Solubility and Activity Coefficients of Atmospheric Surfactants in Aqueous Solution Evaluated Using COSMOtherm

Fatty acids (CH3(CH2)(n-2)COOH) and their salts are an important class of atmospheric surfactants. Here, we use COSMOtherm to predict solubility and activity coefficients for C-2-C-12 fatty acids with even number of carbon atoms and their sodium salts in binary water solutions and also in ternary water-inorganic salt solutions. COSMOtherm is a continuum solvent model implementation which can calculate properties of complex systems using quantum chemistry and thermodynamics. Calculated solubility values of the organic acids in pure water are in good agreement with reported experimental values. The comparison of the COSMOtherm-derived Setschenow constants for ternary solutions comprising NaCl with the corresponding experimental values from the literature shows that COSMOtherm overpredicts the salting out effect in all cases except for the solutions of acetic acid. The calculated activity and mean activity coefficients of fatty acids and fatty acid sodium salts, respectively, show deviation of the systems from ideal solution. The computed mean activity coefficients of the fatty acid salts in binary systems are in better agreement with experimentally derived values for the organic salts with longer aliphatic chain (C-8-C-10). The deviation of the solutions from ideality could lead to biased estimations of cloud condensation nuclei number concentrations if not considered in Kohler calculations and cloud microphysics.Peer reviewe

Technical note : Estimating aqueous solubilities and activity coefficients of mono- and alpha,omega-dicarboxylic acids using COSMOtherm

We have used the COSMOtherm program to estimate activity coefficients and solubilities of mono- and alpha, omega-dicarboxylic acids and water in binary acid-water systems. The deviation from ideality was found to be larger in the systems containing larger acids than in the systems containing smaller acids. COnductor-like Screening MOdel for Real Solvents (COSMO-RS) underestimates experimental monocarboxylic acid activity coefficients by less than a factor of 2, but experimental water activity coefficients are underestimated more especially at high acid mole fractions. We found a better agreement between COSMOtherm-estimated and experimental activity coefficients of monocarboxylic acids when the water clustering with a carboxylic acid and itself was taken into account using the dimerization, aggregation, and reaction extension (COSMO-RS-DARE) of COSMOtherm. COSMO-RS-DARE is not fully predictive, but fit parameters found here for water-water and acid-water clustering interactions can be used to estimate thermodynamic properties of monocarboxylic acids in other aqueous solvents, such as salt solutions. For the dicarboxylic acids, COSMO-RS is sufficient for predicting aqueous solubility and activity coefficients, and no fitting to experimental values is needed. This is highly beneficial for applications to atmospheric systems, as these data are typically not available for a wide range of mixing states realized in the atmosphere, due to a lack of either feasibility of the experiments or sample availability. Based on effective equilibrium constants of different clustering reactions in the binary solutions, acid dimer formation is more dominant in systems containing larger dicarboxylic acids (C-5-C-8), while for monocarboxylic acids (C-1-C-6) and smaller dicarboxylic acids (C-2-C-4), hydrate formation is more favorable, especially in dilute solutions.Peer reviewe

Cloud condensation nuclei activity of six pollenkitts and the influence of their surface activity

The role of surfactants in governing water interactions of atmospheric aerosols has been a recurring topic in cloud microphysics for more than two decades. Studies of detailed surface thermodynamics are limited by the availability of aerosol samples for experimental analysis and incomplete validation of various proposed Köhler model frameworks for complex mixtures representative of atmospheric aerosol. Pollenkitt is a viscous material that coats grains of pollen and plays important roles in pollen dispersion and plant reproduction. Previous work suggests that it may also be an important contributor to pollen water uptake and cloud condensation nuclei (CCN) activity. The chemical composition of pollenkitt varies between species but has been found to comprise complex organic mixtures including oxygenated, lipid, and aliphatic functionalities. This mix of functionalities suggests that pollenkitt may display aqueous surface activity, which could significantly impact pollen interactions with atmospheric water. Here, we study the surface activity of pollenkitt from six different species and its influence on pollenkitt hygroscopicity. We measure cloud droplet activation and concentration-dependent surface tension of pollenkitt and its mixtures with ammonium sulfate salt. Experiments are compared to predictions from several thermodynamic models, taking aqueous surface tension reduction and surfactant surface partitioning into account in various ways. We find a clear reduction of surface tension by pollenkitt in aqueous solution and evidence for impact of both surface tension and surface partitioning mechanisms on cloud droplet activation potential and hygroscopicity of pollenkitt particles. In addition, we find indications of complex nonideal solution effects in a systematic and consistent dependency of pollenkitt hygroscopicity on particle size. The impact of pollenkitt surface activity on cloud microphysics is different from what is observed in previous work for simple atmospheric surfactants and more resembles recent observations for complex primary and secondary organic aerosol, adding new insight to our understanding of the multifaceted role of surfactants in governing aerosol–water interactions. We illustrate how the explicit characterization of pollenkitt contributions provides the basis for modeling water uptake and cloud formation of pollen and their fragments over a wide range of atmospheric conditions.</p

The analysis of size-segregated cloud condensation nuclei counter (CCNC) data and its implications for cloud droplet activation

Ambient aerosol, CCN (cloud condensation nuclei) and hygroscopic properties were measured with a size-segregated CCNC (cloud condensation nuclei counter) in a boreal environment of southern Finland at the SMEAR (Station for Measuring Ecosystem-Atmosphere Relations) II station. The instrumental setup operated at five levels of supersaturation <i>S</i> covering a range from 0.1–1% and measured particles with a size range of 20–300 nm; a total of 29 non-consecutive months of data are presented. The median critical diameter <i>D</i>_c ranged from 150 nm at <i>S</i> of 0.1% to 46 nm at <i>S</i> of 1.0%. The median aerosol hygroscopicity parameter &kappa; ranged from 0.41 at <i>S</i> of 0.1% to 0.14 at <i>S</i> of 1.0%, indicating that ambient aerosol in Hyytiälä is less hygroscopic than the global continental or European continental averages. It is, however, more hygroscopic than the ambient aerosol in an Amazon rainforest, a European high Alpine site or a forested mountainous site. A fairly low hygroscopicity in Hyytiälä is likely a result of a large organic fraction present in the aerosol mass comparative to other locations within Europe. A considerable difference in particle hygroscopicity was found between particles smaller and larger than ~100 nm in diameter, possibly pointing out to the effect of cloud processing increasing &kappa; of particles > 100 nm in diameter. The hygroscopicity of the smaller, ~50 nm particles did not change seasonally, whereas particles with a diameter of ~150 nm showed a decreased hygroscopicity in the summer, likely resulting from the increased VOC emissions of the surrounding boreal forest and secondary organic aerosol (SOA) formation. For the most part, no diurnal patterns of aerosol hygroscopic properties were found. Exceptions to this were the weak diurnal patterns of small, ~50 nm particles in the spring and summer, when a peak in hygroscopicity around noon was observed. No difference in CCN activation and hygroscopic properties was found on days with or without atmospheric new particle formation. During all seasons, except summer, a CCN-inactive fraction was found to be present, rendering the aerosol of 75–300 nm in diameter as internally mixed in the summer and not internally mixed for the rest of the year

Cloud condensation nuclei activity of six pollenkitts and the influence of their surface activity

The role of surfactants in governing water interactions of atmospheric aerosols has been a recurring topic in cloud microphysics for more than two decades. Studies of detailed surface thermodynamics are limited by the availability of aerosol samples for experimental analysis and incomplete validation of various proposed Kohler model frameworks for complex mixtures representative of atmospheric aerosol. Pollenkitt is a viscous material that coats grains of pollen and plays important roles in pollen dispersion and plant reproduction. Previous work suggests that it may also be an important contributor to pollen water uptake and cloud condensation nuclei (CCN) activity. The chemical composition of pollenkitt varies between species but has been found to comprise complex organic mixtures including oxygenated, lipid, and aliphatic functionalities. This mix of functionalities suggests that pollenkitt may display aqueous surface activity, which could significantly impact pollen interactions with atmospheric water. Here, we study the surface activity of pollenkitt from six different species and its influence on pollenkitt hygroscopicity. We measure cloud droplet activation and concentration-dependent surface tension of pollenkitt and its mixtures with ammonium sulfate salt. Experiments are compared to predictions from several thermodynamic models, taking aqueous surface tension reduction and surfactant surface partitioning into account in various ways. We find a clear reduction of surface tension by pollenkitt in aqueous solution and evidence for impact of both surface tension and surface partitioning mechanisms on cloud droplet activation potential and hygroscopicity of pollenkitt particles. In addition, we find indications of complex nonideal solution effects in a systematic and consistent dependency of pollenkitt hygroscopicity on particle size. The impact of pollenkitt surface activity on cloud microphysics is different from what is observed in previous work for simple atmospheric surfactants and more resembles recent observations for complex primary and secondary organic aerosol, adding new insight to our understanding of the multifaceted role of surfactants in governing aerosol-water interactions. We illustrate how the explicit characterization of pollenkitt contributions provides the basis for modeling water uptake and cloud formation of pollen and their fragments over a wide range of atmospheric conditions.Peer reviewe

Gas-to-Particle Partitioning of Cyclohexene- and alpha-Pinene-Derived Highly Oxygenated Dimers Evaluated Using COSMOtherm

Oxidized organic compounds are expected to contribute to secondary organic aerosol (SOA) if they have sufficiently low volatilities. We estimated saturation vapor pressures and activity coefficients (at infinite dilution in water and a model water-insoluble organic phase) of cyclohexene- and alpha-pinene-derived accretion products, "dimers", using the COSMOtherm19 program. We found that these two property estimates correlate with the number of hydrogen bond-donating functional groups and oxygen atoms in the compound. In contrast, when the number of H-bond donors is fixed, no clear differences are seen either between functional group types (e.g., OH or OOH as H-bond donors) or the formation mechanisms (e.g., gas-phase radical recombination vs liquid-phase closed-shell esterification). For the cyclohexene-derived dimers studied here, COSMOtherm19 predicts lower vapor pressures than the SIMPOL.1 group-contribution method in contrast to previous COSMOtherm estimates using older parameterizations and nonsystematic conformer sampling. The studied dimers can be classified as low, extremely low, or ultra-low-volatility organic compounds based on their estimated saturation mass concentrations. In the presence of aqueous and organic aerosol particles, all of the studied dimers are likely to partition into the particle phase and thereby contribute to SOA formation.Peer reviewe

Comparison of six approaches to predicting droplet activation of surface active aerosol – Part 2: Strong surfactants

Surfactants have been a focus of investigation in atmospheric sciences for decades due to their ability to modify the water uptake and cloud formation potential of aerosols. Surfactants adsorb at the surface and can decrease the surface tension of aqueous solutions. In microscopic aqueous droplets with finite amounts of solute, surface adsorption may simultaneously deplete the droplet bulk of the surfactant. While this mechanism is now broadly accepted, the representation in atmospheric and cloud droplet models is still not well constrained. We compare the predictions of five bulk–surface partitioning models documented in the literature to represent aerosol surface activity in Köhler calculations of cloud droplet activation. The models are applied to common aerosol systems, consisting of strong atmospheric surfactants (sodium myristate or myristic acid) and sodium chloride in a wide range of relative mixing ratios. For the same particles, the partitioning models predict similar critical droplet properties at small surfactant mass fractions, but differences between the model predictions increase significantly with the surfactant mass fraction in the particles. Furthermore, significantly different surface tensions are predicted for growing droplets at given ambient conditions along the Köhler curves. The inter-model variation for these strong surfactant particles is different than previously observed for moderately surface active atmospheric aerosol components. Our results highlight the importance of establishing bulk–surface partitioning effects in Köhler calculations for a wide range of conditions and aerosol types relevant to the atmosphere. In particular, conclusions made for a single type of surface active aerosol and surface activity model may not be immediately generalized.</p

Is Decreased Xylem Sap Surface Tension Associated With Embolism and Loss of Xylem Hydraulic Conductivity in Pathogen-Infected Norway Spruce Saplings?

Increased abiotic stress along with increasing temperatures, dry periods and forest disturbances may favor biotic stressors such as simultaneous invasion of bark beetle and ophiostomatoid fungi. It is not fully understood how tree desiccation is associated with colonization of sapwood by fungi. A decrease in xylem sap surface tension (sigma(xylem)) as a result of infection has been hypothesized to cause xylem embolism by lowering the threshold for air-seeding at the pits between conduits and disruptions in tree water transport. However, this hypothesis has not yet been tested. We investigated tree water relations by measuring the stem xylem hydraulic conductivity (K-stem), sigma(xylem), stem relative water content (RWCstem), and water potential (psi(stem)), and canopy conductance (g(canopy)), as well as the compound composition in xylem sap in Norway spruce (Picea abies) saplings. We conducted our measurements at the later stage ofEndoconidiophora polonicainfection when visible symptoms had occurred in xylem. Saplings of two clones (44 trees altogether) were allocated to treatments of inoculated, wounded control and intact control trees in a greenhouse. The saplings were destructively sampled every second week during summer 2016. sigma(xylem), K(stem)and RWC(stem)decreased following the inoculation, which may indicate that decreased sigma(xylem)resulted in increased embolism. g(canopy)did not differ between treatments indicating that stomata responded to psi(stem)rather than to embolism formation. Concentrations of quinic acid, myo-inositol, sucrose and alkylphenol increased in the xylem sap of inoculated trees. Myo-inositol concentrations also correlated negatively with sigma(xylem)and K-stem. Our study is a preliminary investigation of the role of sigma(xylem)inE. polonicainfected trees based on previous hypotheses. The results suggest thatE. polonicainfection can lead to a simultaneous decrease in xylem sap surface tension and a decline in tree hydraulic conductivity, thus hampering tree water transport.Peer reviewe