Quantification of the hygroscopic effect of soot aging in the atmosphere: laboratory simulations

We use a laboratory approach for the quantification of the water uptake by particles with varying amounts of sulfates to simulate the aging of fossil fuel combustion particles in the atmosphere. Diesel fuel and aviation kerosene laboratory-made soots are chosen as representative of the hydrophobic fraction of diesel and aircraft engine-emitted particulates and commercial carbon blacks are used as surrogates for industry emissions. The transformation of soot hydration properties from hydrophobic, through hydrophilic, to hygroscopic is demonstrated based on the amount of water uptake by the laboratory-produced EC soot covered by sulfates as the amount of sulfate increases. The mechanism of water/soot interaction changes from an adsorption on active sites to a water film formation and to the dissolution of water into the water-soluble sulfate, while the amount of sulfate increases. Laboratory simulations show that coverage of EC soot by organics diminishes the effect of sulfuric acid deposition. We demonstrate that the surface chemical properties and the size of primary particles affect the amount of water taken up by the soot particles and their aging in the atmosphere.     

Phase transitions and surface morphology of surfactant-coated aerosol particles

Probe molecule spectroscopy and hygroscopic growth curves characterize the morphology of surfactant-coated aerosol particles as a function of relative humidity (RH). This study focuses on particles composed of either potassium iodide or sodium chloride and sodium dodecyl sulfate (SDS). At high RH, these mixed particles assume a reverse micelle type structure, and at low RH, they comprise a solid core of either KI or NaCl coated with SDS and water. The deliquescence relative humidity (DRH) and efflorescence relative humidity (ERH) of the inorganic fraction of the mixed particles are very similar to those of the pure salts. The surface polarity and morphology sampled by the coumarin 314 probe molecule ranges from that of a water-organic interface to that of an ionic surface and depends strongly on the RH and the amount of SDS. When the SDS coverage of the droplet just prior to efflorescence reaches approximately one monolayer, a thin soap film persists on the surface to values of RH much lower than the ERH. Both the electronic spectroscopy and photoelectric charging efficiency show a separate efflorescence for this layer at RH < 5%. The spectroscopy further reveals that there is a hysteresis associated with this low RH phase transition for both KI and NaCl cores.     

Influence of adjusted hydrophilic–hydrophobic lengths in sulfonated multiblock copoly(ether sulfone) membranes for fuel cell application

Sulfonated multiblock copoly(ether sulfone)s applicable to proton exchange membrane fuel cells (PEMFCs) were synthesized by the coupling reaction of the hydroxyl‐terminated hydrophilic and hydrophobic oligomers with different lengths in the presence of highly reactive decafluorobiphenyl (DFB) as a chain extender to investigate the influence of each length on the membranes' properties, such as water uptake, proton conductivity, and morphology. Multiblock copolymers with high molecular weights (M_n > 50,000, M_w > 150,000) were obtained under mild reaction conditions. The resulting membranes demonstrated good oxidative stability for hot Fenton's reagent and maintained high water uptake (7.3–18.7 wt %) under a low relative humidity (50% RH). Proton conductivity of all membranes at 80 °C and 95% RH was higher than that of Nafion 117 membrane, and good proton conductivity of 7.0 × 10^?3 S/cm was obtained at 80 °C and 50% RH by optimizing the oligomer lengths. The surface morphology of the membranes was investigated by tapping mode atomic force microscopy (AFM), which showed that the multiblock copolymer membranes had a clearer surface hydrophilic/hydrophobic‐separated structure than that of the random copolymer, and contributed to good and effective proton conduction. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7332–7341, 2008     

Intrinsic adhesion properties of poly(vinyl pyrrolidone) to pharmaceutical materials: humidity effect

Poly(vinyl pyrrolidone) (PVP) is widely used for bioengineering and pharmaceutical applications, and its adhesion characteristics are critical. When used as a binder in pharmaceutical granulation, it covers the resultant granules and governs their surface properties. The intrinsic adhesion forces of PVP toward common hydrophobic (magnesium stearate) and hydrophilic (lactose) pharmaceutical materials have been studied as a function of relative humidity (RH). The effect of RH on adhesion force was more significant for the PVP/hydrophilic material than the PVP/hydrophobic material. Adhesion was lowest between 20 and 40% RH, and it increased at RH above 40% and below 20%. This is likely to be due to the development of capillary and triboelectrification forces, respectively. In a nano-indentation experiment using a silicon tip at room temperature, the PVP surface underwent a glass transition at 70% RH. This result suggests that surface softening contributes to the increased PVP adhesion at RH above 70%. To adjust the adhesion properties of PVP, humidity control should be an essential part of research and development. Effect of humidity on the adhesion forces between PVP and lactose (LT) or magnesium stearate (MS).     

Friction and adhesion forces of Bacillus thuringiensis spores on planar surfaces in atmospheric systems

The kinetic friction force and the adhesion force of Bacillus thuringiensis spores on planar surfaces in atmospheric systems were studied using atomic force microscopy. The influence of relative humidity (RH) on these forces varied for different surface properties including hydrophobicity, roughness, and surface charge. The friction force of the spore was greater on a rougher surface than on mica, which is atomically flat. As RH increases, the friction force of the spores decreases on mica whereas it increases on rough surfaces. The influence of RH on the interaction forces between hydrophobic surfaces is not as strong as for hydrophilic surfaces. The friction force of the spore is linear to the sum of the adhesion force and normal load on the hydrophobic surface. The poorly defined surface structure of the spore and the adsorption of contaminants from the surrounding atmosphere are believed to cause a discrepancy between the calculated and measured adhesion forces.     

Reactive uptake of nitric acid onto sodium chloride aerosols across a wide range of relative humidities

Reactive uptake coefficients for nitric acid onto size-selected (d(ve) = 102 and 233 nm) sodium chloride aerosols are determined for relative humidities (RH) between 85% and 10%. Both pure sodium chloride and sodium chloride mixed with magnesium chloride (X(Mg/Na) = 0.114, typical of sea salt) are studied. The aerosol is equilibrated with a carrier gas stream at the desired RH and then mixed with nitric acid vapor at a concentration of 60 ppb in a laminar flow tube reactor. At the end of the reactor, the particle composition is determined in real time with a laser ablation single particle mass spectrometer. For relative humidities above the efflorescence relative humidity (ERH), the particles exist as liquid droplets and the uptake coefficient ranges from 0.05 at 85% RH to >0.1 near the ERH. The droplet sizes, relative humidity and composition dependencies, are readily predicted by thermodynamics. For relative humidities below the ERH, the particles are nominally "solid" and uptake depends on the amount of surface adsorbed water (SAW). The addition of magnesium chloride to the particle phase (0.114 mole ratio of magnesium to sodium) facilitates uptake by increasing the amount of SAW. In the presence of magnesium chloride, the uptake coefficient remains high (>0.1) down to 10% RH, suggesting that the displacement of chloride by nitrate in fine sea salt particles is efficient over the entire range of conditions in the ambient marine environment. In the marine boundary layer, displacement of chloride by nitrate in fine sea salt particles should be nearly complete within a few hours (faster in polluted areas)-a time scale much shorter than the particle residence time in the atmosphere.     

Grand canonical Monte Carlo simulation of the adsorption isotherms of water molecules on model soot particles

The grand canonical Monte Carlo method is used to simulate the adsorption isotherms of water molecules on different types of model soot particles. The soot particles are modeled by graphite-type layers arranged in an onionlike structure that contains randomly distributed hydrophilic sites, such as OH and COOH groups. The calculated water adsorption isotherm at 298 K exhibits different characteristic shapes depending both on the type and the location of the hydrophilic sites and also on the size of the pores inside the soot particle. The different shapes of the adsorption isotherms result from different ways of water aggregation in or/and around the soot particle. The present results show the very weak influence of the OH sites on the water adsorption process when compared to the COOH sites. The results of these simulations can help in interpreting the experimental isotherms of water adsorbed on aircraft soot.     

Capillary force in atomic force microscopy

Under ambient conditions, a water meniscus generally forms between a nanoscale atomic force microscope tip and a hydrophilic surface. Using a lattice gas model for water and thermodynamic integration methods, we calculate the capillary force due to the water meniscus for both hydrophobic and hydrophilic tips at various humidities. As humidity rises, the pull-off force rapidly reaches a plateau value for a hydrophobic tip but monotonically increases for a weakly hydrophilic tip. For a strongly hydrophilic tip, the force increases at low humidities (<30%) and then decreases. We show that mean-field density functional theory reproduces the simulated pull-off force very well.     

Internal structure, hygroscopic and reactive properties of mixed sodium methanesulfonate-sodium chloride particles

Internal structures, hygroscopic properties and heterogeneous reactivity of mixed CH(3)SO(3)Na/NaCl particles were investigated using a combination of computer modeling and experimental approaches. Surfactant properties of CH(3)SO(3)(-) ions and their surface accumulation in wet, deliquesced particles were assessed using molecular dynamics (MD) simulations and surface tension measurements. Internal structures of dry CH(3)SO(3)Na/NaCl particles were investigated using scanning electron microscopy (SEM) assisted with X-ray microanalysis mapping, and time-of-flight secondary ion mass spectrometry (TOF-SIMS). The combination of these techniques shows that dry CH(3)SO(3)Na/NaCl particles are composed of a NaCl core surrounded by a CH(3)SO(3)Na shell. Hygroscopic growth, deliquescence and efflorescence phase transitions of mixed CH(3)SO(3)Na/NaCl particles were determined and compared to those of pure NaCl particles. These results indicate that particles undergo a two step deliquescence transition: first at ～69% relative humidity (RH) the CH(3)SO(3)Na shell takes up water, and then at ～75% RH the NaCl core deliquesces. Reactive uptake coefficients for the particle-HNO(3) heterogeneous reaction were determined at different CH(3)SO(3)Na/NaCl mixing ratios and RH. The net reaction probability decreased notably with increasing CH(3)SO(3)Na and at lower RH.     

Investigations of the hygroscopic properties of ammonium sulfate and mixed ammonium sulfate and glutaric acid micro droplets by means of optical levitation and Raman spectroscopy

In the presented work an optical levitation technique performed by means of a focused laser beam, Mie and Raman spectroscopy have been utilized for measuring hygroscopic growth curves and composition of laboratory generated single ammonium sulfate (AS) and internally mixed ammonium sulfate-glutaric acid (GA) droplets in the micrometer range. The generated particles have been found to immediately supersaturate (above 45wt% for AS) at 297 K after capturing in the laser beam. Further increase of the relative humidity (RH) up to 85% does not dilute the droplets under the saturation point. A spontaneous hygroscopic growth takes place at 73.5-78% RH for pure AS. The particle grows with an average factor of 1.62 at the deliquescence relative humidity (DRH). Efflorescence of AS occurs at 43% RH with a corresponding concentration of more than 85wt%. Independent of the mixing ratios in ranges 25/75, 50/50, 75/25% AS/GA mixed particles don't exist as a metastable supersaturated solution droplets in the 35-85% RH range. Instead of growing with increasing relative humidity internally mixed particles build up a solid crystalline layer on the surface. This crystalline phase is not further influenced by ambient relative humidities.     

Hygroscopic growth of multicomponent aerosol particles influenced by several cycles of relative humidity

Infrared aerosol flow tube experiments were performed for mixtures of ammonium, sulfate, and hydrogen ions at 293 K. The impact of the cycling of relative humidity (RH) on the crystals formed and on the hygroscopic growth was evaluated. Submicron particles having an extent of neutralization (X) between 0.60 and 0.75 were the focus, with special emphasis on the composition of aqueous letovicite (NH4)3H(SO4)2 (X = 0.75) because of its unique behavior. Aqueous letovicite particles crystallized initially as an external mixture of solid particles, forming pure particles of letovicite (NH4)3H(SO4)2(s) (LET) in some cases and internally mixed particles of ammonium sulfate ((NH4)2SO4(s);AS) and ammonium bisulfate (NH4HSO4(s); AHS) in other cases. Cycling between 3% and 48% RH increased the fraction of LET particles in the aerosol population, moving in the direction of the more thermodynamically favored species. However, some internally mixed particles remained even after multiple cycles, possibly indicative of a memory effect of AS as a heterogeneous nucleus for AHS. For all compositions studied, the RH of first water uptake and the magnitude of water uptake at higher RH were compared to model predictions. As expected, the more acidic particles (X = 0.60 and 0.65) took up water at the eutonic RH (37%) of mixed AHS/LET particles, but not as expected, both solids dissolved completely, arguing for an increased water solubility possibly attributable to nanocrystalline materials. Particles of X = 0.70 took up water above 41% RH, suggesting a particle morphology of an outer coating of AHS that prevents water uptake at the lower eutonic RH values of mixed AHS/LET and AHS/AS particles. Particles of X = 0.75 took up water as expected for an externally mixed particle population of LET and AS/AHS particles, although the fraction of each type in the population depended on the RH history. These results show that the hysteresis effect for some particles depends on a multi-node RH history. The implication for atmospheric particles is that the crystals present therein as well as particle morphology, water content, and extent of internal/external mixing might continue to evolve during multiple atmospheric cycles of RH.     

Reversible uptake of water on NaCl nanoparticles at relative humidity below deliquescence point observed by noncontact environmental atomic force microscopy

The behavior of NaCl nanoparticles as a function of relative humidity (RH) has been characterized using non-contact environmental atomic force microscopy (e-AFM) to measure the heights of particles deposited on a prepared hydrophobic surface. Cubic NaCl nanoparticles with sides of 35 and 80 nm were found to take up water reversibly with increasing RH well below the bulk deliquescence relative humidity (DRH) of 75% at 23(°)C, and to form a liquid-like surface layer of thickness 2 to 5 nm, with measurable uptake (>2 nm increase in particle height) beginning at 70% RH. The maximum thickness of the layer increased with increasing RH and increasing particle size over the range studied. The liquid-like behavior of the layer was indicated by a reversible rounding at the upper surface of the particles, fit to a parabolic cross-section, where the ratio of particle height to maximum radius of curvature increases from zero (flat top) at 68% RH to 0.7 ± 0.3 at 74% RH. These observations, which are consistent with a reorganization of mass on the solid NaCl nanocrystal at RH below the DRH, suggest that the deliquescence of NaCl nanoparticles is more complex than an abrupt first-order phase transition. The height measurements are consistent with a phenomenological model that assumes favorable contributions to the free energy of formation of a liquid layer on solid NaCl due both to van der Waals interactions, which depend partly upon the Hamaker constant, A(film), of the interaction between the thin liquid film and the solid NaCl, and to a longer-range electrostatic interaction over a characteristic length of persistence, ξ; the best fit to the data corresponded to A(film)= 1 kT and ξ = 2.33 nm.     

Heterogeneous chemistry of organic acids on soot surfaces

We have investigated the heterogeneous interaction between a number of carboxylic acids and soot generated from different fuel sources and formation mechanisms. A low-pressure fast flow reactor in conjunction with ion drift-chemical ionization mass spectrometry detection was employed to study uptake of monocarboxylic (benzoic, oleic, and steric) and dicarboxylic (glutaric, maleic, oxalic, and phthalic) acids on deposited soot surfaces formed by combustion of methane, propane, and kerosene. Most acids exhibited irreversible uptake on the soot surfaces and the uptake coefficient was measured in the range of 9 x 10(-4) to 1 x 10(-1) estimated based on the geometric surface areas. Brunauer, Emmett, and Teller surface areas of the deposited soot surfaces were measured and the soot bulk and surface chemical compositions were evaluated with Fourier transform infrared spectroscopy and attenuated total reflection spectroscopy. Plausible uptake mechanisms were discussed on the basis of the measured soot physiochemical properties by comparing the mono and dicarboxylic acids.     

Nanoscale Wetting of Single Viruses

The epidemic spread of many viral infections is mediated by the environmental conditions and influenced by the ambient humidity. Single virus particles have been mainly visualized by atomic force microscopy (AFM) in liquid conditions, where the effect of the relative humidity on virus topography and surface cannot be systematically assessed. In this work, we employed multi-frequency AFM, simultaneously with standard topography imaging, to study the nanoscale wetting of individual Tobacco Mosaic virions (TMV) from ambient relative humidity to water condensation (RH > 100%). We recorded amplitude and phase vs. distance curves (APD curves) on top of single virions at various RH and converted them into force vs. distance curves. The high sensitivity of multifrequency AFM to visualize condensed water and sub-micrometer droplets, filling gaps between individual TMV particles at RH > 100%, is demonstrated. Dynamic force spectroscopy allows detecting a thin water layer of thickness ~1 nm, adsorbed on the outer surface of single TMV particles at RH < 60%.     

Switching and structuring of binary reactive polymer brush layers

Switchable binary polymer brushes grafted to Si-wafers were prepared from hydrophilic and hydrophobic polymer components. When exposed to solvents, either the hydrophobic or the hydrophilic component extends in to the liquid phase, depending on the polarity of the solvent. The hydrophilic component was poly-2-vinylpyridine; the hydrophobic component was made photocrosslinkable in that a polystyrene copolymer containing a photodimerizing chromophore was used. In this system surfaces differing in water contact angle between 60° and 100° can be produced by variation of the solvent. The chromophore was phenylindene, which forms crosslinks upon direct UV-irradiation. Therefore, the polystyrene component can be fixed in the extended or collapsed state. It will be shown that by irradiation through an appropriate mask, surfaces can be structured and the structures fixed. In both the systems structural patterns differing in surface properties were produced and fixed photochemically.     

Effect of relative humidity on OH uptake by surfaces of atmospheric importance

An experimental study of the dependence of the OH uptake coefficient gamma OH over a relative humidity of 0-48% was carried out at 100 Torr and room temperature, using a differential bead-filled flow tube coupled to a high-pressure chemical ionization mass spectrometer. Various organic (paraffin wax, pyrene, glutaric acid, and soot) and inorganic (NaCl, KCl, MgCl2, CaCl2, Na2SO4, and sea salt) surfaces served as proxies for tropospheric aerosols. A virtual cylindrical flow tube approximation and a surface coating dilution technique were successfully employed in the study, which included measurements of high radical uptake with an initial probability of near unity. For inorganic salts, the effect of water vapor, enhancement or inhibition of gamma OH, was found to be dependent on the blocking of anions and changes in surface pH. Although OH uptake by NaCl, the major component of sea-salt aerosols, is weakly dependent on water vapor, it is enhanced by a factor of approximately 2 for MgCl2 and determines the net relative humidity dependence of the radical uptake on sea salt, which is enhanced by a factor of approximately 4. For the organic surfaces studied, the enhancement effect of a factor 4 was also observed only for a hydrophilic organic surface, namely, glutaric acid. Results of the uptake studies suggest that the effect of relative humidity is important and should be accounted for in atmospheric modeling of tropospheric aerosol chemistry.     

Kinetic Studies of Heterogeneous Reaction of HO2 Radical by Dicarboxylic Acid Particles

The HO₂ uptake coefficients (γ) for organic submicron aerosol particles were measured using an aerosol flow tube coupled with a chemical conversion/laser‐induced fluorescence technique under ambient conditions (760 Torr and 296 ± 2 K) and different values of relative humidity (RH) (28% and 68%). Determined uptake coefficients for succinic, glutaric, adipic, and pimelic acid aerosol particles at 28% RH were 0.07 ± 0.02, 0.07 ± 0.03, 0.02 ± 0.01, and 0.06 ± 0.03, respectively, whereas the γ values for those particles at 68% RH were 0.18 ± 0.07, 0.15 ± 0.04, 0.06 ± 0.01, and 0.13 ± 0.04, respectively. An increase in γ with increasing RH was observed for all the dicarboxylic acids, suggesting a contribution by water amount in the particle, aqueous phase chemistry, and uptake of HO₂–H₂O. The anomalously low γ values for adipic acid are likely related to its high crystallization RH and thus provide a new clue that the water amount and/or RH have a significant influence on HO₂ uptake.     

Effect of sodium dodecyl sulfate at different hydration conditions on dioleoyl phosphatidylcholine bilayers studied by grazing incidence X-ray diffraction

The effect of the surfactant content and hydration conditions in the phases of dioleoyl phosphatidylcoline (DOPC)/sodium dodecyl sulfate (SDS) mixtures was studied. To this end, surface X-ray diffraction experiments have been performed on bilayers of the mixtures deposited on hydrophobic silicon wafers by dip coating. To investigate the effect of relative humidity (RH) on bilayer organization, a humidity chamber with dry-wet air control was used, and RH values were fixed between 1 and 65%. Our results showed, in addition to the lamellar phase, a rhombohedral phase in mixtures at low hydration conditions (RH < 30%). The d spacing between lamellae increased with the RH and SDS content. This fact could be associated with a swelling effect that is probably due to the localization of water molecules between the polar headgroups of the DOPC and SDS forming the bilayers. The electron-density profiles calculated by Fourier reconstruction of the lamellar stacking for the different samples also confirmed this fact. In addition, the increase in d spacing could be related to the increase in the hydrophilic character of the mixture when the SDS content increases. The rhombohedral phase was more clearly observed in mixtures with high SDS content. Thus, the stalk structure of the rhombohedral phase could be facilitated because of the SDS contribution to inverse structures.     

Use of inverse gas chromatography to characterize cotton fabrics and their interactions with fragrance molecules at controlled relative humidity

The present work focused on the surface characterization and fragrance interactions of a common cotton towel at different relative humidities (RHs) using inverse gas chromatography (IGC) and dynamic vapour sorption. The sigmoidal water sorption isotherms showed a maximum of 16% (w/w) water uptake with limited swelling at 100% RH. This means that water interacts strongly with cotton and might change its initial physico-chemical properties. The same cotton towel was then packed in a glass column and characterized by IGC at different relative humidities, calculating the dispersive and specific surface energy components. The dispersive component of the surface energy decreases slightly as a function of relative humidity (42 mJ/m2 at 0% RH to 36 mJ/m2 at 80% RH) which would be expected from swelling of the humidified cotton. The Gutmann's donor constant Kd increased from 0.28 kJ/mol at 0% RH to 0.42 kJ/mol at 80% RH, indicating that a greater hydrophilic surface exists at 80% RH, which is also as expected. Water, undecane and four fragrance molecules (dimetol, benzyl acetate, decanal and phenylethanol) were used to investigate cotton-fragrance interactions between 0 and 80% RH. The adsorption enthalpies and the Henry's constants were calculated and are discussed. The higher values for the adsorption enthalpies of polar molecules such as dimetol and phenylethanol suggest the presence of hydrogen bonds as the main adsorption mechanism. The Henry's constant of dimetol was also determined by headspace gas chromatography measurements at 20% RH, giving a similar value (230 nmol/Pa g by IGC and 130 nmol/Pa g by headspace GC), supporting the usefulness of IGC for such determinations. This work confirms the usefulness of chromatographic methods to investigate biopolymers such as textiles, starches and hairs.     

海盐颗粒物表面的NO_2非均相反应

为了深入理解沿海城市大气环境中NO2和海盐颗粒物的非均相反应规律,本研究使用漫反射红外傅立叶变换光谱(DRIFTS)比较研究了0%和20%相对湿度(relative humidty,RH)下NO2在湿海盐颗粒物表面的非均相反应.动力学测量表明硝酸盐的生成对NO2是二级反应,并且0%和20%相对湿度条件下,NO2分子浓度为1.96×1015molcules·cm-3时,反应增长阶段反应摄取系数分别为(5.51±0.19)×10-7和1.26×10-6.结果还显示相对湿度在30%以下时,海盐表面MgCl2·6H2O、CaCl2·2H2O所在点位通过释放结合水和吸附水汽,在海盐表面形成液态水的斑点,增强了反应持续能力.因此氯化钠表面非均相反应的研究可能会低估海盐颗粒物的非均相反应活性.