertainties to the measured gas- vs. particle-phase fractions of less oxidized SVOCs, and therefore, caution should be taken when linking the molecular composition to the particle volatility when interpreting the PTR-ToF-MS data. Our analysis suggests that understanding the fragmentation mechanism of SVOCs and accounting for the neutral losses of small moieties during the molecular feature extraction from the raw PTR mass spectra could reduce, to a large extent, the uncertainties associated with the gas–particle partitioning measurement of SVOCs in the ambient atmosphere.

Effective mass accommodation for partitioning of organic compounds into surface films with different viscosities.

Indoor surfaces can act as reservoirs and reaction media influencing the concentrations and type of species that people are exposed to indoors. Mass accommodation and partitioning are impacted by the phase state and viscosity of indoor surface films. We developed the kinetic multi-layer model KM-FILM to simulate organic film formation and growth, but it is computationally expensive to couple such comprehensive models with indoor air box models. Recently, a novel effective mass accommodation coefficient (αeff) was introduced for efficient and effective treatments of gas-particle partitioning. In this study, we extended this approach to a film geometry with αeff as a function of penetration depth into the film, partitioning coefficient, bulk diffusivity, and condensed-phase reaction rate constant. Comparisons between KM-FILM and the αeff method show excellent agreement under most conditions, but with deviations before the establishment of quasi-equilibrium within the penetration depth. We found that the deposition velocity of species and overall film growth are impacted by bulk diffusivity in highly viscous films (Db ∼<10-15 cm2 s-1). Reactions that lead to non-volatile products can increase film thicknesses significantly, with the extent of film growth being dependent on the gas-phase concentration, rate coefficient, partitioning coefficient and diffusivity. Amorphous semisolid films with Db > ∼10-17-10-19 cm2 s-1 can be efficient SVOC reservoirs for compounds with higher partitioning coefficients as they can be released back to the gas phase over extended periods of time, while glassy solid films would not be able to act as reservoirs as gas-film partitioning is impeded.

Abraham model correlations for describing the partition of organic compounds from water into the methyl ethyl ketone extraction solvent

ABSTRACT Experimental water-to-methyl ethyl ketone partition coefficients have been determined for 34 different organic solutes at ambient room temperature based on gas–liquid chromatographic measurements. Updated Abraham model correlations were determined for describing solute transfer into methyl ethyl ketone by combining the measured partition coefficient data determined in the present study with published experimental values taken from chemical and engineering literature. Experimental data for 48 compounds were used in determining the revised Abraham model correlations. The revised mathematical correlations were determined to back-calculate the observed partition coefficient data to within an overall average standard deviation of 0.17 log units or less. The partitioning characteristics of the water-to-methyl ethyl ketone system are compared to the characteristics of two other biphasic water-to-ketone partitioning systems.

Mass accommodation and gas–particle partitioning in secondary organic aerosols: dependence on diffusivity, volatility, particle-phase reactions, and penetration depth

Abstract. Mass accommodation is an essential process for gas–particle partitioning of organic compounds in secondary organic aerosols (SOA). The mass accommodation coefficient is commonly described as the probability of a gas molecule colliding with the surface to enter the particle phase. It is often applied, however, without specifying if and how deep a molecule has to penetrate beneath the surface to be regarded as being incorporated into the condensed phase (adsorption vs. absorption). While this aspect is usually not critical for liquid particles with rapid surface–bulk exchange, it can be important for viscous semi-solid or glassy solid particles to distinguish and resolve the kinetics of accommodation at the surface, transfer across the gas–particle interface, and further transport into the particle bulk. For this purpose, we introduce a novel parameter: an effective mass accommodation coefficient αeff that depends on penetration depth and is a function of surface accommodation coefficient, volatility, bulk diffusivity, and particle-phase reaction rate coefficient. Application of αeff in the traditional Fuchs–Sutugin approximation of mass-transport kinetics at the gas–particle interface yields SOA partitioning results that are consistent with a detailed kinetic multilayer model (kinetic multilayer model of gas–particle interactions in aerosols and clouds, KM-GAP; Shiraiwa et al., 2012) and two-film model solutions (Model for Simulating Aerosol Interactions and Chemistry, MOSAIC; Zaveri et al., 2014) but deviate substantially from earlier modeling approaches not considering the influence of penetration depth and related parameters. For highly viscous or semi-solid particles, we show that the effective mass accommodation coefficient remains similar to the surface accommodation coefficient in the case of low-volatility compounds, whereas it can decrease by several orders of magnitude in the case of semi-volatile compounds. Such effects can explain apparent inconsistencies between earlier studies deriving mass accommodation coefficients from experimental data or from molecular dynamics simulations. Our findings challenge the approach of traditional SOA models using the Fuchs–Sutugin approximation of mass transfer kinetics with a fixed mass accommodation coefficient, regardless of particle phase state and penetration depth. The effective mass accommodation coefficient introduced in this study provides an efficient new way of accounting for the influence of volatility, diffusivity, and particle-phase reactions on SOA partitioning in process models as well as in regional and global air quality models. While kinetic limitations may not be critical for partitioning into liquid SOA particles in the planetary boundary layer (PBL), the effects are likely important for amorphous semi-solid or glassy SOA in the free and upper troposphere (FT–UT) as well as in the PBL at low relative humidity and low temperature.

Modeling the Effects of Dimerization and Bulk Diffusion on the Evaporative Behavior of Secondary Organic Aerosol Formed from α-Pinene and 1,3,5-Trimethylbenzene

Author(s): Morino, Y; Sato, K; Jathar, SH; Tanabe, K; Inomata, S; Fujitani, Y; Ramasamy, S; Cappa, CD | Abstract: Volatility determines the gas-particle partitioning of organic compounds. Volatility is thus a key property needed to understand the behavior of organic aerosol (OA) in the atmosphere. Various studies have been conducted to experimentally measure and numerically simulate distributions of OA volatility. The observed OA evaporation rates have generally been slower than the rates assuming instantaneous gas-particle equilibrium and volatility estimated from secondary organic aerosol (SOA) formation experiments. Particle-phase diffusion and/or low-volatility compounds, such as oligomers and highly oxygenated molecules, could limit the evaporation of OA, though the relative contributions of these factors are still uncertain. In this study, we conducted model simulations using a volatility basis set framework with the consideration of kinetic gas-particle partitioning, formation and dissociation of dimers, and particle-phase diffusion to reproduce observed evaporative behaviors of SOA formed from α-pinene ozonolysis and 1,3,5-trimethylbenzene (TMB)/NOx photooxidation. Based on simulations constrained by various volatility distributions derived from chemical analysis or heating experiments, we found that both dimerization and slow particle-phase diffusion contributed to the observed slow evaporation under dry conditions. In contrast, particle-phase diffusion did not practically inhibit SOA evaporation under humid conditions. The similarity of the fitted parameters, including dimer formation/dissociation rates and bulk diffusivity, for SOA from α-pinene and 1,3,5-TMB under dry conditions suggested that these processes are important for both monoterpene and aromatic SOA. Evaporation rates of SOA from α-pinene in this study were slower than the rates reported in previous experimental studies. This difference could be partly explained by differences in the experimental setups, including the treatment of organic vapors.

Two-Phase System Model to Assess Hydrophobic Organic Compound Sorption to Dissolved Organic Matter.

The equilibrium partition of organic compounds to dissolved organic matter (DOM) is an essential process that affects their environmental risks. Traditional models cannot accurately assess this process as the variability of DOM is not properly accounted for. The two-phase system (TPS) model was developed with the consideration of the variability that stems from both organic compounds and DOM. In this study, we examined the applicability of the TPS model for the prediction of the organic carbon-water partition coefficient (KOC) of hydrophobic organic compound (HOC) sorption to aquatic and sediment DOM using a diverse set of 17 organic compounds and 53 DOM samples. The TPS model showed good predictive power (RMSE < 0.20) without calibration, outperforming currently used linear free energy relationship models (RMSE > 0.28). The significance of DOM properties in the sorption behavior was quantitatively analyzed based on the TPS model. The spatial pattern of KOC for HOC sorption to aquatic DOM in Lake Taihu, the third largest freshwater lake in China, was assessed using the TPS model. Our results suggest that the TPS model has great potential to facilitate the routine assessment of the partition behavior of HOCs in aquatic systems for environmental risk assessment.

Isotherm nonlinearity and nonlinear partitioning of organic compounds into resin XAD-7: Insight from displacement experiments

Nonlinear sorption and isotherm nonlinearity of organic compounds by widely used porous resins such as XAD-7 are commonly interpreted as adsorption due to their large surface area. However, through displacement experiments using saturated 4-nitrophenol as the displacer, we observed that the nonlinear sorption and isotherm nonlinearity of selected organic compounds (i.e., naphthalene, nitrobenzenes, phenols and anilines) by XAD-7 was captured by a nonlinear partition mechanism rather than the adsorption mechanism. Nonlinear sorption of organic compounds by XAD-7 includes a nonlinear/displaced fraction and a linear/non-displaced fraction. A dual-mode (DM) model, including a nonlinear Dubinin-Ashtakhov (DA) model component and a linear model component, was developed to describe the nonlinear/displaced fraction and the linear/non-displaced fraction, respectively. The capacity of these two fractions are dependent on their solubility in water or octanol with positively linear relationships but not their molecular size, supporting the nonlinear partitioning mechanism. Besides van-der-waals force, hydrogen-bonding is primarily responsible for the nonlinear partitioning of phenols and anilines into XAD-7, while π-π interaction is responsible for the nonlinear partitioning of naphthalene and nitrobenzenes. The explored nonlinear partitioning mechanism for XAD-7 implies that the nonlinear sorption of organic compounds by porous resins should be recognized for their recovery and applications as sorbents.

Mulitphase Atmospheric Chemistry in Liquid Water: Impacts and Controllability of Organic Aerosol.

Liquid water is a dominant and critical tropospheric constituent. Over polluted land masses low level cumulus clouds interact with boundary layer aerosol. The planetary boundary layer (PBL) is the lowest atmospheric layer and is directly influenced by Earth's surface. Water-aerosol interactions are critical to processes that govern the fate and transport of trace species in the Earth system and their impacts on air quality, radiative forcing, and regional hydrological cycling. In the PBL, air parcels rise adiabatically from the surface, and anthropogenically influenced hygroscopic aerosols take up water and serve as cloud condensation nuclei (CCN) to form clouds. Water-soluble gases partition to liquid water in wet aerosols and cloud droplets and undergo aqueous-phase photochemistry. Most cloud droplets evaporate, and low volatility material formed during aqueous phase chemistry remains in the condensed phase and adds to aerosol mass. The resulting cloud-processed aerosol has different physicochemical properties compared to the original CCN. Organic species that undergo multiphase chemistry in atmospheric liquid water transform gases to highly concentrated, nonideal ionic aqueous solutions and form secondary organic aerosol (SOA). In recent years, SOA formation modulated by atmospheric waters has received considerable interest.Key uncertainties are related to the chemical nature of hygroscopic aerosols that become CCN and their interaction with organic species. Gas-to-droplet or gas-to-aqueous aerosol partitioning of organic compounds is affected by the intrinsic chemical properties of the organic species in addition to the pre-existing condensed phase. Environmentally relevant conditions for atmospheric aerosol are nonideal. Salt identity and concentration, in addition to aerosol phase state, can dramatically affect organic gas miscibility for many compounds, in particular when ionic strength and salt molality are outside the bounds of limiting laws. For example, Henry's law and Debye-Hückel theory are valid only for dilute aqueous systems uncharacteristic of real atmospheric conditions. Chemical theory is incomplete, and at ambient conditions, this chemistry plays a determining role in total aerosol mass and particle size, controlling factors for air quality and climate-relevant aerosol properties.Accurate predictive skill to understand the impacts of societal choices and policies on air quality and climate requires that models contain correct chemical mechanisms and appropriate feedbacks. Globally, SOA is a dominant contributor to the atmospheric organic aerosol burden, and most mass can be traced back to precursor gas-phase volatile organic compounds (VOCs) emitted from the biosphere. However, organic aerosol concentrations in the Amazon Rainforest, the largest emitter of biogenic VOCs, are generally lower than in U.S. national parks. The Interagency Monitoring of Protected Visual Environments (IMPROVE) air quality network, with sites located predominantly in national parks, provides the longest continuous record of organic aerosol measurements in the U.S. Analysis of IMPROVE data provides a useful chemical climatology of changing air resources in response to environmental rules and shifting economic trends. IMPROVE data provides an excellent test bed for case studies to assess model skill to accurately predict changes in organic aerosol concentrations in the context of a changing climate.

The partition of organic compounds from water into the methyl isobutyl ketone extraction solvent with updated Abraham model equation

ABSTRACT Experimental water-to-methyl isobutyl ketone partition coefficients have been determined for 27 different organic solutes based on gas chromatographic measurements. Updated Abraham model correlations were determined for describing solute transfer into methyl isobutyl ketone by combining the measured partition coefficient data determined in the present study with published experimental values taken from chemical and engineering literature. One hundred nineteen compounds were used in determining the revised Abraham model correlations. After calculations, the revised mathematical correlations were found to match the experimental data to within an overall average standard deviation of 0.21 log units.

Prediction of Apolar Compound Sorption to Aquatic Natural Organic Matter Accounting for Natural Organic Matter Hydrophobicity Using Aqueous Two-Phase Systems.

The equilibrium partitioning of organic compounds to natural organic matter (NOM) plays a key role in their environmental fate as well as bioavailability. In this study, a prediction model for organic compound sorption to NOM was theoretically derived based on two-phase systems. In this model, the hydrophobicity of NOM was scaled by their partition coefficients in an aqueous two-phase system (KATPS) and that of organics was scaled by their octanol-water partition coefficients (KOW). The model uses only KATPS and KOW as variables. Coefficients in the model were determined using a data set including the organic carbon-water partition coefficient (KOC) of four polycyclic aromatic hydrocarbons (PAHs) sorption to 10 NOM samples collected from surface waters. The resulting model was validated using additional NOM samples and reference NOM, which suggested good prediction power for PAH sorption to aquatic NOM. The model performance was compared with commonly used linear free energy relationship models, and its applicability was discussed. Sorption behavior unexpected by this model is attributed to additional sorption mechanisms other than partitioning. Overall, this approach allows prediction of KOC for apolar organic compound sorption to aquatic NOM simply using their respective partition coefficients in two-phase systems based on a specific model.

Optical levitation measurement on hygroscopic behaviour and SVOC vapour pressure of single organic/inorganic aqueous aerosol

Quantifying the gas/particle partitioning of organic compounds is of great significance to the understanding of atmospheric aerosol indirect effect. Accurate determination of the hygroscopicities and vapour pressures of semi-volatile organic compounds (SVOC) is of crucial importance in studying their partitioning behaviour into atmospheric aerosol, as the influences on SVOCs evaporation from participation of inorganic species remains unclear. In this study we first present thermodynamic quantitative simulation and tweezed single particle measurement of hygroscopicity and volatility of single aerosol droplets. With thermodynamics simulation of the hygroscopicity, SVOC time dependent evaporation and potential chloride depletion reaction in a single trapped droplet, we illustrate influences from different process towards the trapped droplet. In optical tweezers measurement, the trapped droplet in the aerosol optical tweezers acts as a microcavity, which stimulates the cavity enhanced Raman spectroscopy (CERS) signal. Size and composition of the particle are calculated from Mie fit to the positions of the "whispering gallery modes" in the CERS fingerprint. Hygroscopic behaviours and SVOC saturated vapour pressure can then be extracted from the correlation between the changing droplet radius and solute concentration (derived from experimentally determined real part of refractive index (RI)) with good accuracy and reliability.

Predicting the Partitioning of Organic Compounds through Polymer Materials: Quantum Mechanical Applications

AbstractHazardous organic compounds can permeate gas pipelines and geomembranes made of organic polymer materials in landfills and leak into the surrounding environment, contaminating groundwater. ...

A reference data set for validating vapor pressure measurement techniques: homologous series of polyethylene glycols

Abstract. To predict atmospheric partitioning of organic compounds between gas and aerosol particle phase based on explicit models for gas phase chemistry, saturation vapor pressures of the compounds need to be estimated. Estimation methods based on functional group contributions require training sets of compounds with well-established saturation vapor pressures. However, vapor pressures of semivolatile and low-volatility organic molecules at atmospheric temperatures reported in the literature often differ by several orders of magnitude between measurement techniques. These discrepancies exceed the stated uncertainty of each technique which is generally reported to be smaller than a factor of 2. At present, there is no general reference technique for measuring saturation vapor pressures of atmospherically relevant compounds with low vapor pressures at atmospheric temperatures. To address this problem, we measured vapor pressures with different techniques over a wide temperature range for intercomparison and to establish a reliable training set. We determined saturation vapor pressures for the homologous series of polyethylene glycols (H − (O − CH2 − CH2)n − OH) for n = 3 to n = 8 ranging in vapor pressure at 298 K from 10−7 to 5×10−2 Pa and compare them with quantum chemistry calculations. Such a homologous series provides a reference set that covers several orders of magnitude in saturation vapor pressure, allowing a critical assessment of the lower limits of detection of vapor pressures for the different techniques as well as permitting the identification of potential sources of systematic error. Also, internal consistency within the series allows outlying data to be rejected more easily. Most of the measured vapor pressures agreed within the stated uncertainty range. Deviations mostly occurred for vapor pressure values approaching the lower detection limit of a technique. The good agreement between the measurement techniques (some of which are sensitive to the mass accommodation coefficient and some not) suggests that the mass accommodation coefficients of the studied compounds are close to unity. The quantum chemistry calculations were about 1 order of magnitude higher than the measurements. We find that extrapolation of vapor pressures from elevated to atmospheric temperatures is permissible over a range of about 100 K for these compounds, suggesting that measurements should be performed best at temperatures yielding the highest-accuracy data, allowing subsequent extrapolation to atmospheric temperatures.

Effects of gas–wall partitioning in Teflon tubing and instrumentation on time-resolved measurements of gas-phase organic compounds

Abstract. Recent studies have demonstrated that organic compounds can partition from the gas phase to the walls in Teflon environmental chambers and that the process can be modeled as absorptive partitioning. Here these studies were extended to investigate gas–wall partitioning of organic compounds in Teflon tubing and inside a proton-transfer-reaction mass spectrometer (PTR-MS) used to monitor compound concentrations. Rapid partitioning of C8–C14 2-ketones and C11–C16 1-alkenes was observed for compounds with saturation concentrations (c∗) in the range of 3 × 104 to 1 × 107 µg m−3, causing delays in instrument response to step-function changes in the concentration of compounds being measured. These delays vary proportionally with tubing length and diameter and inversely with flow rate and c∗. The gas–wall partitioning process that occurs in tubing is similar to what occurs in a gas chromatography column, and the measured delay times (analogous to retention times) were accurately described using a linear chromatography model where the walls were treated as an equivalent absorbing mass that is consistent with values determined for Teflon environmental chambers. The effect of PTR-MS surfaces on delay times was also quantified and incorporated into the model. The model predicts delays of an hour or more for semivolatile compounds measured under commonly employed conditions. These results and the model can enable better quantitative design of sampling systems, in particular when fast response is needed, such as for rapid transients, aircraft, or eddy covariance measurements. They may also allow estimation of c∗ values for unidentified organic compounds detected by mass spectrometry and could be employed to introduce differences in time series of compounds for use with factor analysis methods. Best practices are suggested for sampling organic compounds through Teflon tubing.

Equilibrium partitioning of organic compounds to OASIS HLB® as a function of compound concentration, pH, temperature and salinity

Oasis hydrophilic lipophilic balance® (Oasis HLB) is commonly employed in solid phase extraction (SPE) of environmental contaminants and within polar organic chemical integrative passive samplers (POCIS). In this study batch experiments were carried out to evaluate the relative affinity of a range of relevant organic pollutants to Oasis HLB in aqueous systems. The influence of sorbate concentration, temperature, pH, and salinity on the equilibrium sorption was investigated. Equilibrium partition ratios (KD) of 28 compounds were determined, ranging over three orders of magnitude from 1.16 × 103 L/kg (atenolol) to 1.07 × 106 L/kg (isoproturon). The Freundlich model was able to describe the equilibrium partitioning to Oasis HLB, and an analysis of the thermodynamic parameters revealed the spontaneous and exothermic nature of the partitioning process. Ionic strength had only a minor effect on the partitioning, whereas pH had a considerable effect but only for ionizable compounds. The results show that apolar interactions between the Oasis HLB and analyte mainly determine the equilibrium partitioning. These research findings can be used to optimize the application of SPE and POCIS for analyses of environmental contaminants even in complex mixtures.

Effect of Sodium Sulfate, Ammonium Chloride, Ammonium Nitrate, and Salt Mixtures on Aqueous Phase Partitioning of Organic Compounds.

Dissolved inorganic salts influence the partitioning of organic compounds into the aqueous phase. This influence is especially significant in atmospheric aerosol, which usually contains large amounts of ions, including sodium, ammonium, chloride, sulfate, and nitrate. However, empirical data on this salt effect are very sparse. Here, the partitioning of numerous organic compounds into solutions of Na2SO4, NH4Cl, and NH4NO3 was measured and compared with existing data for NaCl and (NH4)2SO4. Salt mixtures were also tested to establish whether the salt effect is additive. In general, the salt effect showed a decreasing trend of Na2SO4 > (NH)2SO4 > NaCl > NH4Cl > NH4NO3 for the studied organic compounds, implying the following relative strength of the salt effect of individual anions: SO42- > Cl- > NO3- and of cations: Na+ > NH4+. The salt effect of different salts is moderately correlated. Predictive models for the salt effect were developed based on the experimental data. The experimental data indicate that the salt effect of mixtures may not be entirely additive. However, the deviation from additivity, if it exists, is small. Data of very high quality are required to establish whether the effect of constituent ions or salts is additive or not.

Particulate matter and black carbon optical properties and emission factors from prescribed fires in the southeastern United States

AbstractAerosol optical properties of biomass burning emissions are critical parameters determining how these emissions impact the Earth's climate. Despite their importance, field measurements of aerosol optical properties from fires remain scarce. Aerosol emissions from prescribed fires of forested and grass plots in the southeastern United States were measured and compared to emissions from laboratory simulations. Fine particulate matter (PM2.5), black carbon (BC), and aerosol light scattering and absorption were characterized for all fires. Refractory BC emission factors (EFs) measured at ground level (~2 m) were 0.76 ± 0.15 g/kg, comparable to the 0.93 ± 0.32 g/kg measured aloft (~100–600 m). However, PM EFs measured by aircraft were only 18% (5.4 ± 2.0 g/kg) of those measured on the ground (28.8 ± 9.8 g/kg). Such large differences in PM EFs for the same fire have not been previously reported and may plausibly be due to the differing particle measurement methodologies being applied but also likely related to partitioning of organic compounds to the gas phase as the plume dilutes aloft. Higher PM EFs on the ground may also be related to a higher contribution from smoldering combustion. The absorption Ångström exponents (αa) for the high intensity South Carolina fires were 3.92 ± 0.6, which was larger than prescribed forest fire in Florida (2.84) and the grass fire in Florida (2.71), implying a larger absorption contribution from brown carbon from higher‐intensity fires. Aerosol optical properties from laboratory simulations did not represent field measurements.

Analysis of partitioning of organic compounds and proteins in aqueous polyethylene glycol-sodium sulfate aqueous two-phase systems in terms of solute–solvent interactions

Partition behavior of nine small organic compounds and six proteins was examined in poly(ethylene glycol)-8000-sodium sulfate aqueous two-phase systems containing 0.5M osmolyte (sorbitol, sucrose, trehalose, TMAO) and poly(ethylene glycol)-10000-sodium sulfate system, all in 0.01M sodium phosphate buffer, pH 6.8. The differences between the solvent properties of the coexisting phases (solvent dipolarity/polarizability, hydrogen bond donor acidity, and hydrogen bond acceptor basicity) were characterized with solvatochromic dyes using the solvatochromic comparison method. Differences between the electrostatic properties of the phases were determined by analysis of partitioning of sodium salts of dinitrophenylated (DNP-) amino acids with aliphatic alkyl side-chain. It was found out that the partition coefficient of all compounds examined (including proteins) may be described in terms of solute–solvent interactions. The results obtained in the study show that solute–solvent interactions of nonionic organic compounds and proteins in polyethylene glycol-sodium sulfate aqueous two-phase system differ from those in polyethylene glycol-dextran system.

Calculating Equilibrium Phase Distribution during the Formation of Secondary Organic Aerosol Using COSMOtherm.

Challenges in the parametrization of compound distribution between the gas and particle phase contribute significantly to the uncertainty in the prediction of secondary organic aerosol (SOA) formation and are rooted in the complexity and variability of atmospheric condensed matter, which includes water, salts, and a multitude of organic oxidation products, often in two separated phases. Here, we explore the use of the commercial quantum-chemistry-based software COSMOtherm to predict equilibrium partitioning and Setchenow coefficients of a suite of oxidation products of α-pinene ozonolysis in an aerosol that is assumed to separate into an organic-enriched phase and an electrolyte-enriched aqueous phase. The predicted coefficients are used to estimate the phase distribution of the organic compounds, water and ammonium sulfate, the resulting phase composition, and the SOA yield. Four scenarios that differ in terms of organic loading, liquid water content, and chemical aging are compared. The organic compounds partition preferentially to the organic phase rather than the aqueous phase for the studied aerosol scenarios, partially due to the salting-out effect. Extremely low volatile organic compounds are predicted to be the dominant species in the organic aerosols at low loadings and an important component at higher loadings. The highest concentration of oxidation products in the condensed phase is predicted for a scenario assuming the presence of non-phase-separated cloud droplets. Partitioning into an organic aerosol phase composed of the oxidation products is predicted to be similar to partitioning into a phase composed of a single organic surrogate molecule, suggesting that the calculation procedure can be simplified without major loss of accuracy. COSMOtherm is shown to produce results that are comparable to those obtained using group contribution methods. COSMOtherm is likely to have a much larger application domain than those group contribution methods because it is based on fundamental principles with little calibration.