78 results on '"Nønne L, Prisle"'
Search Results
2. Inversion model for extracting chemically resolved depth profiles across liquid interfaces of various configurations from XPS data: PROPHESY
- Author
-
Matthew Ozon, Konstantin Tumashevich, Jack J. Lin, and Nønne L. Prisle
- Subjects
x-ray photoelectron spectroscopy ,depth profile ,inversion algorithm ,atmospheric surfaces ,acquisition model ,Nuclear and particle physics. Atomic energy. Radioactivity ,QC770-798 ,Crystallography ,QD901-999 - Abstract
PROPHESY, a technique for the reconstruction of surface-depth profiles from X-ray photoelectron spectroscopy data, is introduced. The inversion methodology is based on a Bayesian framework and primal-dual convex optimization. The acquisition model is developed for several geometries representing different sample types: plane (bulk sample), cylinder (liquid microjet) and sphere (droplet). The methodology is tested and characterized with respect to simulated data as a proof of concept. Possible limitations of the method due to uncertainty in the attenuation length of the photo-emitted electron are illustrated.
- Published
- 2023
- Full Text
- View/download PDF
3. Quantitative alignment parameter estimation for analyzing X-ray photoelectron spectra
- Author
-
Matthew Ozon, Konstantin Tumashevich, and Nønne L. Prisle
- Subjects
x-ray photoelectron spectroscopy ,experimental alignment parameter ,measurement model ,liquid jet ,quantitative data inversion ,Nuclear and particle physics. Atomic energy. Radioactivity ,QC770-798 ,Crystallography ,QD901-999 - Abstract
The interpretation of X-ray photoelectron spectroscopy (XPS) data relies on measurement models that depend on several parameters, including the photoelectron attenuation length and X-ray photon flux. However, some of these parameters are not known, because they are not or cannot be measured. The unknown geometrical parameters can be lumped together in a multiplicative factor, the alignment parameter. This parameter characterizes the ability of the exciting light to interact with the sample. Unfortunately, the absolute value of the alignment parameter cannot be measured directly, in part because it depends on the measurement model. Instead, a proxy for the experimental alignment is often estimated, which is closely related to the alignment parameter. Here, a method for estimating the absolute value of the alignment parameter based on the raw XPS spectra (i.e. non-processed photoelectron counts), the geometry of the sample and the photoelectron attenuation length is presented. The proposed parameter estimation method enables the quantitative analysis of XPS spectra using a simplified measurement model. All computations can be executed within the open and free Julia language framework PROPHESY. To demonstrate feasibility, the alignment parameter estimation method is first tested on simulated data with known acquisition parameters. The method is then applied to experimental XPS data and a strong correlation between the estimated alignment parameter and the typically used alignment proxy is shown.
- Published
- 2023
- Full Text
- View/download PDF
4. Ultrafast diffusion exchange nuclear magnetic resonance
- Author
-
Otto Mankinen, Vladimir V. Zhivonitko, Anne Selent, Sarah Mailhiot, Sanna Komulainen, Nønne L. Prisle, Susanna Ahola, and Ville-Veikko Telkki
- Subjects
Science - Abstract
Analysis of exchange processes is time consuming by two-dimensional exchange NMR spectroscopy. Here the authors demonstrate a single-scan ultrafast Laplace NMR approach based on spatial encoding to measure molecular diffusion, with an increase by a factor six in the sensitivity per unit time.
- Published
- 2020
- Full Text
- View/download PDF
5. Is Decreased Xylem Sap Surface Tension Associated With Embolism and Loss of Xylem Hydraulic Conductivity in Pathogen-Infected Norway Spruce Saplings?
- Author
-
Teemu Paljakka, Kaisa Rissanen, Anni Vanhatalo, Yann Salmon, Tuula Jyske, Nønne L. Prisle, Riikka Linnakoski, Jack J. Lin, Tapio Laakso, Risto Kasanen, Jaana Bäck, and Teemu Hölttä
- Subjects
embolism ,Endoconidiophora polonica ,hydraulic conductivity ,Picea abies (Norway spruce) ,plant-pathogen interactions ,surface tension ,Plant culture ,SB1-1110 - Abstract
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 (σxylem) 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 (Kstem), σxylem, stem relative water content (RWCstem), and water potential (Ψstem), and canopy conductance (gcanopy), as well as the compound composition in xylem sap in Norway spruce (Picea abies) saplings. We conducted our measurements at the later stage of Endoconidiophora polonica infection 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. σxylem, Kstem and RWCstem decreased following the inoculation, which may indicate that decreased σxylem resulted in increased embolism. gcanopy did not differ between treatments indicating that stomata responded to Ψstem 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 σxylem and Kstem. Our study is a preliminary investigation of the role of σxylem in E. polonica infected trees based on previous hypotheses. The results suggest that E. polonica infection can lead to a simultaneous decrease in xylem sap surface tension and a decline in tree hydraulic conductivity, thus hampering tree water transport.
- Published
- 2020
- Full Text
- View/download PDF
6. A continuous flow diffusion chamber study of sea salt particles acting as cloud nuclei: deliquescence and ice nucleation
- Author
-
Xiangrui Kong, Martin J. Wolf, Michael Roesch, Erik S. Thomson, Thorsten Bartels-Rausch, Peter A. Alpert, Markus Ammann, Nønne L. Prisle, and Daniel J. Cziczo
- Subjects
sea salt ,deliquescence ,homogeneous ice nucleation ,heterogeneous ice nucleation ,continuous flow diffusion chamber ,Meteorology. Climatology ,QC851-999 - Abstract
Phase changes of sea salt particles alter their physical and chemical properties, which is significant for Earth’s chemistry and energy budget. In this study, a continuous flow diffusion chamber is used to investigate deliquescence, homogeneous and heterogeneous ice nucleation between 242 K and 215 K, of four salts: pure NaCl, pure MgCl2, synthetic sea water salt, and salt distilled from sampled sea water. Anhydrous particles, aqueous droplets and ice particles were discriminated using a polarisation-sensitive optical particle counter coupled with a machine learning analysis technique. The measured onset deliquescence relative humidities agree with previous studies, where sea water salts deliquescence at lower humidities than pure NaCl. Deliquesced salt droplets homogenously freeze when the relative humidity reaches a sufficiently high value at temperatures below 233 K. From 224 K and below, deposition nucleation freezing on a fraction of NaCl particles was observed at humidities lower than the deliquescence relative humidity. At these low temperatures, otherwise unactivated salt particles deliquesced at the expected deliquescence point, followed by homogeneous freezing at temperatures as low as 215 K. Thus, the observed sea salt particles exhibit a triad of temperature-dependent behaviours. First, they act as cloud condensation particles (CCNs) > 233 K, second they can be homogeneous freezing nuclei (HFNs) < 233 K and finally they act as ice nucleating particles (INPs) for heterogeneous nucleation
- Published
- 2018
- Full Text
- View/download PDF
7. Supplementary material to 'Comparison of six approaches to predicting droplet activation of surface active aerosol – Part 2: strong surfactants'
- Author
-
Sampo Vepsäläinen, Silvia M. Calderón, and Nønne L. Prisle
- Published
- 2023
8. Impact of Tetrabutylammonium on the Oxidation of Bromide by Ozone
- Author
-
Jacinta Edebeli, Huanyu Yang, Xiangrui Kong, Markus Ammann, Fabrizio Orlando, Shuzhen Chen, Luca Artiglia, Anthony Boucly, Nønne L. Prisle, and Pablo Corral Arroyo
- Subjects
X-ray photoelectron spectroscopy ,Atmospheric Science ,Ozone ,tetrabutylammonium ,Inorganic chemistry ,02 engineering and technology ,Reaction intermediate ,010402 general chemistry ,01 natural sciences ,Chloride ,Article ,Tetrabutylammonium ,Bromide ,Surface propensity ,Ion-pairs ,Liquid jet ,Halogen chemistry ,chemistry.chemical_compound ,Pulmonary surfactant ,Geochemistry and Petrology ,medicine ,halogen chemistry ,Ozonide ,Reactivity (chemistry) ,liquid jet ,ion-pairs ,bromide ,Aqueous solution ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,ozone ,chemistry ,13. Climate action ,Space and Planetary Science ,0210 nano-technology ,surface propensity ,medicine.drug - Abstract
The reaction of ozone with sea-salt derived bromide is relevant for marine boundary layer atmospheric chemistry. The oxidation of bromide by ozone is enhanced at aqueous interfaces. Ocean surface water and sea spray aerosol are enriched in organic compounds, which may also have a significant effect on this reaction at the interface. Here, we assess the surface propensity of cationic tetrabutylammonium at the aqueous liquid-vapor interface by liquid microjet X-ray photoelectron spectroscopy (XPS) and the effect of this surfactant on ozone uptake to aqueous bromide solutions. The results clearly indicate that the positively charged nitrogen group in tetrabutylammonium (TBA), along with its surface activity, leads to an enhanced interfacial concentration of both bromide and the bromide ozonide reaction intermediate. In parallel, off-line kinetic experiments for the same system demonstrate a strongly enhanced ozone loss rate in the presence of TBA, which is attributed to an enhanced surface reaction rate. We used liquid jet XPS to obtain detailed chemical composition information from the aqueous-solution-vapor interface of mixed aqueous solutions containing bromide or bromide and chloride with and without TBA surfactant. Core level spectra of Br 3d, C 1s, Cl 2p, N 1s, and O 1s were used for this comparison. A model was developed to account for the attenuation of photoelectrons by the carbon-rich layer established by the TBA surfactant. We observed that the interfacial density of bromide is increased by an order of magnitude in solutions with TBA. The salting-out of TBA in the presence of 0.55 M sodium chloride is apparent. The increased interfacial bromide density can be rationalized by the association constants for bromide and chloride to form ion-pairs with TBA. Still, the interfacial reactivity is not increasing simply proportionally with the increasing interfacial bromide concentration in response to the presence of TBA. The steady state concentration of the bromide ozonide intermediate increases by a smaller degree, and the lifetime of the intermediate is 1 order of magnitude longer in the presence of TBA. Thus, the influence of cationic surfactants on the reactivity of bromide depends on the details of the complex environment at the interface. ISSN:2472-3452
- Published
- 2021
9. Correction to 'Missed Evaporation from Atmospherically Relevant Inorganic Mixtures Confounds Experimental Aerosol Studies'
- Author
-
Jenny Rissler, Calle Preger, Axel C. Eriksson, Jack J. Lin, Nønne L. Prisle, and Birgitta Svenningsson
- Subjects
Environmental Chemistry ,General Chemistry - Published
- 2023
10. Adsorptive uptake of water by semisolid secondary organic aerosols
- Author
-
Aki Pajunoja, Andrew T. Lambe, Jani Hakala, Narges Rastak, Molly J. Cummings, James F. Brogan, Liqing Hao, Mikhail Paramonov, Juan Hong, Nønne L. Prisle, Jussi Malila, Sami Romakkaniemi, Kari E. J. Lehtinen, Ari Laaksonen, Markku Kulmala, Paola Massoli, Timothy B. Onasch, Neil M. Donahue, Ilona Riipinen, Paul Davidovits, Douglas R. Worsnop, Tuukka Petäjä, and Annele Virtanen
- Published
- 2015
- Full Text
- View/download PDF
11. Technical note: Estimating aqueous solubilities and activity coefficients of mono- and α,ω-dicarboxylic acids using COSMOtherm
- Author
-
Reyhaneh Heshmatnezhad, Noora Hyttinen, Nønne L. Prisle, Jonas Elm, and Theo Kurtén
- Subjects
Activity coefficient ,chemistry.chemical_classification ,Atmospheric Science ,Aqueous solution ,010504 meteorology & atmospheric sciences ,Carboxylic acid ,Dimer ,Oxalic acid ,Technical note ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences ,chemistry.chemical_compound ,COSMO-RS ,chemistry ,13. Climate action ,Computational chemistry ,Equilibrium constant ,0105 earth and related environmental sciences - Abstract
We have used the COSMOtherm program to estimate activity coefficients and solubilities of mono- and α,ω-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 (C5–C8), while for monocarboxylic acids (C1–C6) and smaller dicarboxylic acids (C2–C4), hydrate formation is more favorable, especially in dilute solutions.
- Published
- 2020
12. Model for estimating activity coefficients in binary and ternary ionic surfactant solutions
- Author
-
Jussi Malila, Nønne L. Prisle, and Silvia M. Calderón
- Subjects
Activity coefficient ,chemistry.chemical_classification ,Atmospheric Science ,Aqueous solution ,Materials science ,010504 meteorology & atmospheric sciences ,Ionic bonding ,Thermodynamics ,Electrolyte ,010501 environmental sciences ,01 natural sciences ,chemistry ,Pulmonary surfactant ,Critical micelle concentration ,Environmental Chemistry ,Counterion ,Ternary operation ,0105 earth and related environmental sciences - Abstract
We introduce the CMC based Ionic Surfactant Activity model (CISA) to calculate activity coefficients in ternary aqueous solutions of an ionic surfactant and an inorganic salt. The surfactant can be either anionic or cationic and in the present development, the surfactant and inorganic salts share a common counterion. CISA incorporates micellization into the Pitzer–Debye–Hückel (PDH) framework for activities of mixed electrolyte solutions. To reduce computing requirements, a parametrization of the critical micelle concentration (CMC) is used to estimate the degree of micellization instead of explicit equilibrium calculations. For both binary and ternary systems, CISA only requires binary experimentally-based parameters to describe water–ion interactions and temperature–composition dependency of the CMC. The CISA model is intended in particular for atmospheric applications, where higher-order solution interaction parameters are typically not constrained by experiments and the description must be reliable across a wide range of compositions. We evaluate the model against experimental activity data for binary aqueous solutions of ionic surfactants sodium octanoate and sodium decanoate, as common components of atmospheric aerosols, and sodium dodecylsulfate, the most commonly used model compound for atmospheric surfactants. Capabilities of the CISA model to describe ternary systems are tested for the water–sodium decanoate–sodium chloride system, a common surrogate for marine background cloud condensation nuclei and to our knowledge the only atmospherically relevant system for which ternary activity data is available. For these systems, CISA is able to provide continuous predictions of activity coefficients both below and above CMC and in all cases gives an improved description of the water activity above the CMC, compared to the alternative model of Burchfield and Wolley [J. Phys. Chem., 88(10), 2149–2155 (1984)]. The water activity is a key parameter governing the formation and equilibrium growth of cloud droplets. The CISA model can be extended from the current form to include the effect of other inorganic salts with the existing database of binary PDH parameters and using appropriate mixing rules to account for ion specificity in the micellization process.
- Published
- 2020
13. Improving Solubility and Activity Estimates of Multifunctional Atmospheric Organics by Selecting Conformers in COSMOtherm
- Author
-
Nønne L. Prisle and Noora Hyttinen
- Subjects
Activity coefficient ,Aqueous solution ,010304 chemical physics ,Chemistry ,010402 general chemistry ,01 natural sciences ,Article ,0104 chemical sciences ,13. Climate action ,Computational chemistry ,0103 physical sciences ,Physical and Theoretical Chemistry ,Solubility ,Conformational isomerism - Abstract
We estimated aqueous solubilities and activity coefficients of atmospherically relevant highly oxidized multifunctional organic compounds in binary mixtures with water at temperatures between 278.15 and 338.15 K, using the COSMOtherm program. Physicochemical properties of organic aerosol constituents are needed in the modeling of atmospheric aerosol processes. As experimental data are often impossible to obtain, reliable estimates from theoretical approaches are a promising path to fill this gap. We investigated the effect of intramolecular hydrogen bonds on the estimation of these condensed-phase properties, attempting to improve the agreement between experimental and estimated values. Citric, tartaric, malic, and maleic acids, which are often used in atmospheric models as representatives of oxidized compounds, were selected to benchmark our calculations. In addition, we estimated aqueous solubilities and activity coefficients of α-pinene-derived organosulfates and highly oxidized isoprene-derived organic compounds, for which no experimental data are available. Our results indicate that the absolute aqueous solubility and activity coefficient estimates of citric, tartaric, malic, and maleic acids, and likely other multifunctional organics, can be improved significantly by selecting conformers on the basis of their intramolecular hydrogen bonding in COSMOtherm calculations.
- Published
- 2020
14. The surface tension of surfactant-containing, finite volume droplets
- Author
-
Bryan R. Bzdek, Jonathan P. Reid, Nønne L. Prisle, and Jussi Malila
- Subjects
Materials science ,cloud droplet number concentration ,010504 meteorology & atmospheric sciences ,aerosol ,surfactant ,010402 general chemistry ,01 natural sciences ,complex mixtures ,Surface tension ,Reaction rate ,Physics::Fluid Dynamics ,Pulmonary surfactant ,surface tension ,Cloud condensation nuclei ,Köhler 16 equation ,Physics::Atmospheric and Oceanic Physics ,0105 earth and related environmental sciences ,Supersaturation ,Multidisciplinary ,Finite volume method ,0104 chemical sciences ,Aerosol ,Chemistry ,cloud condensation nuclei ,13. Climate action ,Chemical physics ,Physical Sciences ,Particle - Abstract
Significance Atmospheric aerosol particles cool Earth’s climate by serving as cloud droplet seeds. This cooling effect represents both the single most uncertain and the largest negative radiative forcing. Cloud droplet activation is strongly influenced by aerosol particle surface tension, which in climate models is assumed equivalent to that of pure water. We directly measure the surface tensions of surfactant-coated, high surface-to-volume ratio droplets, demonstrating that their surface tensions are significantly lower than pure water but do not match the surface tension of the solution from which they were produced and depend on finite droplet size. These results suggest surfactants could potentially significantly modify radiative forcing and highlight the need for a better understanding of atmospheric surfactant concentrations and properties., Surface tension influences the fraction of atmospheric particles that become cloud droplets. Although surfactants are an important component of aerosol mass, the surface tension of activating aerosol particles is still unresolved, with most climate models assuming activating particles have a surface tension equal to that of water. By studying picoliter droplet coalescence, we demonstrate that surfactants can significantly reduce the surface tension of finite-sized droplets below the value for water, consistent with recent field measurements. Significantly, this surface tension reduction is droplet size-dependent and does not correspond exactly to the macroscopic solution value. A fully independent monolayer partitioning model confirms the observed finite-size-dependent surface tension arises from the high surface-to-volume ratio in finite-sized droplets and enables predictions of aerosol hygroscopic growth. This model, constrained by the laboratory measurements, is consistent with a reduction in critical supersaturation for activation, potentially substantially increasing cloud droplet number concentration and modifying radiative cooling relative to current estimates assuming a water surface tension. The results highlight the need for improved constraints on the identities, properties, and concentrations of atmospheric aerosol surfactants in multiple environments and are broadly applicable to any discipline where finite volume effects are operative, such as studies of the competition between reaction rates within the bulk and at the surface of confined volumes and explorations of the influence of surfactants on dried particle morphology from spray driers.
- Published
- 2020
15. Solubility and Activity Coefficients of Atmospheric Surfactants in Aqueous Solution Evaluated Using COSMOtherm
- Author
-
Theo Kurtén, Noora Hyttinen, Georgia Michailoudi, Nønne L. Prisle, Department of Chemistry, and Institute for Atmospheric and Earth System Research (INAR)
- Subjects
Activity coefficient ,ORGANIC FILMS ,DROPLET ACTIVATION ,Inorganic chemistry ,Sodium decanoate ,010402 general chemistry ,114 Physical sciences ,01 natural sciences ,CLOUD CONDENSATION NUCLEI ,chemistry.chemical_compound ,0103 physical sciences ,PARTICLES ,Cloud condensation nuclei ,Physical and Theoretical Chemistry ,Solubility ,Sulfate ,Aqueous solution ,010304 chemical physics ,Chemistry ,AEROSOL ,0104 chemical sciences ,Aerosol ,MODEL ,VAPOR-PRESSURES ,13. Climate action ,SODIUM DECANOATE ,lipids (amino acids, peptides, and proteins) ,FATTY-ACIDS ,SULFATE - Abstract
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.
- Published
- 2019
16. Droplet activation of moderately surface active organic aerosol predicted with six approaches to surface activity
- Author
-
Sampo Vepsäläinen, Nønne L. Prisle, Jussi Malila, and Silvia M. Calderón
- Subjects
Surface tension ,Supersaturation ,Range (particle radiation) ,Adsorption ,Pulmonary surfactant ,13. Climate action ,Chemical physics ,Chemistry ,Particle size ,complex mixtures ,Mass fraction ,Aerosol - Abstract
Surface active compounds (surfactants) found in atmospheric aerosols can decrease droplet surface tension as they adsorb to the droplet surfaces simultaneously depleting the droplet bulk. These processes may influence the activation properties of aerosols into cloud droplets and investigation of their role in cloud microphysics has been ongoing for decades. In this study, we have used six different approaches documented in the literature to represent surface activity in Köhler calculations predicting cloud droplet activation properties for particles consisting of one of three different moderately surface active organics mixed with ammonium sulphate in different ratios. We find that the different models predict comparable activation properties at small organic mass fractions in the dry particles for all three moderately surface active organics tested, even with large differences in the predicted degree of bulk-to-surface partitioning of the surface active component. However, differences between the models regarding both the predicted critical diameter and supersaturation for the same dry particle size increase with the organic fraction in the particles. Comparison with available experimental data shows that assuming complete bulk-to-surface partitioning of the organic component (total depletion of the bulk) along the full droplet growth curve does not adequately represent the activation properties of particles with high moderate surfactant mass fractions. Accounting for the surface tension depression mitigates some of the effect. Models that include the possibility for partial bulk-to-surface partitioning yield comparable results to the experimental data, even at high organic mass fractions in the particles. The study highlights the need for using thermodynamically consistent model frameworks to treat surface activity of atmospheric aerosols and for firm experimental validation of model predictions across a wide range of states relevant to the atmosphere.
- Published
- 2021
17. Supplementary material to 'Droplet activation of moderately surface active organic aerosol predicted with six approaches to surface activity'
- Author
-
Sampo Vepsäläinen, Silvia M. Calderón, Jussi Malila, and Nønne L. Prisle
- Published
- 2021
18. Estimating the saturation vapor pressures of isoprene oxidation products C5H12O6 and C5H10O6 using COSMO-RS
- Author
-
Noora Hyttinen, Joel A. Thornton, Emma L. D'Ambro, Theo Kurtén, and Nønne L. Prisle
- Subjects
Atmospheric Science ,010504 meteorology & atmospheric sciences ,Chemistry ,Hydrogen bond ,Vapor pressure ,Thermodynamics ,010501 environmental sciences ,01 natural sciences ,COSMO-RS ,13. Climate action ,Intramolecular force ,Molecule ,Saturation (chemistry) ,Conformational isomerism ,Volatility (chemistry) ,0105 earth and related environmental sciences - Abstract
We have used COSMO-RS (the conductor-like screening model for real solvents), as implemented in the COSMOtherm program, to compute the saturation vapor pressures at 298 K of two photo-oxidation products of isoprene: the dihydroxy dihydroperoxide C5H12O6, and the dihydroperoxy hydroxy aldehyde, C5H10O6. The predicted saturation vapor pressures were significantly higher (by up to a factor of 1000) than recent experimental results, very likely due to the overestimation of the effects of intramolecular hydrogen bonds, which tend to increase saturation vapor pressures by stabilizing molecules in the gas phase relative to the liquid. Modifying the hydrogen bond enthalpy parameter used by COSMOtherm can improve the agreement with experimental results – however the optimal parameter value is likely to be system-specific. Alternatively, vapor pressure predictions can be substantially improved (to within a factor of 5 of the experimental values for the two systems studied here) by selecting only conformers with a minimum number of intramolecular hydrogen bonds. The computed saturation vapor pressures were very sensitive to the details of the conformational sampling approach, with the default scheme implemented in the COSMOconf program proving insufficient for the task, for example by predicting significant differences between enantiomers, which should have identical physical properties. Even after exhaustive conformational sampling, COSMOtherm predicts significant differences in saturation vapor pressures between both structural isomers and diastereomers. For C5H12O6, predicted differences in psat between structural isomers are up to 2 orders of magnitude, and differences between stereoisomers are up to a factor of 20 – though these differences are very likely exaggerated by the overestimation of the effect of intramolecular H-bonds. For C5H10O6, the maximum predicted differences between the three studied structural isomers and their diastereomer pairs are around a factor of 8 and a factor of 2, respectively, when only conformers lacking intramolecular hydrogen bonds are included in the calculations. In future studies of saturation vapor pressures of polyfunctional atmospheric oxidation products using COSMOtherm, we recommend first performing thorough conformational sampling and subsequently selecting conformers with a minimal number of intramolecular H-bonds.
- Published
- 2018
19. A Monolayer Partitioning Scheme for Droplets of Surfactant Solutions
- Author
-
Jussi Malila and Nønne L. Prisle
- Subjects
Surface (mathematics) ,Materials science ,010504 meteorology & atmospheric sciences ,Atmospheric Composition and Structure ,010402 general chemistry ,01 natural sciences ,surfactants ,Surface tension ,Oceanography: Biological and Chemical ,Paleoceanography ,Pulmonary surfactant ,partitioning ,Monolayer ,Environmental Chemistry ,Cloud condensation nuclei ,Surface layer ,Research Articles ,0105 earth and related environmental sciences ,Aerosols ,Global and Planetary Change ,Geochemical Cycles ,Atmospheric models ,Idealized Model ,Aerosols and Particles ,0104 chemical sciences ,Condensed Matter::Soft Condensed Matter ,cloud condensation nuclei ,Pollution: Urban and Regional ,Geochemistry ,Chemical physics ,Atmospheric Processes ,General Earth and Planetary Sciences ,Cloud Physics and Chemistry ,Ternary operation ,Clouds and Aerosols ,aerosols ,Research Article - Abstract
Bulk‐surface partitioning of surface active species affects both cloud droplet activation by aerosol particles and heterogeneous atmospheric chemistry. Various approaches are given in the literature to capture this effect in atmospheric models. Here we present a simple, yet physically self‐contained, monolayer model for prediction of both composition and thickness of the surface layer of an aqueous droplet. The monolayer surface model is based on assuming a finite surface layer and mass balance of all species within the droplet. Model predictions are presented for binary and ternary aqueous surfactant model systems and compared to both experimental and model data from the literature and predictions using a common Gibbsian model approach. Deviations from Gibbsian surface thermodynamics due to volume constraints imposed by the finite monolayer lead to stronger predicted surface tension reduction at smaller droplet sizes with the monolayer model. Process dynamics of the presented monolayer model are also contrasted to other recently proposed approaches to treating surface partitioning in droplets, with different underlying assumptions., Key Points We present a physically consistent model for predicting composition and thickness of a surface monolayer on aqueous solution dropletsModel predictions are presented for binary and ternary water‐surfactant‐salt systems and compared to a Gibbsian model and experimental dataThe monolayer model predicts lower surface tensions than the Gibbsian model for droplet sizes relevant for atmospheric cloud activation
- Published
- 2018
20. Managing Urban Traffic Emissions with Focus on People and Atmospheric Impacts
- Author
-
Nønne L. Prisle and Mira Hulkkonen
- Subjects
050210 logistics & transportation ,Focus (computing) ,13. Climate action ,11. Sustainability ,0502 economics and business ,05 social sciences ,Business ,010501 environmental sciences ,01 natural sciences ,Environmental planning ,12. Responsible consumption ,0105 earth and related environmental sciences - Published
- 2021
21. Aqueous-phase behavior of glyoxal and methylglyoxal observed with carbon and oxygen K-edge X-ray absorption spectroscopy
- Author
-
Georgia Michailoudi, Jack J. Lin, Hayato Yuzawa, Masanari Nagasaka, Marko Huttula, Nobuhiro Kosugi, Theo Kurtén, Minna Patanen, Nønne L. Prisle
- Published
- 2021
- Full Text
- View/download PDF
22. Composition dependent density of ternary aqueous solutions of ionic surfactants and salts
- Author
-
Silvia M. Calderón, Nønne L. Prisle
- Published
- 2021
- Full Text
- View/download PDF
23. SO
- Author
-
Torsten, Berndt, Jing, Chen, Kristian H, Møller, Noora, Hyttinen, Nønne L, Prisle, Andreas, Tilgner, Erik H, Hoffmann, Hartmut, Herrmann, and Henrik G, Kjaergaard
- Abstract
The atmospheric reaction of OH radicals with dimethyl disulfide, CH3SSCH3, proceeds primarily via OH addition forming CH3S and CH3SOH as reactive intermediates, and to a lesser extent via H-abstraction resulting in the peroxy radical CH3SSCH2OO in the presence of O2. The latter undergoes a fast two-step isomerization process leading to HOOCH2SSCHO. CH3S and CH3SOH are both converted to SO2 and CH3O2 with near unity yields under atmospheric conditions.
- Published
- 2020
24. Aqueous phase behavior of glyoxal and methylglyoxal observed with carbon and oxygen K-edge X-ray absorption spectroscopy
- Author
-
Georgia Michailoudi, Jack J. Lin, Hayato Yuzawa, Masanari Nagasaka, Marko Huttula, Nobuhiro Kosugi, Theo Kurtén, Minna Patanen, and Nønne L. Prisle
- Subjects
13. Climate action - Abstract
Glyoxal (CHOCHO) and methylglyoxal (CH3C(O)CHO) are well-known components of atmospheric particles and their properties can impact atmospheric chemistry and cloud formation. To get information on their hydration states in aqueous solutions and how they are affected by addition of inorganic salts (sodium chloride (NaCl) and sodium sulfate (Na2SO4)), we applied carbon and oxygen K-edge X-ray absorption spectroscopy (XAS) in transmission mode. The recorded C K-edge spectra show that glyoxal is completely hydrated in the dilute aqueous solutions, in line with previous studies. For methylglyoxal, we identified, supported by quantum chemical calculations, not only C-H, C=O and C-OH bonds, but also fingerprints of C-OH(CH2) and C=C bonds. This implies the presence of both mono- and dihydrated forms of methylglyoxal, as well as products of aldol condensation, and enol tautomers of the monohydrates. The addition of salts was found to introduce only very minor changes to absorption energies and relative intensities of the observed absorption features, indicating that the organic-inorganic interactions at the studied concentrations are not strong enough to affect the spectra in this work. The identified structures of glyoxal and methylglyoxal in aqueous environment support the uptake of these compounds to the aerosol phase in the presence of water and their contribution on secondary organic aerosol formation.
- Published
- 2020
25. Supplementary material to 'Aqueous phase behavior of glyoxal and methylglyoxal observed with carbon and oxygen K-edge X-ray absorption spectroscopy'
- Author
-
Georgia Michailoudi, Jack J. Lin, Hayato Yuzawa, Masanari Nagasaka, Marko Huttula, Nobuhiro Kosugi, Theo Kurtén, Minna Patanen, and Nønne L. Prisle
- Published
- 2020
26. Supplementary material to 'Technical note: Estimating aqueous solubilities and activity coefficients of mono- and α, ω-dicarboxylic acids using COSMO-RS-DARE'
- Author
-
Noora Hyttinen, Reyhaneh Heshmatnezhad, Jonas Elm, Theo Kurtén, and Nønne L. Prisle
- Published
- 2020
27. Supplementary material to 'Pre-deliquescent water uptake in deposited nanoparticles observed with in situ ambient pressure X-ray photoelectron spectroscopy'
- Author
-
Jack J. Lin, Kamal Raj R, Stella Wang, Esko Kokkonen, Mikko-Heikki Mikkelä, Samuli Urpelainen, and Nønne L. Prisle
- Published
- 2020
28. Pre-deliquescent water uptake in deposited nanoparticles observed with in situ ambient pressure X-ray photoelectron spectroscopy
- Author
-
Jack J. Lin, Kamal Raj R, Stella Wang, Esko Kokkonen, Mikko-Heikki Mikkelä, Samuli Urpelainen, and Nønne L. Prisle
- Subjects
13. Climate action - Abstract
We study the adsorption of water onto deposited inorganic sodium chloride and organic malonic acid and sucrose nanoparticles at ambient water pressures corresponding to relative humidities (RH) from 0 to 16 %. To obtain information about water uptake at conditions where not accessible with typical aerosol instrumentation, we use surface-sensitive ambient pressure X-ray photoelectron spectroscopy (APXPS), which has a detection sensitivity from parts per thousand. Our results show that water is already adsorbed on sodium chloride particles at RH well below deliquescence, and that the chemical environment on the particle surface is changing with increasing humidity. While the sucrose particles exhibit only very modest changes on the surface at these relative humidities, the chemical composition and environment of malonic acid particle surfaces is clearly affected. Our observations indicate that water uptake by inorganic and organic aerosol particles could already have an impact on atmospheric chemistry at low relative humidities. We also conclude that the APXPS technique is a viable tool for studying chemical changes on the surfaces of atmospherically relevant aerosol particles which are not accessible with typical online mass- and volume-based methods.
- Published
- 2020
29. Surface Tension of Surfactant-Containing, Finite Volume Droplets
- Author
-
Jim S. Walker, Nønne L. Prisle, Bryan R. Bzdek, Hallie C. Boyer, Jonathan P. Reid, Jussi Malila, Rachael E. H. Miles, and Cari S. Dutcher
- Subjects
Physics::Fluid Dynamics ,Surface tension ,Finite volume method ,Materials science ,Pulmonary surfactant ,Composite material - Abstract
Surface tension influences the fraction of atmospheric particles that become cloud droplets. Recent field studies have indicated that surfactants, which lower the surface tension of macroscopic solutions, are an important component of aerosol mass. However, the surface tension of activating aerosol particles is still unresolved, with most climate models assuming activating particles have a surface tension equal to that of water. For surfactants to be relevant to particle activation into cloud droplets, multiple parameters must be considered. First, the concentration of surfactant in the initial particle must be sufficiently large that surface tension depression is maintained during activation, despite the dilution that occurs as water condenses onto the particle. Second, the high surface to volume ratio of micron and submicron particles necessitates partitioning a larger fraction of the surfactant molecules to the particle surface than in a typical solution, resulting in a depletion of the bulk concentration and an increase in the surface tension relative to a bulk sample. Third, the timescale for establishing equilibrium at the droplet surface must be known. The interplay of these parameters highlights the necessity of direct measurements of picolitre droplet surface tension.This presentation will describe two cutting-edge approaches we have developed to directly measure the surface tension of microscopic droplets. In the first approach, ejection of ~20 µm radius surfactant-containing droplets from a dispenser excites oscillations in droplet shape that can be used to retrieve the droplet surface tension on microsecond timescales. These measurements allow investigation of surfactant partitioning timescales in aerosol and, crucially, test the assumption that droplet surfaces are generally in their equilibrium state. In the second approach, the coalescence of ~8 µm radius droplets is investigated. Coalescence excites droplet shape oscillations which again permit quantification of droplet surface tension. We demonstrate that surfactants can significantly reduce the surface tension of finite sized droplets below the value for water, consistent with recent field measurements. This surface tension reduction is droplet size dependent and does not correspond exactly to the macroscopic solution value. A new monolayer partitioning model confirms the observed size dependent surface tension arises from the high surface-to-volume ratio in finite-sized droplets and enables predictions of aerosol hygroscopic growth. This model, constrained by the laboratory measurements, is consistent with a reduction in critical supersaturation for activation and a 30% increase in cloud droplet number concentration, in line with a radiative cooling effect larger than current estimates assuming a water surface tension by 1 W·m-2. The results imply that one single value for surface tension cannot be used to predict the activated aerosol fraction.
- Published
- 2020
30. New pathways of the reaction of OH radicals with dimethyl sulfide based on CH3SCH2O2 isomerization
- Author
-
Armin Hansel, Wiebke Scholz, Andreas Tilgner, Noora Hyttinen, Nønne L. Prisle, Bernhard Mentler, Torsten Berndt, Erik Hans Hoffmann, Lukas Fischer, and Hartmut Herrmann
- Subjects
chemistry.chemical_compound ,chemistry ,Radical ,Dimethyl sulfide ,Photochemistry ,Isomerization - Abstract
Dimethyl sulfide (DMS), produced by marine organisms, represents the most abundant, biogenic sulfur emission into the Earth´s atmosphere. The gas-phase degradation of DMS is mainly initiated by the reaction with the OH radical forming first CH3SCH2O2 radicals from the dominant H-abstraction channel. A fast CH3SCH2O2 isomerization process was proposed as a result of quantum chemical calculations. In the present study, experimental investigations on the product formation from OH + DMS have been conducted in a free-jet flow system at 295 ± 2 K and 1 bar air. Very efficient detection of CH3SCH2O2 isomerization products has been achieved by iodide-CI-APi-TOF measurements allowing to run the reaction for close to atmospheric conditions. It is experimentally shown that the CH3SCH2O2 radicals undergo a two-step isomerization process finally forming a product consistent with the formula HOOCH2SCHO. The isomerization process is accompanied by OH recycling. The rate-limiting first isomerization step, CH3SCH2O2 → CH2SCH2OOH proceeds with k = (0.23 ± 0.12) s-1 at 295 ± 2 K. Competing bimolecular CH3SCH2O2 reactions with NO, HO2 or RO2 radicals are less important for trace-gas conditions over the oceans. Results of atmospheric chemistry simulations demonstrate the predominance (≥95%) of CH3SCH2O2 isomerization. The rapid peroxy radical isomerization, not yet considered in models, substantially changes the understanding of DMS´s degradation processes in the atmosphere.
- Published
- 2020
31. Model for estimating activity coefficients in binary and ternary ionic surfactant solutions
- Author
-
Silvia M. Calderón, Jussi Malila, Nønne L. Prisle
- Published
- 2020
- Full Text
- View/download PDF
32. Ultrafast diffusion exchange nuclear magnetic resonance
- Author
-
Anne Selent, Sanna Komulainen, Sarah E. Mailhiot, Nønne L. Prisle, Otto Mankinen, Vladimir V. Zhivonitko, Ville-Veikko Telkki, and Susanna Ahola
- Subjects
Materials science ,Science ,General Physics and Astronomy ,02 engineering and technology ,010402 general chemistry ,01 natural sciences ,Chemical reaction ,Article ,General Biochemistry, Genetics and Molecular Biology ,Molecule ,Diffusion (business) ,lcsh:Science ,Molecular diffusion ,Multidisciplinary ,General Chemistry ,Nuclear magnetic resonance spectroscopy ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,Orders of magnitude (time) ,Physical chemistry ,Chemical physics ,Protein folding ,lcsh:Q ,0210 nano-technology ,Ultrashort pulse ,Solution-state NMR - Abstract
The exchange of molecules between different physical or chemical environments due to diffusion or chemical transformations has a crucial role in a plethora of fundamental processes such as breathing, protein folding, chemical reactions and catalysis. Here, we introduce a method for a single-scan, ultrafast NMR analysis of molecular exchange based on the diffusion coefficient contrast. The method shortens the experiment time by one to four orders of magnitude. Consequently, it opens the way for high sensitivity quantification of important transient physical and chemical exchange processes such as in cellular metabolism. As a proof of principle, we demonstrate that the method reveals the structure of aggregates formed by surfactants relevant to aerosol research., Analysis of exchange processes is time consuming by two-dimensional exchange NMR spectroscopy. Here the authors demonstrate a single-scan ultrafast Laplace NMR approach based on spatial encoding to measure molecular diffusion, with an increase by a factor six in the sensitivity per unit time.
- Published
- 2020
33. SO2 formation and peroxy radical isomerization in the atmospheric reaction of OH radicals with dimethyl disulfide
- Author
-
Torsten Berndt, Henrik G. Kjaergaard, Noora Hyttinen, Hartmut Herrmann, Erik Hans Hoffmann, Nønne L. Prisle, Kristian H. Møller, Andreas Tilgner, and Jing Chen
- Subjects
010504 meteorology & atmospheric sciences ,Radical ,Reactive intermediate ,Metals and Alloys ,General Chemistry ,010402 general chemistry ,Photochemistry ,01 natural sciences ,7. Clean energy ,Catalysis ,0104 chemical sciences ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,chemistry.chemical_compound ,chemistry ,Atmospheric reactions ,Materials Chemistry ,Ceramics and Composites ,Dimethyl disulfide ,Isomerization ,0105 earth and related environmental sciences - Abstract
The atmospheric reaction of OH radicals with dimethyl disulfide, CH3SSCH3, proceeds primarily via OH addition forming CH3S and CH3SOH as reactive intermediates, and to a lesser extent via H-abstraction resulting in the peroxy radical CH3SSCH2OO in the presence of O2. The latter undergoes a fast two-step isomerization process leading to HOOCH2SSCHO. CH3S and CH3SOH are both converted to SO2 and CH3O2 with near unity yields under atmospheric conditions.
- Published
- 2020
34. Effects of surface tension time-evolution for CCN activation of a complex organic surfactant
- Author
-
Jussi Malila, Thomas Bjerring Kristensen, Jack J. Lin, Silvia M. Calderón, and Nønne L. Prisle
- Subjects
Work (thermodynamics) ,Materials science ,010504 meteorology & atmospheric sciences ,Thermodynamics ,Context (language use) ,010501 environmental sciences ,Management, Monitoring, Policy and Law ,Köhler theory ,complex mixtures ,01 natural sciences ,Surface tension ,Surface-Active Agents ,Adsorption ,Pulmonary surfactant ,Phase (matter) ,Physics::Atomic and Molecular Clusters ,Surface Tension ,Environmental Chemistry ,Cloud condensation nuclei ,0105 earth and related environmental sciences ,Aerosols ,technology, industry, and agriculture ,Public Health, Environmental and Occupational Health ,General Medicine ,eye diseases ,Solutions ,13. Climate action - Abstract
The physical processes and time scales underlying the evolution of surface tension in atmospheric solution droplets are largely unaccounted for in present models describing cloud droplet formation. Adsorption of surface-active molecules at the surface of a solution droplet depresses the droplet surface tension but also depletes solute from the droplet bulk, which have opposing and sometimes canceling effects in cloud droplet formation. In this work, we study the effect of time-evolving surface tension for cloud droplet activation of particles composed of Nordic Aquatic Fulvic Acid (NAFA) mixed with sodium chloride (NaCl). We model the formation of cloud droplets using Köhler theory with surface tension depression and bulk/surface partitioning evaluated from two different thermodynamic surface models. Continuous ternary parameterizations were constructed from surface tension measurements of macroscopic droplets at different time steps after the formation of a droplet surface. The predicted results are compared to previous measurements of mixed NAFA-NaCl cloud condensation nuclei (CCN) activity and a bulk solution model that does not take the NAFA bulk/surface partitioning equilibrium into account. Whereas the bulk model shows a trend in cloud droplet formation following that of macroscopic surface tension depression with time, the variation with time essentially disappears when bulk/surface partitioning is taken explicitly into account during droplet activation. For all equilibrium time steps considered, the effect of surface tension depression in the NAFA-NaCl system is counteracted by the depletion of solute from the finite-sized droplet bulk phase. Our study highlights that a comprehensive data set is necessary to obtain continuous parameterizations of surface tension and other solution properties required to fully account for the bulk/surface partitioning in growing droplets. To our knowledge, no similar data set currently exists for other aqueous organic systems of atmospheric interest. Additional work is necessary to deconvolve the effects of bulk/surface partitioning in the context of time-evolution on cloud droplet activation and to determine whether the results presented here can be further generalized.
- Published
- 2020
- Full Text
- View/download PDF
35. Supplementary material to 'Thermodynamic properties of isoprene and monoterpene derived organosulfates estimated with COSMOtherm'
- Author
-
Noora Hyttinen, Jonas Elm, Jussi Malila, Silvia M. Calderón, and Nønne L. Prisle
- Published
- 2019
36. Thermodynamic properties of isoprene and monoterpene derived organosulfates estimated with COSMOtherm
- Author
-
Noora Hyttinen, Jonas Elm, Jussi Malila, Silvia M. Calderón, and Nønne L. Prisle
- Abstract
Organosulfates make significant contributions to atmospheric secondary organic aerosol (SOA), but little is still known about the thermodynamic properties of atmospherically relevant organosulfates. We have used the COSMOtherm program to calculate both gas- and condensed-phase properties of previously identified atmospherically relevant monoterpene and isoprene derived organosulfates. Properties include solubilities, activities and saturation vapor pressures, which are critical to the aerosol phase stability and atmospheric impact of organosulfate SOA. Based on the estimated saturation vapor pressures, the organosulfates of this study can all be categorized as semi- or low-volatile, with saturation vapor pressures 4 to 8 orders of magnitude lower than that of sulfuric acid. The estimated pKa values of all the organosulfates indicate a high degree of dissociation in water, leading in turn to high dissociation corrected solubilities. In aqueous mixtures with inorganic sulfate, COSMOtherm predicts a salting out of both the organosulfates and their sodium salts from inorganic co-solutes. The salting-out effect of ammonium sulfate (less acidic) is stronger than of ammonium bisulfate (more acidic). Finally, COSMOtherm predicts liquid-liquid phase separation in systems containing water and monoterpene derived organosulfates. The COSMOtherm estimated properties support the observed stability of organosulfates as SOA constituents and their long range transport in the atmosphere, but also show significant variation between specific compounds and ambient conditions.
- Published
- 2019
37. Strong Even/Odd Pattern in the Computed Gas-Phase Stability of Dicarboxylic Acid Dimers: Implications for Condensation Thermodynamics
- Author
-
Nønne L. Prisle, Noora Hyttinen, Jack J. Lin, Jonas Elm, Theo Kurtén, Department of Chemistry, and Institute for Atmospheric and Earth System Research (INAR)
- Subjects
ENERGIES ,Dimer ,116 Chemical sciences ,Glutaric acid ,010402 general chemistry ,114 Physical sciences ,01 natural sciences ,MOLECULES ,chemistry.chemical_compound ,SULFURIC-ACID ,AEROSOLS ,PARTICLE FORMATION ,0103 physical sciences ,ALTERNATION ,Physical and Theoretical Chemistry ,PINIC ACID ,DICARBONYLS ,PRECURSORS ,chemistry.chemical_classification ,Adipic acid ,010304 chemical physics ,Chemistry ,Hydrogen bond ,Condensation ,0104 chemical sciences ,VAPOR-PRESSURES ,Crystallography ,Dicarboxylic acid ,Pimelic acid ,Succinic acid - Abstract
The physical properties of small straight-chain dicarboxylic acids are well known to exhibit even/odd alternations with respect to the carbon chain length. For example, odd numbered diacids have lower melting points and higher saturation vapor pressures than adjacent even numbered diacids. This alternation has previously been explained in terms of solid-state properties, such as higher torsional strain of odd number diacids. Using quantum chemical methods, we demonstrate an additional contribution to this alternation in properties resulting from gas-phase dimer formation. Due to a combination of hydrogen bond strength and torsional strain, dimer formation in the gas phase occurs efficiently for glutaric acid (CS) and pimelic acid (C7) but is unfavorable for succinic acid (C4) and adipic acid (C6). Our results indicate that a significant fraction of the total atmospheric gas-phase concentration of glutaric and pimelic acid may consist of dimers.
- Published
- 2019
38. Fast Peroxy Radical Isomerization and OH Recycling in the Reaction of OH Radicals with Dimethyl Sulfide
- Author
-
Erik Hans Hoffmann, Lukas Fischer, Hartmut Herrmann, Torsten Berndt, Bernhard Mentler, Noora Hyttinen, Nønne L. Prisle, Wiebke Scholz, Armin Hansel, and Andreas Tilgner
- Subjects
Anions ,Isomerization ,010504 meteorology & atmospheric sciences ,Radical ,fungi ,chemistry.chemical_element ,010501 environmental sciences ,Molecules ,Photochemistry ,01 natural sciences ,Sulfur ,Addition reactions ,Atmosphere ,chemistry.chemical_compound ,chemistry ,13. Climate action ,Chemical reactions ,Degradation (geology) ,General Materials Science ,Dimethyl sulfide ,Physical and Theoretical Chemistry ,Earth (classical element) ,0105 earth and related environmental sciences - Abstract
Dimethyl sulfide (DMS), produced by marine organisms, represents the most abundant, biogenic sulfur emission into the Earth’s atmosphere. The gas-phase degradation of DMS is mainly initiated by the reaction with the OH radical forming first CH3SCH2O2 radicals from the dominant H-abstraction channel. It is experimentally shown that these peroxy radicals undergo a two-step isomerization process finally forming a product consistent with the formula HOOCH2SCHO. The isomerization process is accompanied by OH recycling. The rate-limiting first isomerization step, CH3SCH2O2 → CH2SCH2OOH, followed by O2 addition, proceeds with k = (0.23 ± 0.12) s–1 at 295 ± 2 K. Competing bimolecular CH3SCH2O2 reactions with NO, HO2, or RO2 radicals are less important for trace-gas conditions over the oceans. Results of atmospheric chemistry simulations demonstrate the predominance (≥95%) of CH3SCH2O2 isomerization. The rapid peroxy radical isomerization, not yet considered in models, substantially changes the understanding of DMS’s degradation processes in the atmosphere.
- Published
- 2019
- Full Text
- View/download PDF
39. Hygroscopic properties and cloud condensation nuclei activation of limonene-derived organosulfates and their mixtures with ammonium sulfate
- Author
-
Marianne Glasius, Tomi Raatikainen, Annele Virtanen, A. M. K. Hansen, Kasper Kristensen, Arttu Ylisirniö, Juan Hong, Nønne L. Prisle, Tuukka Petäjä, Department of Physics, Aerosol-Cloud-Climate -Interactions (ACCI), and Faculty of Science and Forestry
- Subjects
Atmospheric Science ,Ammonium sulfate ,CCN ACTIVITY ,010504 meteorology & atmospheric sciences ,DROPLET ACTIVATION ,SURFACE-TENSION ,Analytical chemistry ,010501 environmental sciences ,Köhler theory ,CHEMICAL-COMPOSITION ,01 natural sciences ,114 Physical sciences ,Surface tension ,HUMIC-LIKE SUBSTANCES ,lcsh:Chemistry ,chemistry.chemical_compound ,SECONDARY ORGANIC AEROSOL ,BOREAL FOREST ENVIRONMENT ,Organic chemistry ,Cloud condensation nuclei ,Solubility ,0105 earth and related environmental sciences ,Supersaturation ,Aqueous solution ,Chemistry ,ATMOSPHERIC AEROSOL ,SUBMICROMETER AEROSOL ,lcsh:QC1-999 ,3. Good health ,PARTICLE HYGROSCOPICITY ,lcsh:QD1-999 ,Particle ,lcsh:Physics - Abstract
Article, Organosulfates have been observed as constituents of atmospheric aerosols in a wide range of environments; however their hygroscopic properties remain uncharacterised. Here, limonene-derived organosulfates with a molecular weight of 250 Da (L-OS 250) were synthesised and used for simultaneous measurements with a hygroscopicity tandem differential mobility analyser (H-TDMA) and a cloud condensation nuclei counter (CCNC) to determine the hygroscopicity parameter, κ, for pure L-OS 250 and mixtures of L-OS 250 with ammonium sulfate (AS) over a wide range of humidity conditions. The κ values derived from measurements with H-TDMA decreased with increasing particle dry diameter for all chemical compositions investigated, indicating that κH-TDMA depends on particle diameter and/or surface effects; however, it is not clear if this trend is statistically significant. For pure L-OS 250, κ was found to increase with increasing relative humidity, indicating dilution/solubility effects to be significant. Discrepancies in κ between the sub- and supersaturated measurements were observed for L-OS 250, whereas κ of AS and mixed L-OS 250/AS were similar. This discrepancy was primarily ascribed to limited dissolution of L-OS 250 at subsaturated conditions. In general, hygroscopic growth factor, critical particle diameter and κ for the mixed L-OS 250/AS particles converged towards the values of pure AS for mixtures with ≥ 20 % w / w AS. Surface tension measurements of bulk aqueous L-OS 250/AS solutions showed that L-OS 250 was indeed surface active, as expected from its molecular structure, decreasing the surface tension of solutions with 24 % from the pure water value at a L-OS 250 concentration of 0.0025 mol L−1. Based on these surface tension measurements, we present the first concentration-dependent parametrisation of surface tension for aqueous L-OS 250, which was implemented to different process-level models of L-OS 250 hygroscopicity and CCN activation. The values of κ obtained from the measurements were compared with κ calculated applying the volume additive Zdanovskii–Stokes–Robinson mixing rule, as well as κ modelled from equilibrium Köhler theory with different assumptions regarding L-OS 250 bulk-to-surface partitioning and aqueous droplet surface tension. This study is to our knowledge the first to investigate the hygroscopic properties and surface activity of L-OS 250; hence it is an important first step towards understanding the atmospheric impact of organosulfates., published version, http://purl.org/eprint/status/PeerReviewed
- Published
- 2015
40. Supplementary material to 'Estimating the saturation vapor pressures of isoprene oxidation products C5H12O6 and C5H10O6 using COSMO-RS'
- Author
-
Theo Kurtén, Noora Hyttinen, Emma L. D'Ambro, Joel Thornton, and Nønne L. Prisle
- Published
- 2018
41. CCN activity of six pollenkitts and the influence of their surface activity
- Author
-
J. Carson Meredith, Jack J. Lin, Sara Purdue, Nønne L. Prisle, Athanasios Nenes, and Haisheng Lin
- Subjects
chemistry.chemical_classification ,Ammonium sulfate ,Aqueous solution ,010504 meteorology & atmospheric sciences ,Salt (chemistry) ,010501 environmental sciences ,medicine.disease_cause ,01 natural sciences ,Surface tension ,chemistry.chemical_compound ,chemistry ,Chemical engineering ,Pulmonary surfactant ,Pollen ,medicine ,Dispersion (chemistry) ,Chemical composition ,0105 earth and related environmental sciences - Abstract
Pollenkitt is a viscous material that coats grains of pollen and plays important roles in pollen dispersion and plant reproduction. It may also be an important contributor to pollen water uptake and 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. The 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 impact on pollenkitt hygroscopicity. We measure cloud 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 activation potential and hygroscopicity. In addition, we find indication of significant impact of complex non-ideal solution effects in systematic and consistent size dependency of pollenkitt hygroscopicity.
- Published
- 2018
42. Statistical Mechanics of Multilayer Sorption: Surface Concentration Modeling and XPS Measurement
- Author
-
Anthony S. Wexler, Nønne L. Prisle, and Anthony R. Toribio
- Subjects
Surface (mathematics) ,Work (thermodynamics) ,Materials science ,Thermodynamics ,Sorption ,Bioengineering ,02 engineering and technology ,Statistical mechanics ,Surface concentration ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Article ,0104 chemical sciences ,Surface tension ,X-ray photoelectron spectroscopy ,Physical Sciences ,Chemical Sciences ,Molecule ,General Materials Science ,Physical and Theoretical Chemistry ,0210 nano-technology - Abstract
© 2018 American Chemical Society. The concentration of solute molecules at the surface of a liquid is a factor in heterogeneous reactions, surface tension, and Marangoni-effect-driven surface flows. Increasingly, X-ray photoelectron spectroscopy (XPS) has enabled surface concentrations to be measured. In prior work, we employed statistical mechanics to derive expressions for surface tension as a function of solute activity in a binary solution. Here we use a Gibbs relation to derive concomitant expressions for surface concentration. Surface tension data from the literature for five alcohols are used to identify parameters in the surface tension equation. These parameters are then used in the surface concentration equation to predict surface concentrations. Comparison of these predictions to those measured with XPS shows a factor of three difference between measured and predicted surface concentrations. Potential reasons for the discrepancy are discussed, including lack of surface-bulk equilibrium in the measurements.
- Published
- 2018
43. Notably improved inversion of differential mobility particle sizer data obtained under conditions of fluctuating particle number concentrations
- Author
-
Jarno Vanhatalo, Nønne L. Prisle, P. P. Aalto, Kaarle Hämeri, Bjarke Mølgaard, Department of Physics, Environmental Sciences, Biostatistics Helsinki, Aerosol-Cloud-Climate -Interactions (ACCI), and Environmental and Ecological Statistics Group
- Subjects
Atmospheric Science ,010504 meteorology & atmospheric sciences ,Particle number ,lcsh:TA715-787 ,lcsh:Earthwork. Foundations ,Inversion (meteorology) ,Time resolution ,01 natural sciences ,114 Physical sciences ,Condensation particle counter ,lcsh:Environmental engineering ,010104 statistics & probability ,symbols.namesake ,13. Climate action ,Urban background ,Statistics ,symbols ,Statistical physics ,lcsh:TA170-171 ,0101 mathematics ,Gaussian process ,0105 earth and related environmental sciences ,Mathematics - Abstract
The differential mobility particle sizer (DMPS) is designed for measurements of particle number size distributions. It performs a number of measurements while scanning over different particle sizes. A standard assumption in the data-processing (inversion) algorithm is that the size distribution remains the same throughout each scan. For a DMPS deployed in an urban area this assumption is likely to be violated most of the time, and the resulting size distribution data are unreliable. To improve the reliability, we developed a new algorithm using a statistical model in which the problematic assumption was replaced with more realistic smoothness assumptions, which were expressed through Gaussian process prior probabilities. We tested the model with data from a twin DMPS located at an urban background site in Helsinki and found that it provides size distribution data which are much more realistic. Furthermore, particle number concentrations extracted from the DMPS data were compared with data from a condensation particle counter. At 10 min resolution, the correlation for a period of 10 days was 0.984 with the new algorithm and 0.967 with the old one. Moreover, the time resolution was improved, and at 30 s resolution we obtained positive correlations for 89 % of the scans. Thus, the quality of the inverted data was clearly improved.
- Published
- 2018
44. Modeling CCN activity of chemically unresolved model HULIS, including surface tension, non-ideality, and surface partitioning
- Author
-
Bjarke Mølgaard and Nønne L. Prisle
- Subjects
Supersaturation ,Aqueous solution ,010504 meteorology & atmospheric sciences ,Chemistry ,Thermodynamics ,010501 environmental sciences ,complex mixtures ,01 natural sciences ,Kelvin equation ,Aerosol ,Surface tension ,symbols.namesake ,Pulmonary surfactant ,13. Climate action ,Phase (matter) ,symbols ,Cloud condensation nuclei ,0105 earth and related environmental sciences - Abstract
Cloud condensation nuclei (CCN) activity of aerosol particles comprising surface active Nordic Aquatic Fulvic Acid (NAFA) and NaCl was modeled with four different approaches to account for NAFA bulk-to-surface partitioning and the combined influence of NAFA and NaCl on surface tension and water activity of activating droplets. Calculations were made for particles with dry diameters of 30–230 nm and compositions covering the full range of relative NAFA and NaCl mixing ratios. Continuous ternary parametrizations of aqueous surface tension and water activity with respect to independently varying NAFA and NaCl mass concentrations were developed from previous measurements on macroscopic bulk solutions and implemented to a Köhler model framework. This enabled comprehensive thermodynamic predictions of cloud droplet activation, including equilibrium surface partitioning, for particles comprising chemically unresolved organic NAFA mixtures. NAFA here serves as a model for surface active atmospheric humic-like substances (HULIS) and for chemically complex organic aerosol in general. Surfactant effects are gauged via predictions of a suite of properties for activating droplets, including critical supersaturation and droplet size, bulk phase composition, surface tension, Kelvin effect, and water activity. Assuming macroscopic solution properties for activating droplets leads to gross overestimations of reported experimental CCN activation, mainly by overestimating surface tension reduction from NAFA solute in droplets. Failing to account for bulk-to-surface partitioning of NAFA introduces severe biases in evaluated droplet bulk and surface composition and critical size, which here specifically affect cloud activation thermodynamics, but more generally could also impact heterogeneous chemistry on droplet surfaces. Model frameworks based on either including surface partitioning and/or neglecting surface tension reduction give similar results for both critical supersaturation and droplet properties and reproduce reported experimental CCN activity well. These perhaps counterintuitive results reflect how the bulk phase is nearly depleted in surface active organic from surface partitioning in submicron droplets with large surface area for a given bulk volume. As a result, NAFA has very little impact on surface tension and water activity at the point of droplet activation. In other words, the predicted surfactant strength of NAFA is significantly lower in sub-micron activating droplets than in macroscopic aqueous solutions of the same overall composition. These results show similar effects of chemically complex surfactants as have previously been seen only for simple surfactants with well-defined molecular properties and add to the growing appreciation of the complex role of surface activity in cloud droplet activation.
- Published
- 2018
- Full Text
- View/download PDF
45. A continuous flow diffusion chamber study of sea salt particles acting as cloud nuclei: deliquescence and ice nucleation
- Author
-
Erik S. Thomson, Michael Roesch, Daniel J. Cziczo, Markus Ammann, Xiangrui Kong, Peter A. Alpert, Thorsten Bartels-Rausch, Martin J. Wolf, Nønne L. Prisle, Massachusetts Institute of Technology. Department of Civil and Environmental Engineering, Massachusetts Institute of Technology. Department of Earth, Atmospheric, and Planetary Sciences, Kong, Xiangrui, Wolf, Martin Johann, Roesch, Michael, and Cziczo, Daniel James
- Subjects
Diffusion chamber ,Atmospheric Science ,food.ingredient ,010504 meteorology & atmospheric sciences ,heterogeneous ice nucleation ,deliquescence ,lcsh:QC851-999 ,010402 general chemistry ,01 natural sciences ,food ,Phase (matter) ,skin and connective tissue diseases ,0105 earth and related environmental sciences ,Continuous flow ,homogeneous ice nucleation ,Sea salt ,continuous flow diffusion chamber ,Energy budget ,0104 chemical sciences ,13. Climate action ,Chemical physics ,Ice nucleus ,lcsh:Meteorology. Climatology ,sense organs ,sea salt ,Earth (classical element) - Abstract
Phase changes of sea salt particles alter their physical and chemical properties, which is significant for Earth’s chemistry and energy budget. In this study, continuous flow diffusion chamber is used to investigate deliquescence, homogeneous and heterogeneous ice nucleation between 242 K and 215 K, of four salts: pure NaCl, pure MgCl2, synthetic sea water salt, and salt distilled from sampled sea water. Anhydrous particles, aqueous droplets and ice particles were discriminated using a polarisation-sensitive optical particle counter coupled with a machine learning analysis technique. The measured onset deliquescence relative humidities agree with previous studies, where sea water salts deliquescence at lower humidities than pure NaCl. Deliquesced salt droplets homogenously freeze when the relative humidity reaches a sufficiently high value at temperatures below 233 K. From 224 K and below, deposition nucleation freezing on a fraction of NaCl particles was observed at humidities lower than the deliquescence relative humidity. At these low temperatures, otherwise unactivated salt particles deliquesced at the expected deliquescence point, followed by homogeneous freezing at temperatures as low as 215 K. Thus, the observed sea salt particles exhibit a triad of temperature-dependent behaviours. First, they act as cloud condensation particles (CCNs) > 233 K, second they can be homogeneous freezing nuclei (HFNs) < 233 K and finally they act as ice nucleating particles (INPs) for heterogeneous nucleation, National Science Foundation (U.S.) (Grant AGS-1461305), National Science Foundation (U.S.) (Grant AGS-1461347)
- Published
- 2018
- Full Text
- View/download PDF
46. Shifted equilibria of organic acids and bases in the aqueous surface region
- Author
-
Olle Björneholm, Carl Caleman, Delphine Kawecki, Isaak Unger, Marie Madeleine Walz, Victor Ekholm, Nønne L. Prisle, Corina Valtl, Josephina Werner, Ingmar Persson, Clara-Magdalena Saak, and Gunnar Öhrwall
- Subjects
Hydronium ,Analytical chemistry ,General Physics and Astronomy ,02 engineering and technology ,010402 general chemistry ,Mole fraction ,Physical Chemistry ,01 natural sciences ,Chemical equation ,chemistry.chemical_compound ,X-ray photoelectron spectroscopy ,Physical and Theoretical Chemistry ,Alkyl ,Fysikalisk kemi ,chemistry.chemical_classification ,Aqueous solution ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,Chemistry ,chemistry ,13. Climate action ,ddc:540 ,Hydroxide ,Acid–base reaction ,0210 nano-technology - Abstract
Physical chemistry, chemical physics 20(36), 23281 - 23293 (2018). doi:10.1039/C8CP01898G, Acid–base equilibria of carboxylic acids and alkyl amines in the aqueous surface region were studied using surface-sensitive X-ray photoelectron spectroscopy and molecular dynamics simulations. Solutions of these organic compounds were examined as a function of pH, concentration and chain length to investigate the distribution of acid and base form in the surface region as compared to the aqueous bulk. Results from these experiments show that the neutral forms of the studied acid–base pairs are strongly enriched in the aqueous surface region. Moreover, we show that for species with at least four carbon atoms in their alkyl-chain, their charged forms are also found to be abundant in the surface region. Using a combination of XPS and MD results, a model is proposed that effectively describes the surface composition. Resulting absolute surface concentration estimations show clearly that the total organic mole fractions in the surface region change drastically as a function of solution pH. The origin of the observed surface phenomena, hydronium/hydroxide concentrations in the aqueous surface region and why standard chemical equations, used to describe equilibria in dilute bulk solution are not valid in the aqueous surface region, are discussed in detail. The reported results are of considerable importance especially for the detailed understanding of properties of small aqueous droplets that can be found in the atmosphere., Published by RSC Publ., Cambridge
- Published
- 2018
47. Adsorptive uptake of water by semisolid secondary organic aerosols
- Author
-
Annele Virtanen, Mikhail Paramonov, Liqing Hao, Ari Laaksonen, James F. Brogan, Aki Pajunoja, Markku Kulmala, Ilona Riipinen, Jani Hakala, Neil M. Donahue, Tuukka Petäjä, Douglas R. Worsnop, Sami Romakkaniemi, Timothy B. Onasch, Kari E. J. Lehtinen, M. J. Cummings, Narges Rastak, Nønne L. Prisle, Jussi Malila, Juan Hong, Paola Massoli, Paul Davidovits, Andrew T. Lambe, Department of Physics, Aerosol-Cloud-Climate -Interactions (ACCI), and Polar and arctic atmospheric research (PANDA)
- Subjects
Meteorology ,aerosol ,hygroscopicity ,114 Physical sciences ,ACTIVATION ,BOREAL FOREST ,Phase (matter) ,SDG 13 - Climate Action ,SOA ,PARTICLES ,HYGROSCOPIC GROWTH ,Solubility ,Dissolution ,1172 Environmental sciences ,CCN ,Supersaturation ,Atmospheric models ,solubility ,Humidity ,GAP ,ATMOSPHERE ,FRAMEWORK ,Aerosol ,Geophysics ,adsorption ,MASS-SPECTROMETER ,13. Climate action ,Environmental chemistry ,General Earth and Planetary Sciences ,Environmental science ,Climate model - Abstract
Aerosol climate effects are intimately tied to interactions with water. Here we combine hygroscopicity measurements with direct observations about the phase of secondary organic aerosol (SOA) particles to show that water uptake by slightly oxygenated SOA is an adsorption-dominated process under subsaturated conditions, where low solubility inhibits water uptake until the humidity is high enough for dissolution to occur. This reconciles reported discrepancies in previous hygroscopicity closure studies. We demonstrate that the difference in SOA hygroscopic behavior in subsaturated and supersaturated conditions can lead to an effect up to about 30% in the direct aerosol forcinghighlighting the need to implement correct descriptions of these processes in atmospheric models. Obtaining closure across the water saturation point is therefore a critical issue for accurate climate modeling.
- Published
- 2015
48. Estimates of global dew collection potential on artificial surfaces
- Author
-
Henri Vuollekoski, Ella-Maria Kyrö, Tuukka Petäjä, Risto Makkonen, Mikko Sipilä, Jussi S. Ylhäisi, Matthias Vogt, Heikki Järvinen, Jonathan Duplissy, Victoria A. Sinclair, Markku Kulmala, Petri Räisänen, Nønne L. Prisle, Department of Physics, Aerosol-Cloud-Climate -Interactions (ACCI), and Polar and arctic atmospheric research (PANDA)
- Subjects
1171 Geosciences ,FOG-WATER COLLECTION ,Meteorological reanalysis ,010504 meteorology & atmospheric sciences ,education ,0207 environmental engineering ,ERA-INTERIM ,02 engineering and technology ,Atmospheric sciences ,114 Physical sciences ,lcsh:Technology ,01 natural sciences ,lcsh:TD1-1066 ,REANALYSIS ,Hydrology (agriculture) ,HEAT-TRANSFER ,lcsh:Environmental technology. Sanitary engineering ,020701 environmental engineering ,lcsh:Environmental sciences ,0105 earth and related environmental sciences ,lcsh:GE1-350 ,Hydrology ,lcsh:T ,COASTAL ,lcsh:Geography. Anthropology. Recreation ,ISRAEL ,PERFORMANCE ,NEGEV DESERT ,6. Clean water ,lcsh:G ,13. Climate action ,Environmental science ,Dew - Abstract
The global potential for collecting usable water from dew on an artificial collector sheet was investigated by utilizing 34 years of meteorological reanalysis data as input to a dew formation model. Continental dew formation was found to be frequent and common, but daily yields were mostly below 0.1 mm. Nevertheless, some water-stressed areas such as parts of the coastal regions of northern Africa and the Arabian Peninsula show potential for large-scale dew harvesting, as the yearly yield may reach up to 100 L m−2 for a commonly used polyethylene foil. Statistically significant trends were found in the data, indicating overall changes in dew yields of between ±10% over the investigated time period.
- Published
- 2015
49. Computational Study of the Effect of Glyoxal–Sulfate Clustering on the Henry’s Law Coefficient of Glyoxal
- Author
-
Kurt V. Mikkelsen, Rainer Volkamer, Christopher J. Kampf, Eleanor M. Waxman, Jonas Elm, Theo Kurtén, and Nønne L. Prisle
- Subjects
010504 meteorology & atmospheric sciences ,010501 environmental sciences ,01 natural sciences ,chemistry.chemical_compound ,Computational chemistry ,Pressure ,Molecule ,Organic chemistry ,Computer Simulation ,Physical and Theoretical Chemistry ,Sulfate ,Equilibrium constant ,0105 earth and related environmental sciences ,Aerosols ,Aqueous solution ,Atmosphere ,Sulfates ,Aqueous two-phase system ,Water ,Glyoxal ,Henry's law ,Solvation shell ,Models, Chemical ,chemistry ,Solvents - Abstract
We have used quantum chemical methods to investigate the molecular mechanism behind the recently reported ( Kampf , C. J. ; Environ. Sci. Technol . 2013 , 47 , 4236 - 4244 ) strong dependence of the Henry's law coefficient of glyoxal (C2O2H2) on the sulfate concentration of the aqueous phase. Although the glyoxal molecule interacts only weakly with sulfate, its hydrated forms (C2O3H4 and C2O4H6) form strong complexes with sulfate, displacing water molecules from the solvation shell and increasing the uptake of glyoxal into sulfate-containing aqueous solutions, including sulfate-containing aerosol particles. This promotes the participation of glyoxal in reactions leading to secondary organic aerosol formation, especially in regions with high sulfate concentrations. We used our computed equilibrium constants for the complexation reactions to assess the magnitude of the Henry's law coefficient enhancement and found it to be in reasonable agreement with experimental results. This indicates that the complexation of glyoxal hydrates with sulfate can explain the observed uptake enhancement.
- Published
- 2014
50. Probing RbBr solvation in freestanding sub-2nm water clusters
- Author
-
Minna Patanen, Marko Huttula, Nønne L. Prisle, Kari Jänkälä, Mikko Heikki Mikkelä, Lauri Hautala, Paavo Turunen, and Maxim Tchaplyguine
- Subjects
010304 chemical physics ,Chemistry ,Solvation ,Analytical chemistry ,General Physics and Astronomy ,Synchrotron radiation ,010402 general chemistry ,01 natural sciences ,Spectral line ,0104 chemical sciences ,Solvent ,Concentration dependent ,Crystallography ,X-ray photoelectron spectroscopy ,0103 physical sciences ,Anhydrous ,Core level ,Physical and Theoretical Chemistry - Abstract
Concentration dependent solvation of RbBr in freestanding sub-2 nm water clusters was studied using core level photoelectron spectroscopy with synchrotron radiation. Spectral features recorded from dilute to saturated clusters indicate that either solvent shared or contact ion pairs are present in increasing amount when the concentration exceeds 2 mol kg−1. For comparison, spectra from anhydrous RbBr clusters are also presented.
- Published
- 2017
Catalog
Discovery Service for Jio Institute Digital Library
For full access to our library's resources, please sign in.