Surface tension of atmospheric wet aerosol and cloud/fog droplets in relation to their organic carbon content and chemical composition (original) (raw)
Related papers
The surface tension of aqueous solutions of some atmospheric water-soluble organic compounds
Atmospheric Environment, 2004
The surface tensions of aqueous solutions of levoglucosan, 3-hydroxybutanoic acid, 3-hydroxybenzoic acid, azelaic acid, pinonic acid, and humic acid have been measured. These compounds are suggested as model substances for the water-soluble organic compounds (WSOC) in atmospheric aerosols and droplets which may play an important role in the aerosol cycle because of their surface-active potentials. The reductions in surface tension induced by single and mixed WSOC in aqueous solution of pure water is remarkable. However, the results of this investigation cannot explain the strong reduction in surface tension in real cloud and fog water samples at concentrations of WSOC below 1 mg/mL.
Journal of Geophysical Research: Atmospheres, 2006
Humic-like substances (HULIS) were isolated by a solid-phase extraction procedure from PM2.5 fraction urban-type atmospheric aerosol samples collected in downtown Budapest, Hungary, in the nonheating season. Their amount was derived, and the surface tension properties of their pure solutions were investigated. Carbon content of HULIS accounted for 54% of the water-soluble organic carbon and for 19% of organic carbon in the aerosol. Solution of pure HULIS in concentrations corresponding to real incipient cloud droplets decreased the surface tension of water by about 30%, and the major decrease occurred within several tens of seconds. In diluted solutions, however, the thermodynamic equilibrium in surface tension was only reached after several hours, but the equilibrium depression value was still remarkable, about 18%. Detailed analysis of the relaxation curves implied that the kinetics of the surface tension depression should be regarded as and described by a diffusion-controlled process. The surface tension curves as a function of the HULIS concentration after an elapsed time of up to about 100 s resembled the curves observed earlier, but the shape of and tendency in the equilibrium curve (the isotherm) was rather different. The deviations were linked to physicochemical properties of certain classes of compounds within the HULIS. The surface tension depended on the solution pH as well; the smallest depression was observed at about pH = 5, and it was increased by an additional 13% for strong acidic or basic conditions; hence the role of surface tension in cloud droplet formation under acid rain conditions is further amplified.
Atmospheric Environment, 2007
Elemental analysis, Fourier transform infrared coupled to attenuated total reflectance (FTIR-ATR) and solid-state cross polarization with magic angle spinning-13 C-nuclear magnetic resonance (CPMAS 13 C NMR) spectroscopies were used to compare the chemical features of water-soluble organic compounds (WSOC) from atmospheric aerosols with those of aquatic humic and fulvic acids. The influence of different meteorological conditions on the structural composition of aerosol WSOC was also evaluated. Prior to the structural characterisation, the WSOC samples were separated into hydrophobic acids and hydrophilic acids fractions by using a XAD-8/XAD-4 isolation procedure. Results showed that WSOC hydrophobic acids are mostly aliphatic (40-62% of total NMR peak area), followed by oxygenated alkyls (15-21%) and carboxylic acid (5.4-13.4%) functional groups. Moreover, the aromatic content of aerosol WSOC samples collected between autumn and winter seasons is higher ($18-19%) than that of samples collected during warmer periods ($6-10%). The presence of aromatic signals typical of lignin-derived structures in samples collected during low-temperature conditions highlights the major contribution of wood burning processes in domestic fireplaces into the bulk chemical properties of WSOC from aerosols. According to our investigations, aerosol WSOC hydrophobic acids and aquatic fulvic and humic acids hold similar carbon functional groups; however, they differ in terms of the relative carbon distribution. Elemental analysis indicates that H and N contents of WSOC hydrophobic acids samples surpass those of aquatic fulvic and humic acids. In general, the obtained results suggest that WSOC hydrophobic acids have a higher aliphatic character and a lower degree of oxidation than those of standard fulvic and humic acids. The study here reported suggests that aquatic fulvic and humic acids may not be good models for WSOC from airborne particulate matter.
Reviews of Geophysics, 1983
Surface-active organic molecules are common constituents of atmospheric aerosol particles, raindrops, and snowflakes. If these compounds are present as surface films, transfer of gases into the atmospheric water systems could be impeded, evaporation could be slowed, and the aqueous chemical reactions could be influenced. To investigate these possibilities, we have reviewed the chemical literature pertaining to organic films on aqueous surfaces: their composition, structure, properties, and effects. We then review the surface-active organic compounds in atmospheric water. We report the results of new measurements of surface tension of aqueous solutions of common atmospheric organic compounds (fi-pinene, n-hexanol, eugenol, and anethole) and demonstrate that the compounds produce films with properties similar to those of the more well known surfactants. We conclude that organic films are probably common on atmospheric aerosol particles and that they may occur under certain circumstances on fog droplets, cloud droplets, and snowflakes. If present, they will increase the lifetimes of aerosol particles, fog droplets, and cloud droplets, both by inhibiting water vapor evaporation and by reducing the efficiency with which these atmospheric components are scavenged. The presence of the films will not cause a significant reduction of solar radiation within the aqueous solution. It appears likely, however, that the transport of gaseous molecules into and out of the aqueous solution will be impeded by factors of several hundred or more when organic films are present. Since incorporated gas molecules provide much of the oxidizing potential of atmospheric water droplets, the organic films will play a major role in droplet chemistry by strongly inhibiting solution oxidation.
Journal of Geophysical Research: Atmospheres, 2016
Size-resolved fog water samples were collected in two consecutive winters at Kanpur, a heavily polluted urban area of India. Samples were analyzed by an aerosol mass spectrometer after drying and directly in other instruments. Residues of fine fog droplets (diameter: 4-16 μm) are found to be more enriched with oxidized (oxygen to carbon ratio, O/C = 0.88) and low volatility organics than residues of coarse (diameter > 22 μm) and medium size (diameter: 16-22 μm) droplets with O/C of 0.68 and 0.74, respectively. These O/C ratios are much higher than those observed for background ambient organic aerosols, indicating efficient oxidation in fog water. Accompanying box model simulations reveal that longer residence times, together with high aqueous OH concentrations in fine droplets, can explain these trends. High aqueous OH concentrations in smaller droplets are caused by their highest surface-volume ratio and high Fe and Cu concentrations, allowing more uptake of gas phase OH and enhanced Fenton reaction rates, respectively. Although some volatile organic species may have escaped during droplet evaporation, these findings indicate that aqueous processing of dissolved organics varies with droplet size. Therefore, large (regional, global)-scale models need to consider the variable reaction rates, together with metal-catalyzed radical formation throughout droplet populations for accurately predicting aqueous secondary organic aerosol formation.
Atmospheric Environment - ATMOS ENVIRON, 2002
A novel approach is described for the fractionation of water-soluble organic carbon (WSOC) in atmospheric aerosols and cloud drops. The method is based on the preliminary adsorption of the sample, acidified at pH 2, on a polymeric styrene-divinylbenzene resin (XAD-2) and subsequent elution with a series of solvents, which leads to the fractionation of the sample into three classes of compounds. The method was set up using synthetic mixtures of organic compounds and then applied to selected samples of atmospheric aerosols and cloud drops. All samples and collected fractions were analysed using size exclusion chromatography (SEC). This method proved particularly useful both in providing information on the organic content of the samples and for the characterisation of the macromolecular compounds (MMCs) in the samples. Synthetic samples were prepared using humic, fulvic and tannic acid to simulate naturally occurring MMCs. In the first fraction, eluted with HCl, only the most soluble organic compounds (oxalic acid, formic acid and acetic acid) were collected. In the second fraction, eluted with methanol, the major part of the organic material was collected together with the more hydrophilic constituents of the humic substances. In the third fraction, it was possible to separately recover the more hydrophobic component of the humic substances. A large number of atmospheric samples (fog, aerosol, cloud) were then analysed using SEC. Most of these samples evidenced a noteworthy chromatogram at 254 nm. Moreover, the chromatographic area evidenced a clear linear correlation with the total organic carbon (TOC) values. The fractionation method on XAD-2 was finally applied to selected atmospheric samples, yielding three classes of organic compounds. In each sample, a non-negligible amount of compounds with dimensional and chemical properties similar to humic substances were collected in the third fraction. The carbon content in this latter fraction was estimated both by TOC and by means of the correlation between TOC and SEC area. r
Solubility properties of surfactants in atmospheric aerosol and cloud/fog water samples
Journal of Geophysical Research, 2003
1] Organic films on deliquesced aerosols and cloud droplets lower the surface tension of water and may inhibit the exchange of water vapor and gases between the gas and the liquid phase, with important implications for aerosol and cloud microphysics and heterogeneous chemistry. This study provides an estimate of the solubility properties of surfactants in aerosol and fog/cloud water samples on the basis of the dilatational rheological properties of the surface films. The variations of surface tension induced by the fast expansion/compression of the films were measured by means of a drop shape tensiometer and were linked to the capacity of surfactants to exchange between the surface layer and bulk solution, and ultimately to their water-solubility. The results are in agreement with the properties of standards of soluble surfactants and can be interpreted by the theory of formation of hydrophilic adsorption layers. These findings suggest that the water-soluble organic compounds (WSOC) are the main contributors to the formation of films on cloud/fog droplets. It follows that the surface coverage of film-forming compounds is mainly controlled by the bulk concentration of WSOC, regardless of the available surface area. This also supports that the surface tension decreases observed under laboratory conditions actually occur in the atmosphere. Citation: Decesari, S., M. C. Facchini, M. Mircea, F. Cavalli, and S. Fuzzi, Solubility properties of surfactants in atmospheric aerosol and cloud/fog water samples,
Wetting of Hydrophobic Organic Surfaces and Its Implications to Organic Aerosols in the Atmosphere
The Journal of Physical Chemistry A, 2000
The interaction between water and organic substances is of extreme importance in physical, biological, and geological chemistries. Understanding the interactions between water and organic interfaces is one of the earliest chemical quandaries. In this research, self-assembled monolayers (SAMs) were used as a tool to investigate the interaction between water molecules and hydrophobic surfaces. Real-time adsorption and desorption kinetics of water on hydrophobic SAM surfaces was monitored using a new type of field effect transistor (FET)-like device called MOCSER (molecular controlled semiconductor resistor) coated with SAMs. A quartz crystal microbalance (QCM) was used as a complementary technique to give an estimate of total water mass adsorbed. It is shown that water adsorption depends on relative humidity and is reversible. The amount of adsorbed water increased with surface corrugation. The measurements suggest that adsorption takes place as small water clusters, originating on irregularities on the surface organic layer. Molecular dynamics simulations were carried out to study the interactions of water and hydrophobic surfaces as well. These simulations also suggest the formation of water microdroplets on hydrophobic surfaces, and indicate a strong correlation between increased surface corrugation and adsorption. This paper examines the possible consequences of these interactions on the properties of organic aerosols in the troposphere.
Atmospheric Chemistry and Physics, 2005
Critical supersaturations for internally mixed particles of adipic acid, succinic acid and sodium chloride were determined experimentally for dry particles sizes in the range 40-130 nm. Surface tensions of aqueous solutions of the dicarboxylic acids and sodium chloride corresponding to concentrations at activation were measured and parameterized as a function of carbon content. The activation of solid particles as well as solution droplets were studied and particle phase was found to be important for the critical supersaturation. Experimental data were modelled using Köhler theory modified to account for limited solubility and surface tension lowering.