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Sample records for air-water interface awi

  1. Methylglyoxal at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Wren, S. N.; Gordon, B. P.; McWilliams, L.; Valley, N. A.; Richmond, G.

    2014-12-01

    Recently, it has been suggested that aqueous-phase processing of atmospheric α-dicarbonyl compounds such as methylglyoxal (MG) could constitute an important source of secondary organic aerosol (SOA). The uptake of MG to aqueous particles is higher than expected due to the fact that its carbonyl moieties can hydrate to form diols, as well as the fact that MG can undergo aldol condensation reactions to form larger oligomers in solution. MG is known to be surface active but an improved description of its surface behaviour is crucial to understanding MG-SOA formation, in addition to understanding its gas-to-particle partitioning and cloud forming potential. Here, we employ a combined experimental and theoretical approach involving vibrational sum frequency generation spectroscopy (VSFS), surface tensiometry, molecular dynamics simulations, and density functional theory calculations to study MG's surface adsorption, in both the presence and absence of salts. We are particularly interested in determining MG's hydration state at the surface. Our experimental results indicate that MG slowly adsorbs to the air-water interface and strongly perturbs the water structure there. This perturbation is enhanced in the presence of NaCl. Together our experimental and theoretical results suggest that singly-hydrated MG is the dominant form of MG at the surface.

  2. Method for Collecting Air-Water Interface Microbes Suitable for Subsequent Microscopy and Molecular Analysis in both Research and Teaching Laboratories

    PubMed Central

    Henk, Margaret C.

    2004-01-01

    A method has been developed for collecting air-water interface (AWI) microbes and biofilms that enables analysis of the same sample with various combinations of bright-field and fluorescence light microscopy optics, scanning and transmission electron microscopy (TEM), and atomic force microscopy. The identical sample is then subjected to molecular analysis. The sampling tool consists of a microscope slide supporting appropriate substrates, TEM grids, for example, that are removable for the desired protocols. The slide with its substrates is then coated with a collodion polymer membrane to which in situ AWI organisms adhere upon contact. This sampling device effectively separates the captured AWI bacterial community from the bulk water community immediately subtending. Preliminary data indicate that the AWI community differs significantly from the water column community from the same sample site when both are evaluated with microscopy and with 16S ribosomal DNA sequence-based culture-independent comparisons. This microbe collection method can be used at many levels in research and teaching. PMID:15066847

  3. Non-contact microrheology at the air-water interface

    NASA Astrophysics Data System (ADS)

    Boatwright, Thomas; Shlomovitz, Roie; Levine, Alex; Dennin, Michael

    2012-02-01

    Mechanical properties of biological interfaces, such as cell membranes, have the potential to be measured with optical tweezers. We report on an approach to measure air-water interfacial properties through microrheology of particles near, but not contacting, the surface. An inverted optical tweezer traps beads of micron size or greater in the bulk, and can then translate them perpendicular to the interface. Through the measurement of thermally driven fluctuations, the mobility of the particle is found to vary as a function of submerged depth and the boundary conditions at the interface. Near a rigid wall, the mobility is confirmed to decrease in a way consistent with Faxèn's law. Very close to the free air-water interface, the mobility changes with the opposite sign, increasing by about 30% at the surface, consistent with recent calculations by Shlomovitz and Levine. In addition, the presence of a Langmuir monolayer at the interface is found to significantly change the mobility of the particle close to the interface. With an accurate theory, it should be possible to infer the shear modulus of a monolayer from the fluctuations of the particle beneath the interface. Since particles are not embedded in the monolayer, this technique avoids impacting the system of study.

  4. Proton Transfers at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Mishra, Himanshu

    Proton transfer reactions at the interface of water with hydrophobic media, such as air or lipids, are ubiquitous on our planet. These reactions orchestrate a host of vital phenomena in the environment including, for example, acidification of clouds, enzymatic catalysis, chemistries of aerosol and atmospheric gases, and bioenergetic transduction. Despite their importance, however, quantitative details underlying these interactions have remained unclear. Deeper insight into these interfacial reactions is also required in addressing challenges in green chemistry, improved water quality, self-assembly of materials, the next generation of micro-nanofluidics, adhesives, coatings, catalysts, and electrodes. This thesis describes experimental and theoretical investigation of proton transfer reactions at the air-water interface as a function of hydration gradients, electrochemical potential, and electrostatics. Since emerging insights hold at the lipid-water interface as well, this work is also expected to aid understanding of complex biological phenomena associated with proton migration across membranes. Based on our current understanding, it is known that the physicochemical properties of the gas-phase water are drastically different from those of bulk water. For example, the gas-phase hydronium ion, H3O +(g), can protonate most (non-alkane) organic species, whereas H 3O+(aq) can neutralize only relatively strong bases. Thus, to be able to understand and engineer water-hydrophobe interfaces, it is imperative to investigate this fluctuating region of molecular thickness wherein the 'function' of chemical species transitions from one phase to another via steep gradients in hydration, dielectric constant, and density. Aqueous interfaces are difficult to approach by current experimental techniques because designing experiments to specifically sample interfacial layers (< 1 nm thick) is an arduous task. While recent advances in surface-specific spectroscopies have provided

  5. Powder wettability at a static air-water interface.

    PubMed

    Dupas, Julien; Forny, Laurent; Ramaioli, Marco

    2015-06-15

    The reconstitution of a beverage from a dehydrated powder involves several physical mechanisms that determine the practical difficulty to obtain a homogeneous drink in a convenient way and within an acceptable time for the preparation of a beverage. When pouring powder onto static water, the first hurdle to overcome is the air-water interface. We propose a model to predict the percentage of powder crossing the interface in 45 s, namely the duration relevant for this application. We highlight theoretically the determinant role of the contact angle and of the particle size distribution. We validate experimentally the model for single spheres and use it to predict the wettability performance of commercial food powders for different contact angles and particles sizes. A good agreement is obtained when comparing the predictions and the wettability of the tested powders. PMID:25721855

  6. Microscopic dynamics of nanoparticle monolayers at air-water interface.

    PubMed

    Bhattacharya, R; Basu, J K

    2013-04-15

    We present results of surface mechanical and particle tracking measurements of nanoparticles trapped at the air-water interface as a function of their areal density. We monitor both the surface pressure (Π) and isothermal compression modulus (ϵ) as well as the dynamics of nanoparticle clusters, using fluorescence confocal microscopy while they are compressed to very high density near the two dimensional close packing density Φ∼0.82. We observe non-monotonic variation in both ϵ and the dynamic heterogeneity, characterized by the dynamical susceptibility χ4 with Φ, in such high density monolayers. We provide insight into the underlying nature of such transitions in close packed high density nanoparticle monolayers in terms of the morphology and flexibility of these soft colloidal particles. We discuss the significance our results in the context of related studies on two dimensional granular or colloidal systems. PMID:23411354

  7. Proton Transfers at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Mishra, Himanshu

    Proton transfer reactions at the interface of water with hydrophobic media, such as air or lipids, are ubiquitous on our planet. These reactions orchestrate a host of vital phenomena in the environment including, for example, acidification of clouds, enzymatic catalysis, chemistries of aerosol and atmospheric gases, and bioenergetic transduction. Despite their importance, however, quantitative details underlying these interactions have remained unclear. Deeper insight into these interfacial reactions is also required in addressing challenges in green chemistry, improved water quality, self-assembly of materials, the next generation of micro-nanofluidics, adhesives, coatings, catalysts, and electrodes. This thesis describes experimental and theoretical investigation of proton transfer reactions at the air-water interface as a function of hydration gradients, electrochemical potential, and electrostatics. Since emerging insights hold at the lipid-water interface as well, this work is also expected to aid understanding of complex biological phenomena associated with proton migration across membranes. Based on our current understanding, it is known that the physicochemical properties of the gas-phase water are drastically different from those of bulk water. For example, the gas-phase hydronium ion, H3O +(g), can protonate most (non-alkane) organic species, whereas H 3O+(aq) can neutralize only relatively strong bases. Thus, to be able to understand and engineer water-hydrophobe interfaces, it is imperative to investigate this fluctuating region of molecular thickness wherein the 'function' of chemical species transitions from one phase to another via steep gradients in hydration, dielectric constant, and density. Aqueous interfaces are difficult to approach by current experimental techniques because designing experiments to specifically sample interfacial layers (< 1 nm thick) is an arduous task. While recent advances in surface-specific spectroscopies have provided

  8. Soy milk oleosome behaviour at the air-water interface.

    PubMed

    Waschatko, Gustav; Junghans, Ann; Vilgis, Thomas A

    2012-01-01

    Soy milk is a highly stable emulsion mainly due to the presence of oleosomes, which are oil bodies and function as lipid storage organelles in plants, e.g., in seeds. Oleosomes are micelle-like structures with an outer phospholipid monolayer, an interior filled with triacylglycerides (TAGs), and oleosins anchored hairpin-like into the structure with their hydrophilic parts remaining outside the oleosomes, completely covering their surface (K. Hsieh and A. H. C. Huang, Plant Physiol., 2004, 136, 3427-3434). Oleosins are alkaline proteins of 15-26 kDa (K. Hsieh and A. H. C. Huang, Plant Physiol., 2004, 136, 3427-3434) which are expressed during seed development and maturation and play a major role in the stability of oil bodies. Additionally, the oil bodies of seeds seem to have the highest impact on coalescence, probably due to the required protection against environmental stress during dormancy and germination compared to, e.g., vertebrates' lipoproteins. Surface pressure investigations and Brewster angle microscopy of oleosomes purified from raw soy milk were executed to reveal their diffusion to the air-water interface, rupture, adsorption and structural modification over time at different subphase conditions. Destroying the surface portions of the oleosins by tryptic digestion induced coalescence of oleosomes (J. Tzen and A. Huang, J. Cell. Biol., 1992, 117, 327-335) and revealed severe changes in their adsorption kinetics. Such investigations will help to determine the effects behind oleosome stability and are necessary for a better understanding of the principal function of oleosins and their interactions with phospholipids.

  9. Detachment of deposited colloids by advancing and receding air-water interfaces.

    PubMed

    Aramrak, Surachet; Flury, Markus; Harsh, James B

    2011-08-16

    Moving air-water interfaces can detach colloidal particles from stationary surfaces. The objective of this study was to quantify the effects of advancing and receding air-water interfaces on colloid detachment as a function of interface velocity. We deposited fluorescent, negatively charged, carboxylate-modified polystyrene colloids (diameter of 1 μm) into a cylindrical glass channel. The colloids were hydrophilic with an advancing air-water contact angle of 60° and a receding contact angle of 40°. After colloid deposition, two air bubbles were sequentially introduced into the glass channel and passed through the channel at different velocities (0.5, 7.7, 72, 982, and 10,800 cm/h). The passage of the bubbles represented a sequence of receding and advancing air-water interfaces. Colloids remaining in the glass channel after each interface passage were visualized with confocal microscopy and quantified by image analysis. The advancing air-water interface was significantly more effective in detaching colloids from the glass surface than the receding interface. Most of the colloids were detached during the first passage of the advancing air-water interface, while the subsequent interface passages did not remove significant amounts of colloids. Forces acting on the colloids calculated from theory corroborate our experimental results, and confirm that the detachment forces (surface tension forces) during the advancing air-water interface movement were stronger than during the receding movement. Theory indicates that, for hydrophilic colloids, the advancing interface movement generally exerts a stronger detachment force than the receding, except when the hysteresis of the colloid-air-water contact angle is small and that of the channel-air-water contact angle is large.

  10. Properties of diphytanoyl phospholipids at the air-water interface.

    PubMed

    Yasmann, Anthony; Sukharev, Sergei

    2015-01-01

    Diphytanoylphosphatidyl choline (DPhPC) is a synthetic ester lipid with methylated tails found in archaeal ether lipids. Because of the stability of DPhPC bilayers and the absence of phase transitions over a broad range of temperatures, the lipid is used as an artificial membrane matrix for the reconstitution of channels, pumps, and membrane-active peptides. We characterized monomolecular films made of DPhPC and its natural ether analog DOPhPC at the air-water interface. We measured compression isotherms and dipole potentials of films made of DPhPC, DPhPE, and DOPhPC. We determined that at 40 mN/m the molecular area of DPhPC is 81.2 Å(2), consistent with X-ray and neutron scattering data obtained in liposomes. This indicates that 40 mN/m is the monolayer-bilayer equivalence pressure for this lipid. At this packing density, the compressibility modulus (Cs(-1 )= 122 ± 7 mN/m) and interfacial dipole potential (V = 355 ± 16 mV) were near their maximums. The molecular dipole moment was estimated to be 0.64 ± 0.02 D. The ether DOPhPC compacted to 70.4 Å(2)/lipid at 40 mN/m displaying a peak compressibility similar to that of DPhPC. The maximal dipole potential of the ether lipid was about half of that for DPhPC at this density, and the elemental dipole moment was about a quarter. The spreading of DPhPC and DOPhPC liposomes reduced the surface tension of the aqueous phase by 46 and 49 mN/m, respectively. This corresponds well to the monolayer collapse pressure. The equilibration time shortened as the temperature increased from 20 to 60 °C, but the surface pressure at equilibrium did not change. The data illustrates the properties of branched chains and the contributions of ester bonds in setting the mechanical and electrostatic parameters of diphytanoyl lipids. These properties determine an environment in which reconstituted voltage- or mechano-activated proteins may function. Electrostatic properties are important in the preparation of asymmetric folded bilayers

  11. Capillary forces between sediment particles and an air-water interface.

    PubMed

    Chatterjee, Nirmalya; Lapin, Sergey; Flury, Markus

    2012-04-17

    In the vadose zone, air-water interfaces play an important role in particle fate and transport, as particles can attach to the air-water interfaces by action of capillary forces. This attachment can either retard or enhance the movement of particles, depending on whether the air-water interfaces are stationary or mobile. Here we use three standard PTFE particles (sphere, circular cylinder, and tent) and seven natural mineral particles (basalt, granite, hematite, magnetite, mica, milky quartz, and clear quartz) to quantify the capillary forces between an air-water interface and the different particles. Capillary forces were determined experimentally using tensiometry, and theoretically assuming volume-equivalent spherical, ellipsoidal, and circular cylinder shapes. We experimentally distinguished between the maximum capillary force and the snap-off force when the air-water interface detaches from the particle. Theoretical and experimental values of capillary forces were of similar order of magnitude. The sphere gave the smallest theoretical capillary force, and the circular cylinder had the largest force due to pinning of the air-water interface. Pinning was less pronounced for natural particles when compared to the circular cylinder. Ellipsoids gave the best agreement with measured forces, suggesting that this shape can provide a reasonable estimation of capillary forces for many natural particles.

  12. LIF measurements of oxygen concentration gradients along flat and wavy air-water interfaces

    NASA Astrophysics Data System (ADS)

    Woodrow, Philip T., Jr.; Duke, Steve R.

    Instantaneous spatially-varying measurements of concentration gradients occurring during aeration for flat, stagnant air-water interfaces and for interfaces with mechanically-generated waves are presented. Measurements were obtained in a laboratory wave tank using a laser-induced fluorescence (LIF) technique that images planar oxygen concentration fields near air-water interfaces. Pulsed nitrogen laser light focused to a thin sheet induces the fluorescence of pyrene butyric acid (in micromolar concentration) in deoxygenated water. The PBA fluorescence is quenched by dissolved oxygen. A high-resolution CCD camera images in two dimensions the intensities of the fluorescence field, providing spatial measurements of oxygen concentration with magnification of 7 μm per pixel. The concentration fields, gradients, and boundary layer thicknesses along the flat and wavy air-water interfaces are quantified and compared to previous measurements associated with sheared gas-liquid interfaces and with wind-generated waves.

  13. Estimating pH at the Air/Water Interface with a Confocal Fluorescence Microscope.

    PubMed

    Yang, Haiya; Imanishi, Yasushi; Harata, Akira

    2015-01-01

    One way to determine the pH at the air/water interface with a confocal fluorescence microscope has been proposed. The relation between the pH at the air/water interface and that in a bulk solution has been formulated in connection with the adsorption equilibrium and the dissociation equilibrium of the dye adsorbed. Rhodamine B (RhB) is used as a surface-active fluorescent pH probe. The corrected fluorescence spectrum of RhB molecules at the air/water interface with the surface density of 1.0 nmol m(-2) level shows pH-dependent shifts representing an acid-base equilibrium. Two ways to determine the unknown acid-base equilibrium constant of RhB molecules at the air/water interface have been discussed. With surface-tension measurements, the adsorption properties, maximum surface density, and adsorption equilibrium constants were estimated for both cationic and zwitterionic forms of RhB molecules at the air/water interface.

  14. Does colloid shape affect detachment of colloids by a moving air-water interface?

    PubMed

    Aramrak, Surachet; Flury, Markus; Harsh, James B; Zollars, Richard L; Davis, Howard P

    2013-05-14

    Air-water interfaces interact strongly with colloidal particles by capillary forces. The magnitude of the interaction force depends on, among other things, the particle shape. Here, we investigate the effects of particle shape on colloid detachment by a moving air-water interface. We used hydrophilic polystyrene colloids with four different shapes (spheres, barrels, rods, and oblong disks), but otherwise identical surface properties. The nonspherical shapes were created by stretching spherical microspheres on a film of polyvinyl alcohol (PVA). The colloids were then deposited onto the inner surface of a glass channel. An air bubble was introduced into the channel and passed through, thereby generating a receding followed by an advancing air-water interface. The detachment of colloids by the air-water interfaces was visualized with a confocal microscope, quantified by image analysis, and analyzed statistically to determine significant differences. For all colloid shapes, the advancing air-water interface caused pronounced colloid detachment (>63%), whereas the receding interface was ineffective in colloid detachment (<1.5%). Among the different colloid shapes, the barrels were most readily removed (94%) by the advancing interface, followed by the spheres and oblong disks (80%) and the rods (63%). Colloid detachment was significantly affected by colloid shape. The presence of an edge, as it occurs in a barrel-shaped colloid, promoted colloid detachment because the air-water interface is being pinned at the edge of the colloid. This suggests that the magnitude of colloid mobilization and transport in porous media is underestimated for edged particles and overestimated for rodlike particles when a sphere is used as a model colloid.

  15. Detachment of colloids from a solid surface by a moving air-water interface.

    PubMed

    Sharma, Prabhakar; Flury, Markus; Zhou, Jun

    2008-10-01

    Colloid attachment to liquid-gas interfaces is an important process used in industrial applications to separate suspended colloids from the fluid phase. Moving gas bubbles can also be used to remove colloidal dust from surfaces. Similarly, moving liquid-gas interfaces lead to colloid mobilization in the natural subsurface environment, such as in soils and sediments. The objective of this study was to quantify the effect of moving air-water interfaces on the detachment of colloids deposited on an air-dried glass surface, as a function of colloidal properties and interface velocity. We selected four types of polystyrene colloids (positive and negative surface charge, hydrophilic and hydrophobic). The colloids were deposited on clean microscope glass slides using a flow-through deposition chamber. Air-water interfaces were passed over the colloid-deposited glass slides, and we varied the number of passages and the interface velocity. The amounts of colloids deposited on the glass slides were visualized using confocal laser scanning microscopy and quantified by image analysis. Our results showed that colloids attached under unfavorable conditions were removed in significantly greater amounts than those attached under favorable conditions. Hydrophobic colloids were detached more than hydrophilic colloids. The effect of the air-water interface on colloid removal was most pronounced for the first two passages of the air-water interface. Subsequent passages of air-water interfaces over the colloid-deposited glass slides did not cause significant additional colloid removal. Increasing interface velocity led to decreased colloid removal. The force balances, calculated from theory, supported the experimental findings, and highlight the dominance of detachment forces (surface tension forces) over the attachment forces (DLVO forces).

  16. Surface behavior of malonic acid adsorption at the air/water interface.

    PubMed

    Blower, Patrick G; Shamay, Eric; Kringle, Loni; Ota, Stephanie T; Richmond, Geraldine L

    2013-03-28

    The presence of organic materials adsorbed to the surfaces of aerosol particles has been demonstrated to be a determining factor in relevant atmospheric processes. Malonic acid is a small, water-soluble organic acid that is common in aerosols and is surface-active. A comprehensive investigation of the adsorption of malonic acid to the air/water interface was accomplished using vibrational sum frequency spectroscopy (VSFS) and surface tension measurements as functions of concentration and pH. Malonic acid was found to be weakly solvated at the air/water interface, and its orientation as a function of concentration was explored through different VSFS polarization schemes. pH-dependent experiments revealed that the surface-active species is the fully protonated species. Computational analyses were used to obtain depth-specific geometries of malonic acid at the air/water interface that confirm and enrich the experimental results. PMID:23384061

  17. Physicochemical Study of Viral Nanoparticles at the Air/Water Interface.

    PubMed

    Torres-Salgado, Jose F; Comas-Garcia, Mauricio; Villagrana-Escareño, Maria V; Durán-Meza, Ana L; Ruiz-García, Jaime; Cadena-Nava, Ruben D

    2016-07-01

    The assembly of most single-stranded RNA (ssRNA) viruses into icosahedral nucleocapsids is a spontaneous process driven by protein-protein and RNA-protein interactions. The precise nature of these interactions results in the assembly of extremely monodisperse and structurally indistinguishable nucleocapsids. In this work, by using a ssRNA plant virus (cowpea chlorotic mottle virus [CCMV]) as a charged nanoparticle we show that the diffusion of these nanoparticles from the bulk solution to the air/water interface is an irreversible adsorption process. By using the Langmuir technique, we measured the diffusion and adsorption of viral nucleocapsids at the air/water interface at different pH conditions. The pH changes, and therefore in the net surface charge of the virions, have a great influence in the diffusion rate from the bulk solution to the air/water interface. Moreover, assembly of mesoscopic and microscopic viral aggregates at this interface depends on the net surface charge of the virions and the surface pressure. By using Brewster's angle microscopy we characterized these structures at the interface. Most common structures observed were clusters of virions and soap-frothlike micron-size structures. Furthermore, the CCMV films were compressed to form monolayers and multilayers from moderate to high surface pressures, respectively. After transferring the films from the air/water interface onto mica by using the Langmuir-Blodgett technique, their morphology was characterized by atomic force microscopy. These viral monolayers showed closed-packing nano- and microscopic arrangements.

  18. Effects of flow on insulin fibril formation at an air/water interface

    NASA Astrophysics Data System (ADS)

    Posada, David; Heldt, Caryn; Sorci, Mirco; Belfort, Georges; Hirsa, Amir

    2009-11-01

    The amyloid fibril formation process, which is implicated in several diseases such as Alzheimer's and Huntington's, is characterized by the conversion of monomers to oligomers and then to fibrils. Besides well-studied factors such as pH, temperature and concentration, the kinetics of this process are significantly influenced by the presence of solid or fluid interfaces and by flow. By studying the nucleation and growth of a model system (insulin fibrils) in a well-defined flow field with an air/water interface, we can identify the flow conditions that impact protein aggregation kinetics both in the bulk solution and at the air/water interface. The present flow system (deep-channel surface viscometer) consists of an annular region bounded by stationary inner and outer cylinders, an air/water interface, and a floor driven at constant rotation. We show the effects of Reynolds number on the kinetics of the fibrillation process both in the bulk solution and at the air/water interface, as well as on the structure of the resultant amyloid aggregates.

  19. Smart nanogels at the air/water interface: structural studies by neutron reflectivity.

    PubMed

    Zielińska, Katarzyna; Sun, Huihui; Campbell, Richard A; Zarbakhsh, Ali; Resmini, Marina

    2016-03-01

    The development of effective transdermal drug delivery systems based on nanosized polymers requires a better understanding of the behaviour of such nanomaterials at interfaces. N-Isopropylacrylamide-based nanogels synthesized with different percentages of N,N'-methylenebisacrylamide as cross-linker, ranging from 10 to 30%, were characterized at physiological temperature at the air/water interface, using neutron reflectivity (NR), with isotopic contrast variation, and surface tension measurements; this allowed us to resolve the adsorbed amount and the volume fraction of nanogels at the interface. A large conformational change for the nanogels results in strong deformations at the interface. As the percentage of cross-linker incorporated in the nanogels becomes higher, more rigid matrices are obtained, although less deformed, and the amount of adsorbed nanogels is increased. The data provide the first experimental evidence of structural changes of nanogels as a function of the degree of cross-linking at the air/water interface. PMID:26697736

  20. Structure of phospholipid monolayers containing poly(ethylene glycol) lipids at the air-water interface

    SciTech Connect

    Majewski, J.; Smith, G.S.; Kuhl, T.L.; Israelachvili, J.N.; Gerstenberg, M.C.

    1997-04-17

    The density distribution of a lipid monolayer at the air-water interface mixed with varying amounts of lipid with poly(ethylene glycol)polymer headgroups (polymer-lipid or PEG-lipid) was measured using neutron reflectometry. The structure of the monolayer at the interface was greatly perturbed by the presence of the bulky polymer-lipid headgroups resulting in a large increase in the thickness of the headgroup region normal to the interface and a systematic roughening of the interface with increasing polymer-lipid content. These results show how bulky hydrophilic moieties cause significant deformations and out-of-place protrusions of phospholipid monolayers and presumably bilayers, vesicles and biological membranes. In terms of polymer physics, very short polymer chains tethered to the air-water interface follow scaling behavior with a mushroom to brush transition with increasing polymer grafting density. 34 refs., 9 figs., 1 tab.

  1. Hydrodynamics of a self-propelled camphor boat at the air-water interface

    NASA Astrophysics Data System (ADS)

    Akella, Sathish; Singh, Dhiraj; Singh, Ravi; Bandi, Mahesh

    2015-11-01

    A camphor tablet, when placed at the air-water interface undergoes sublimation and camphor vapour spreads radially outwards across the surface due to Marangoni forces. This steady camphor influx from tablet onto the air-water interface is balanced by the camphor outflux due to evaporation. When spontaneous fluctuations in evaporation break the axial symmetry of Marangoni force acting radially outwards, the camphor tablet is propelled like a boat along the water surface. We report experiments on the hydrodynamics of a self-propelled camphor boat at air-water interfaces. We observe three different modes of motion, namely continuous, harmonic and periodic, due to the volatile nature of camphor. We explain these modes in terms of ratio of two time-scales: the time-scale over which viscous forces are dominant over the Marangoni forces (τη) and the time-scale over which Marangoni forces are dominant over the viscous forces (τσ). The continuous, harmonic and periodic motions are observed when τη /τσ ~ 1 , τη /τσ >= 1 and τη /τσ >> 1 respectively. Experimentally, the ratio of the time scales is varied by changing the interfacial tension of the air-water interface using Sodium Dodecyl Sulfate. This work was supported by the Collective Interactions Unit, OIST Graduate University.

  2. Understanding the structure of hydrophobic surfactants at the air/water interface from molecular level.

    PubMed

    Zhang, Li; Liu, Zhipei; Ren, Tao; Wu, Pan; Shen, Jia-Wei; Zhang, Wei; Wang, Xinping

    2014-11-25

    Understanding the behavior of fluorocarbon surfactants at the air/water interface is crucial for many applications, such as lubricants, paints, cosmetics, and fire-fighting foams. In this study, molecular dynamics (MD) simulations were employed to investigate the microscopic properties of non-ionic fluorocarbon surfactants at the air/water interface. Several properties, including the distribution of head groups, the distribution probability of the tilt angle between hydrophobic tails with respect to the xy plane, and the order parameter of surfactants, were computed to probe the structure of hydrophobic surfactants at the air/water interface. The effects of the monomer structure on interfacial phenomena of non-ionic surfactants were investigated as well. It is observed that the structure of fluorocarbon surfactants at the air/water interface is more ordered than that of hydrocarbons, which is dominated by the van der Waals interaction between surfactants and water molecules. However, replacing one or two CF2 with one or two CH2 group does not significantly influence the interfacial structure, suggesting that hydrocarbons may be promising alternatives to perfluorinated surfactants.

  3. The behavior of NaOH at the air-water interface, a computational study

    SciTech Connect

    Wick, Collin D.; Dang, Liem X.

    2010-07-14

    Molecular dynamics simulations with a polarizable multi-state empirical valence bond model were carried out to investigate NaOH dissociation and pairing in water bulk and at the air-water interface. It was found that NaOH readily dissociates in the bulk, and the effect of the air-water interface on NaOH dissociation is fairly minor. Also, NaOH complexes were found to be strongly repelled from the air-water interface, which is consistent with surface tension measurements. At the same time, a very strong preference for the hydroxide anion to be oriented towards the air was found that persisted a few angstroms towards the liquid from the Gibbs dividing surface of the air-water interface. This was due to a preference for the hydroxide anion to have its hydrogen pointing towards the air, and the fact that the sodium ion was more likely to be found near the hydroxide oxygen than hydrogen. As a consequence, the simulation results show that surfaces of NaOH solutions should be negatively charged, in agreement with experimental observations, but also that the hydroxide has little surface affinity. This provides the possibility that the surface of water can be devoid of hydroxide anions, but still have a strong negative charge. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  4. It's Alive!: Students Observe Air-Water Interface Samples Rich with Organisms

    ERIC Educational Resources Information Center

    Avant, Thomas

    2002-01-01

    This article describes an experiment, designed by Cindy Henk, manager of the Socolofsky Microscopy Center at Louisiana State University (LSU), that involved collecting and viewing microorganisms in the air-water interface. The experiment was participated by Leesville High School microbiology students. The students found that the air-water…

  5. Charge dependent condensation of macro-ions at air-water interfaces

    NASA Astrophysics Data System (ADS)

    Bera, Mrinal; Antonio, Mark

    2015-03-01

    Ordering of ions at and near air-water interfaces is a century old problem for researchers and has implications on a host of physical, chemical and biological processes. The dynamic nature of water surface and the surface fluctuations created by thermally excited capillary waves have always limited measurement of near surface ionic-distributions. We demonstrate that this limitation can be overcome by using macro-ions of sizes larger than the capillary wave roughness ~3Å. Our attempts to measure distributions of inorganic macro-ions in the form of Keggin heteropolyanions (HPAs) of sizes ~10Å have unraveled novel charge-dependent condensation of macro-ions beneath air-water interfaces. Our results demonstrate that HPAs with -3 charges condense readily beneath air-water interfaces. This is in contrast to the absence of surface preference for HPAs with -4 charges. The similarity of HPA-HPA separations near air-water interfaces and in bulk crystal structures suggests the presence of the planar Zundel ions (H5O2+), which interact with HPAs and the water surface to facilitate the charge dependent condensation beneath the air-water interfaces.This work and the use of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility at Argonne National Laboratory, is based upon work supported by the U.S. DOE, Office of Science, Office of Basic Energy Science, Division of Chemical Sciences, Biosciences and Geosciences, under contract No DE-AC02-06CH11357.

  6. Physicochemical Study of Viral Nanoparticles at the Air/Water Interface.

    PubMed

    Torres-Salgado, Jose F; Comas-Garcia, Mauricio; Villagrana-Escareño, Maria V; Durán-Meza, Ana L; Ruiz-García, Jaime; Cadena-Nava, Ruben D

    2016-07-01

    The assembly of most single-stranded RNA (ssRNA) viruses into icosahedral nucleocapsids is a spontaneous process driven by protein-protein and RNA-protein interactions. The precise nature of these interactions results in the assembly of extremely monodisperse and structurally indistinguishable nucleocapsids. In this work, by using a ssRNA plant virus (cowpea chlorotic mottle virus [CCMV]) as a charged nanoparticle we show that the diffusion of these nanoparticles from the bulk solution to the air/water interface is an irreversible adsorption process. By using the Langmuir technique, we measured the diffusion and adsorption of viral nucleocapsids at the air/water interface at different pH conditions. The pH changes, and therefore in the net surface charge of the virions, have a great influence in the diffusion rate from the bulk solution to the air/water interface. Moreover, assembly of mesoscopic and microscopic viral aggregates at this interface depends on the net surface charge of the virions and the surface pressure. By using Brewster's angle microscopy we characterized these structures at the interface. Most common structures observed were clusters of virions and soap-frothlike micron-size structures. Furthermore, the CCMV films were compressed to form monolayers and multilayers from moderate to high surface pressures, respectively. After transferring the films from the air/water interface onto mica by using the Langmuir-Blodgett technique, their morphology was characterized by atomic force microscopy. These viral monolayers showed closed-packing nano- and microscopic arrangements. PMID:26999022

  7. Interaction between graphene oxide and Pluronic F127 at the air-water interface.

    PubMed

    Li, Shanghao; Guo, Jingru; Patel, Ravi A; Dadlani, Anup L; Leblanc, Roger M

    2013-05-14

    Triblock copolymer Pluronic F127 (PF127) has previously been demonstrated to disperse graphene oxide (GO) in electrolyte solution and block the hydrophobic interaction between GO and l-tryptophan and l-tyrosine. However, the nature of this interaction between PF127 and GO remains to be characterized and elucidated. In the present study, we aimed to characterize and understand the interaction between GO and PF127 using a 2-dimensional Langmuir monolayer methodology at the air-water interface by surface pressure-area isotherm measurement, stability, adsorption, and atomic force microscopy (AFM) imaging. Based on the observation of surface pressure-area isotherms, adsorption, and stability of PF127 and PF127/GO mixture at the air-water interface, GO is suggested to change the conformation of PF127 at the air-water interface and also drag PF127 from the interface to the bulk subphase. Atomic force microscopy (AFM) image supports this assumption, as GO and PF127 can be observed by spreading the subphase solution outside the compressing barriers, as shown in the TOC graphic.

  8. Demonstration of adaptive optics for mitigating laser propagation through a random air-water interface

    NASA Astrophysics Data System (ADS)

    Land, Phillip; Majumdar, Arun K.

    2016-05-01

    This paper describes a new concept of mitigating signal distortions caused by random air-water interface using an adaptive optics (AO) system. This is the first time the concept of using an AO for mitigating the effects of distortions caused mainly by a random air-water interface is presented. We have demonstrated the feasibility of correcting the distortions using AO in a laboratory water tank for investigating the propagation effects of a laser beam through an airwater interface. The AO system consisting of a fast steering mirror, deformable mirror, and a Shack-Hartmann Wavefront Sensor for mitigating surface water distortions has a unique way of stabilizing and aiming a laser onto an object underneath the water. Essentially the AO system mathematically takes the complex conjugate of the random phase caused by air-water interface allowing the laser beam to penetrate through the water by cancelling with the complex conjugates. The results show the improvement of a number of metrics including Strehl ratio, a measure of the quality of optical image formation for diffraction limited optical system. These are the first results demonstrating the feasibility of developing a new sensor system such as Laser Doppler Vibrometer (LDV) utilizing AO for mitigating surface water distortions.

  9. Thermodynamics of iodide adsorption at the instantaneous air-water interface

    NASA Astrophysics Data System (ADS)

    Stern, Abraham C.; Baer, Marcel D.; Mundy, Christopher J.; Tobias, Douglas J.

    2013-03-01

    We performed molecular dynamics simulations using both polarizable and non-polarizable force fields to study the adsorption of iodide to the air-water interface. A novel aspect of our analysis is that the progress of ion adsorption is measured as the distance from the instantaneous interface, which is defined by a coarse-graining scheme proposed recently by Willard and Chandler ["Instantaneous liquid interfaces," J. Phys. Chem. B 114, 1954-1958 (2010), 10.1021/jp909219k]. Referring structural and thermodynamic quantities to the instantaneous interface unmasks molecular-scale details that are obscured by thermal fluctuations when the same quantities are referred to an average measure of the position of the interface, such as the Gibbs dividing surface. Our results suggest that an ion adsorbed at the interface resides primarily in the topmost water layer, and the interfacial location of the ion is favored by enthalpy and opposed by entropy.

  10. Hydrodynamics of a fixed camphor boat at the air-water interface

    NASA Astrophysics Data System (ADS)

    Singh, Dhiraj; Akella, Sathish; Singh, Ravi; Mandre, Shreyas; Bandi, Mahesh

    2015-11-01

    A camphor tablet, when introduced at the air-water interface undergoes sublimation and the camphor vapour spreads radially outwards across the surface. This radial spreading of camphor is due to Marangoni forces setup by the camphor concentration gradient. We report experiments on the hydrodynamics of this process for a camphor tablet held fixed at the air-water interface. During the initial transient, the time-dependent spread radius R (t) of camphor scales algebraically with time t (R (t) ~t 1 / 2) in agreement with empirical scalings reported for spreading of volatile oils on water surface. But unlike surfactants, the camphor stops spreading when the influx of camphor from the tablet onto the air-water interface is balanced by the outflux of camphor due to evaporation, and a steady-state condition is reached. The spreading camphor however, shears the underlying fluid and sets up bulk convective flow. We explain the coupled steady-state dynamics between the interfacial camphor spreading and bulk convective flow with a boundary layer approximation, supported by experimental evidence. This work was supported by the Collective Interactions Unit, OIST Graduate University.

  11. Anisotropic orientational motion of molecular adsorbates at the air-water interface

    SciTech Connect

    Zimdars, D.; Dadap, J.I.; Eisenthal, K.B.; Heinz, T.F.

    1999-04-29

    The ultrafast orientational motions of coumarin 314 (C314) adsorbed at the air/water interface were investigated by time-resolved surface second harmonic generation (TRSHG). The theory and method of using TRSHG to detect both out-of-plane and in-plane orientational motions are discussed. The interfacial solute motions were found to be anisotropic, with differing out-of-plane and in-plane reorientation time constants. This report presents the first direct observation of in-plane orientational motion of a molecule (C314) at the air/water interface using TRSHG. The in-plane reorientation time constant is 600 {+-} 40 ps. The out-of-plane reorientation time constant is 350 {+-} 20 ps. The out-of-plane orientational motion of C314 is similar to the previous results on rhodamine 6G at the air/water interface which indicated increased interfacial friction compared with bulk aqueous solution. The surface reorientation times are 2--3 times slower than the bulk isotropic orientational diffusion time.

  12. Solvent-dependent properties of poly(vinylidene fluoride) monolayers at the air-water interface.

    PubMed

    Zhu, Huie; Matsui, Jun; Yamamoto, Shunsuke; Miyashita, Tokuji; Mitsuishi, Masaya

    2015-03-14

    The present work addresses the solvent-dependent properties of Langmuir films of poly(vinylidene fluoride) (PVDF) and amphiphilic poly(N-dodecylacrylamide) (pDDA) at different mixing ratios. After introducing pDDA nanosheets, PVDF Langmuir films obtain a tremendously enhanced modulus as well as high transfer ratios using the vertical dipping method caused by the support of the pDDA two-dimensional hydrogen bonding network. Brewster angle microscopy (BAM) was used to investigate PVDF monolayers at the air-water interface in situ. Spreading from different solvents, the PVDF molecules take completely different aggregation states at the air-water interface. The PVDF molecules aggregate to become large domains when spread from N-methyl-2-pyrrolidone (NMP). However, the volatile and low-polarity methylethyl ketone (MEK) made the PVDF molecules more dispersive on the water surface. This study also discovers a versatile crystallization control of PVDF homopolymer from complete β phase (NMP) to complete α phase (MEK) at the air-water interface, thereby eliciting useful information for further manipulation of film morphologies and film applications. PMID:25622932

  13. Properties of amphiphilic oligonucleotide films at the air/water interface and after film transfer.

    PubMed

    Keller, R; Kwak, M; de Vries, J W; Sawaryn, C; Wang, J; Anaya, M; Müllen, K; Butt, H-J; Herrmann, A; Berger, R

    2013-11-01

    The self-assembly of amphiphilic hybrid materials containing an oligonucleotide sequence at the air/water interface was investigated by means of pressure-molecular area (Π-A) isotherms. In addition, films were transferred onto solid substrates and imaged using scanning force microscopy. We used oligonucleotide molecules with lipid tails, which consisted of a single stranded oligonucleotide 11 mer containing two hydrophobically modified 5-(dodec-1-ynyl)uracil nucleobases (dU11) at the 5'-end of the oligonucleotide sequence. The air/water interface was used as confinement for the self-assembling process of dU11. Scanning force microscopy of films transferred via Langmuir-Blodgett technique revealed mono-, bi- (Π ≥ 2 mN/m) and multilayer formation (Π ≥ 30 mN/m). The first layer was 1.6 ± 0.1 nm thick. It was oriented with the hydrophilic oligonucleotide moiety facing the hydrophilic substrate while the hydrophobic alkyl chains faced air. In the second layer the oligonucleotide moiety was found to face the air. The second layer was found to cover up to 95% of the sample area. Our measurements indicated that the rearrangement of the molecules into bi- and multiple bilayers happened already at the air/water interface. Similar results were obtained with a second type of oligonucleotide amphiphile, an oligonucleotide block copolymer, which was composed of an oligonucleotide 11 mer covalently attached at the terminus to polypropyleneoxide (PPO).

  14. Interfacial characterization of Pluronic PE9400 at biocompatible (air-water and limonene-water) interfaces.

    PubMed

    Pérez-Mosqueda, Luis M; Maldonado-Valderrama, Julia; Ramírez, Pablo; Cabrerizo-Vílchez, Miguel A; Muñoz, José

    2013-11-01

    In this work, we provide an accurate characterization of non-ionic triblock copolymer Pluronic PE9400 at the air-water and limonene-water interfaces, comprising a systematic analysis of surface tension isotherms, dynamic curves, dilatational rheology and desorption profiles. The surface pressure isotherms display two different slopes of the Π-c plot suggesting the existence of two adsorption regimes for PE9400 at both interfaces. Application of a theoretical model, which assumes the coexistence of different adsorbed states characterized by their molar areas, allows quantification of the conformational changes occurring at the adsorbed layer, indentifying differences between the conformations adopted at the air-water and the limonene-water interface. The presence of two maxima in the dilatational modulus vs. interfacial pressure importantly corroborates this conformational change from a 2D flat conformation to 3D brush one. Moreover, the dilatational response provides mechanical diferences between the interfacial layers formed at the two interfaces analyzed. Dynamic surface pressure data were transformed into a dimensionless form and fitted to another model which considers the influence of the reorganization process on the adsorption dynamics. Finally, the desorption profiles reveal that Pluronic PE9400 is irreversibly adsorbed at both interfaces regardless of the interfacial conformation and nature of the interface. The systematic characterization presented in this work provides important new findings on the interfacial properties of pluronics which can be applied in the rational development of new products, such as biocompatible limonene-based emulsions and/or microemulsions.

  15. New Mechanistic Pathways for Criegee-Water Chemistry at the Air/Water Interface.

    PubMed

    Zhu, Chongqin; Kumar, Manoj; Zhong, Jie; Li, Lei; Francisco, Joseph S; Zeng, Xiao Cheng

    2016-09-01

    Understanding Criegee chemistry has become one of central topics in atmospheric research recently. The reaction of Criegee intermediates with gas-phase water clusters has been widely viewed as a key Criegee reaction in the troposphere. However, the effect of aerosols or clouds on Criegee chemistry has received little attention. In this work, we have investigated the reaction between the smallest Criegee intermediate, CH2OO, and water clusters in the gas phase, as well as at the air/water surface using ab initio quantum chemical calculations and adaptive buffered force quantum mechanics/molecular mechanics (QM/MM) dynamics simulations. Our simulation results show that the typical time scale for the reaction of CH2OO with water at the air/water interface is on the order of a few picoseconds, 2-3 orders of magnitude shorter than that in the gas phase. Importantly, the adbf-QM/MM dynamics simulations suggest several reaction pathways for the CH2OO + water reaction at the air/water interface, including the loop-structure-mediated mechanism and the stepwise mechanism. Contrary to the conventional gas-phase CH2OO reaction, the loop-structure is not a prerequisite for the stepwise mechanism. For the latter, a water molecule and the CH2OO at the air/water interface, upon their interaction, can result in the formation of (H3O)(+) and (OH)CH2(OO)(-). Thereafter, a hydrogen bond can be formed between (H3O)(+) and the terminal oxygen atom of (OH)CH2(OO)(-), leading to direct proton transfer and the formation of α-hydroxy methylperoxide, HOCH2OOH. The mechanistic insights obtained from this simulation study should motivate future experimental studies of the effect of water clouds on Criegee chemistry.

  16. New Mechanistic Pathways for Criegee-Water Chemistry at the Air/Water Interface.

    PubMed

    Zhu, Chongqin; Kumar, Manoj; Zhong, Jie; Li, Lei; Francisco, Joseph S; Zeng, Xiao Cheng

    2016-09-01

    Understanding Criegee chemistry has become one of central topics in atmospheric research recently. The reaction of Criegee intermediates with gas-phase water clusters has been widely viewed as a key Criegee reaction in the troposphere. However, the effect of aerosols or clouds on Criegee chemistry has received little attention. In this work, we have investigated the reaction between the smallest Criegee intermediate, CH2OO, and water clusters in the gas phase, as well as at the air/water surface using ab initio quantum chemical calculations and adaptive buffered force quantum mechanics/molecular mechanics (QM/MM) dynamics simulations. Our simulation results show that the typical time scale for the reaction of CH2OO with water at the air/water interface is on the order of a few picoseconds, 2-3 orders of magnitude shorter than that in the gas phase. Importantly, the adbf-QM/MM dynamics simulations suggest several reaction pathways for the CH2OO + water reaction at the air/water interface, including the loop-structure-mediated mechanism and the stepwise mechanism. Contrary to the conventional gas-phase CH2OO reaction, the loop-structure is not a prerequisite for the stepwise mechanism. For the latter, a water molecule and the CH2OO at the air/water interface, upon their interaction, can result in the formation of (H3O)(+) and (OH)CH2(OO)(-). Thereafter, a hydrogen bond can be formed between (H3O)(+) and the terminal oxygen atom of (OH)CH2(OO)(-), leading to direct proton transfer and the formation of α-hydroxy methylperoxide, HOCH2OOH. The mechanistic insights obtained from this simulation study should motivate future experimental studies of the effect of water clouds on Criegee chemistry. PMID:27509207

  17. Thermodynamics of Iodide Adsorption at the Instantaneous Air-Water Interface.

    SciTech Connect

    Stern, Abraham C.; Baer, Marcel D.; Mundy, Christopher J.; Tobias, Douglas J.

    2013-03-21

    We perform simulations using both polarizable and non-polarizable force fields to study the adsorption of iodide to the air-water interface. A novel aspect of our analysis is that the progress of the adsorption is measured as the distance from the instantaneous interface, which is defined by a coarse-graining scheme proposed recently by Willard and Chandler.\\cite{chandler1} Referring structural and thermodynamic quantities to the instantaneous interface unmasks molecular-scale details that are obscured by thermal fluctuations when the same quantities are referred to an average measure of the position of the interface, such as the Gibbs dividing surface. Our results suggest that an ion adsorbed at the interface resides primarily in the topmost layer water.

  18. Molecular Adsorption Steers Bacterial Swimming at the Air/Water Interface

    PubMed Central

    Morse, Michael; Huang, Athena; Li, Guanglai; Maxey, Martin R.; Tang, Jay X.

    2013-01-01

    Microbes inhabiting Earth have adapted to diverse environments of water, air, soil, and often at the interfaces of multiple media. In this study, we focus on the behavior of Caulobacter crescentus, a singly flagellated bacterium, at the air/water interface. Forward swimming C. crescentus swarmer cells tend to get physically trapped at the surface when swimming in nutrient-rich growth medium but not in minimal salt motility medium. Trapped cells move in tight, clockwise circles when viewed from the air with slightly reduced speed. Trace amounts of Triton X100, a nonionic surfactant, release the trapped cells from these circular trajectories. We show, by tracing the motion of positively charged colloidal beads near the interface that organic molecules in the growth medium adsorb at the interface, creating a high viscosity film. Consequently, the air/water interface no longer acts as a free surface and forward swimming cells become hydrodynamically trapped. Added surfactants efficiently partition to the surface, replacing the viscous layer of molecules and reestablishing free surface behavior. These findings help explain recent similar studies on Escherichia coli, showing trajectories of variable handedness depending on media chemistry. The consistent behavior of these two distinct microbial species provides insights on how microbes have evolved to cope with challenging interfacial environments. PMID:23823220

  19. Propensity of Hydrated Excess Protons and Hydroxide Anions for the Air-Water Interface.

    PubMed

    Tse, Ying-Lung Steve; Chen, Chen; Lindberg, Gerrick E; Kumar, Revati; Voth, Gregory A

    2015-10-01

    Significant effort has been undertaken to better understand the molecular details governing the propensity of ions for the air-water interface. Facilitated by computationally efficient reactive molecular dynamics simulations, new and statistically conclusive molecular-scale results on the affinity of the hydrated excess proton and hydroxide anion for the air-water interface are presented. These simulations capture the dynamic bond breaking and formation processes (charge defect delocalization) that are important for correctly describing the solvation and transport of these complex species. The excess proton is found to be attracted to the interface, which is correlated with a favorable enthalpic contribution and consistent with reducing the disruption in the hydrogen bond network caused by the ion complex. However, a recent refinement of the underlying reactive potential energy function for the hydrated excess proton shows the interfacial attraction to be weaker, albeit nonzero, a result that is consistent with the experimental surface tension measurements. The influence of a weak hydrogen bond donated from water to the protonated oxygen, recently found to play an important role in excess hydrated proton transport in bulk water, is seen to also be important for this study. In contrast, the hydroxide ion is found to be repelled from the air-water interface. This repulsion is characterized by a reduction of the energetically favorable ion-water interactions, which creates an enthalpic penalty as the ion approaches the interface. Finally, we find that the fluctuation in the coordination number around water sheds new light on the observed entropic trends for both ions. PMID:26366480

  20. Linear and nonlinear microrheology of lysozyme layers forming at the air-water interface.

    PubMed

    Allan, Daniel B; Firester, Daniel M; Allard, Victor P; Reich, Daniel H; Stebe, Kathleen J; Leheny, Robert L

    2014-09-28

    We report experiments studying the mechanical evolution of layers of the protein lysozyme adsorbing at the air-water interface using passive and active microrheology techniques to investigate the linear and nonlinear rheological response, respectively. Following formation of a new interface, the linear shear rheology, which we interrogate through the Brownian motion of spherical colloids at the interface, becomes viscoelastic with a complex modulus that has approximately power-law frequency dependence. The power-law exponent characterizing this frequency dependence decreases steadily with increasing layer age. Meanwhile, the nonlinear microrheology, probed via the rotational motion of magnetic nanowires at the interface, reveals a layer response characteristic of a shear-thinning power-law fluid with a flow index that decreases with age. We discuss two possible frameworks for understanding this mechanical evolution: gelation and the formation of a soft glass phase. PMID:24969505

  1. Linear and nonlinear microrheology of lysozyme layers forming at the air-water interface.

    PubMed

    Allan, Daniel B; Firester, Daniel M; Allard, Victor P; Reich, Daniel H; Stebe, Kathleen J; Leheny, Robert L

    2014-09-28

    We report experiments studying the mechanical evolution of layers of the protein lysozyme adsorbing at the air-water interface using passive and active microrheology techniques to investigate the linear and nonlinear rheological response, respectively. Following formation of a new interface, the linear shear rheology, which we interrogate through the Brownian motion of spherical colloids at the interface, becomes viscoelastic with a complex modulus that has approximately power-law frequency dependence. The power-law exponent characterizing this frequency dependence decreases steadily with increasing layer age. Meanwhile, the nonlinear microrheology, probed via the rotational motion of magnetic nanowires at the interface, reveals a layer response characteristic of a shear-thinning power-law fluid with a flow index that decreases with age. We discuss two possible frameworks for understanding this mechanical evolution: gelation and the formation of a soft glass phase.

  2. Role of mixed boundaries on flow in open capillary channels with curved air-water interfaces.

    PubMed

    Zheng, Wenjuan; Wang, Lian-Ping; Or, Dani; Lazouskaya, Volha; Jin, Yan

    2012-09-01

    Flow in unsaturated porous media or in engineered microfluidic systems is dominated by capillary and viscous forces. Consequently, flow regimes may differ markedly from conventional flows, reflecting strong interfacial influences on small bodies of flowing liquids. In this work, we visualized liquid transport patterns in open capillary channels with a range of opening sizes from 0.6 to 5.0 mm using laser scanning confocal microscopy combined with fluorescent latex particles (1.0 μm) as tracers at a mean velocity of ∼0.50 mm s(-1). The observed velocity profiles indicate limited mobility at the air-water interface. The application of the Stokes equation with mixed boundary conditions (i.e., no slip on the channel walls and partial slip or shear stress at the air-water interface) clearly illustrates the increasing importance of interfacial shear stress with decreasing channel size. Interfacial shear stress emerges from the velocity gradient from the adjoining no-slip walls to the center where flow is trapped in a region in which capillary forces dominate. In addition, the increased contribution of capillary forces (relative to viscous forces) to flow on the microscale leads to increased interfacial curvature, which, together with interfacial shear stress, affects the velocity distribution and flow pattern (e.g., reverse flow in the contact line region). We found that partial slip, rather than the commonly used stress-free condition, provided a more accurate description of the boundary condition at the confined air-water interface, reflecting the key role that surface/interface effects play in controlling flow behavior on the nanoscale and microscale.

  3. Photosensitized Formation of Secondary Organic Aerosols above the Air/Water Interface.

    PubMed

    Bernard, F; Ciuraru, R; Boréave, A; George, C

    2016-08-16

    In this study, we evaluated photosensitized chemistry at the air-sea interface as a source of secondary organic aerosols (SOA). Our results show that, in addition to biogenic emissions, abiotic processes could also be important in the marine boundary layer. Photosensitized production of marine secondary organic aerosol was studied in a custom-built multiphase atmospheric simulation chamber. The experimental chamber contained water, humic acid (1-10 mg L(-1)) as a proxy for dissolved organic matter, and nonanoic acid (0.1-10 mM), a fatty acid proxy which formed an organic film at the air-water interface. Dark secondary reaction with ozone after illumination resulted in SOA particle concentrations in excess of 1000 cm(-3), illustrating the production of unsaturated compounds by chemical reactions at the air-water interface. SOA numbers via photosensitization alone and in the absence of ozone did not exceed background levels. From these results, we derived a dependence of SOA numbers on nonanoic acid surface coverage and dissolved organic matter concentration. We present a discussion on the potential role of the air-sea interface in the production of atmospheric organic aerosol from photosensitized origins. PMID:27434860

  4. Free Energies of Cavity and Noncavity Hydrated Electrons Near the Instantaneous Air/Water Interface.

    PubMed

    Casey, Jennifer R; Schwartz, Benjamin J; Glover, William J

    2016-08-18

    The properties of the hydrated electron at the air/water interface are computed for both a cavity and a noncavity model using mixed quantum/classical molecular dynamics simulation. We take advantage of our recently developed formalism for umbrella sampling with a restrained quantum expectation value to calculate free-energy profiles of the hydrated electron's position relative to the water surface. We show that it is critical to use an instantaneous description of the air/water interface rather than the Gibbs' dividing surface to obtain accurate potentials of mean force. We find that noncavity electrons, which prefer to encompass several water molecules, avoid the interface where water molecules are scarce. In contrast, cavity models of the hydrated electron, which prefer to expel water, have a local free-energy minimum near the interface. When the cavity electron occupies this minimum, its absorption spectrum is quite red-shifted, its binding energy is significantly lowered, and its dynamics speed up quite a bit compared with the bulk, features that have not been found by experiment. The surface activity of the electron therefore serves as a useful test of cavity versus noncavity electron solvation. PMID:27479028

  5. Photosensitized Formation of Secondary Organic Aerosols above the Air/Water Interface.

    PubMed

    Bernard, F; Ciuraru, R; Boréave, A; George, C

    2016-08-16

    In this study, we evaluated photosensitized chemistry at the air-sea interface as a source of secondary organic aerosols (SOA). Our results show that, in addition to biogenic emissions, abiotic processes could also be important in the marine boundary layer. Photosensitized production of marine secondary organic aerosol was studied in a custom-built multiphase atmospheric simulation chamber. The experimental chamber contained water, humic acid (1-10 mg L(-1)) as a proxy for dissolved organic matter, and nonanoic acid (0.1-10 mM), a fatty acid proxy which formed an organic film at the air-water interface. Dark secondary reaction with ozone after illumination resulted in SOA particle concentrations in excess of 1000 cm(-3), illustrating the production of unsaturated compounds by chemical reactions at the air-water interface. SOA numbers via photosensitization alone and in the absence of ozone did not exceed background levels. From these results, we derived a dependence of SOA numbers on nonanoic acid surface coverage and dissolved organic matter concentration. We present a discussion on the potential role of the air-sea interface in the production of atmospheric organic aerosol from photosensitized origins.

  6. Formation, disruption and mechanical properties of a rigid hydrophobin film at an air-water interface

    NASA Astrophysics Data System (ADS)

    Walker, Lynn; Kirby, Stephanie; Anna, Shelley; CMU Team

    Hydrophobins are small, globular proteins with distinct hydrophilic and hydrophobic regions that make them extremely surface active. The behavior of hydrophobins at surfaces has raised interest in their potential industrial applications, including use in surface coatings, food foams and emulsions, and as dispersants. Practical use of hydrophobins requires an improved understanding of the interfacial behavior of these proteins, both individually and in the presence of surfactants. Cerato-ulmin (CU) is a hydrophobin that has been shown to strongly stabilize air bubbles and oil droplets through the formation of a persistent protein film at the interface. In this work, we characterize the adsorption behavior of CU at air/water interfaces by measuring the surface tension and interfacial rheology as a function of adsorption time. CU is found to strongly, irreversibly adsorb at air/water interfaces; the magnitude of the dilatational modulus increases with adsorption time and surface pressure, until the CU eventually forms a rigid film. The persistence of this film is tested through the addition of SDS, a strong surfactant, to the bulk. SDS is found to co-adsorb to interfaces pre-coated with a CU film. At high concentrations, the addition of SDS significantly decreases the dilatational modulus, indicating disruption and displacement of CU. These results lend insight into the complex interfacial interactions between hydrophobins and surfactants. Funding from GoMRI.

  7. Semifluorinated Alkanes at the Air-Water Interface: Tailoring Structure and Rheology at the Molecular Scale.

    PubMed

    Theodoratou, Antigoni; Jonas, Ulrich; Loppinet, Benoit; Geue, Thomas; Stangenberg, Rene; Keller, Rabea; Li, Dan; Berger, Rüdiger; Vermant, Jan; Vlassopoulos, Dimitris

    2016-04-01

    Semifluorinated alkanes form monolayers with interesting properties at the air-water interface due to their pronounced amphi-solvophobic nature and the stiffness of the fluorocarbons. In the present work, using a combination of structural and dynamic probes, we investigated how small molecular changes can be used to control the properties of such an interface, in particular its organization, rheology, and reversibility during compression-expansion cycles. Starting from a reference system perfluor(dodecyl)dodecane, we first retained the linear structure but changed the linkage groups between the alkyl chains and the fluorocarbons, by introducing either a phenyl group or two oxygens. Next, the molecular structure was changed from linear to branched, with four side chains (two fluorocarbons and two hydrocarbons) connected to extended aromatic cores. Neutron reflectivity at the air-water interface and scanning force microscopy on deposited films show how the changes in the molecular structure affect molecular arrangement relative to the interface. Rheological and compression-expansion measurements demonstrate the significant consequences of these changes in molecular structure and interactions on the interfacial properties. Remarkably, even with these simple molecules, a wide range of surface rheological behaviors can be engineered, from viscous over viscoelastic to brittle solids, for very similar values of the surface pressure.

  8. Real-time investigation of protein unfolding at an air-water interface at the 1 s time scale.

    PubMed

    Yano, Yohko F; Arakawa, Etsuo; Voegeli, Wolfgang; Matsushita, Tadashi

    2013-11-01

    Protein unfolding at an air-water interface has been demonstrated such that the X-ray reflectivity can be measured with an acquisition time of 1 s using a recently developed simultaneous multiple-angle-wavelength-dispersive X-ray reflectometer. This has enabled the electron density profile of the adsorbed protein molecules to be obtained in real time. A globular protein, lysozyme, adsorbed at the air-water interface is found to unfold into a flat shape within 1 s.

  9. Spectroscopic signatures of ozone at the air-water interface and photochemistry implications.

    PubMed

    Anglada, Josep M; Martins-Costa, Marilia; Ruiz-López, Manuel F; Francisco, Joseph S

    2014-08-12

    First-principles simulations suggest that additional OH formation in the troposphere can result from ozone interactions with the surface of cloud droplets. Ozone exhibits an affinity for the air-water interface, which modifies its UV and visible light spectroscopic signatures and photolytic rate constant in the troposphere. Ozone cross sections on the red side of the Hartley band (290- to 350-nm region) and in the Chappuis band (450-700 nm) are increased due to electronic ozone-water interactions. This effect, combined with the potential contribution of the O3 + hν → O((3)P) + O2(X(3)Σg(-)) photolytic channel at the interface, leads to an enhancement of the OH radical formation rate by four orders of magnitude. This finding suggests that clouds can influence the overall oxidizing capacity of the troposphere on a global scale by stimulating the production of OH radicals through ozone photolysis by UV and visible light at the air-water interface.

  10. A Mechanism for the Entrapment of DNA at an Air-Water Interface

    PubMed Central

    Eickbush, Thomas H.; Moudrianakis, Evangelos N.

    1977-01-01

    Addition of the intercalating dye quinacrine to a low ionic strength solution of DNA in quantities sufficient to saturate the high affinity sites in the DNA will result in the accumulation of the DNA at the solution interface. This entrapment of DNA at the air-water interface has been assayed by the adsorption of DNA to untreated carbon-coated electron microscope grids touched to the solution surface. Other intercalating dyes can also bring about this entrapment, if they possess a side arm large enough to occupy one of the DNA grooves when the dye is intercalated into the DNA. The extension and unwinding of the DNA helix brought about by the intercalating chromophore of the dye molecules are not requirements for the entrapment process. Spermidine, a simple polyamine that will bind to the DNA minor groove but that has no intercalating chromophore, was found to bring about this entrapment. Even simple mono- and divalent cations in the absence of the above ligands were found to promote a low level of surface entrapment. A model for the entrapment of DNA at the air-water interface is proposed in which one (or both) of the hydrophobic grooves of the DNA becomes a surface-active agent as a consequence of the association of various ligands and charge neutralization. ImagesFIGURE 1FIGURE 6 PMID:890027

  11. Aggregation behaviors of gelatin with cationic gemini surfactant at air/water interface.

    PubMed

    Wu, Dan; Xu, Guiying; Feng, Yujun; Li, Yiming

    2007-03-10

    The dilational rheological properties of gelatin with cationic gemini surfactant 1,2-ethane bis(dimethyl dodecyl ammonium bromide) (C(12)C(2)C(12)) at air/water interface were investigated using oscillating barriers method at low frequency (0.005-0.1 Hz), which was compared with single-chain surfactant dodecyltrimethyl ammonium bromide (DTAB). The results indicate that the maximum dilational modulus and the film stability of gelatin-C(12)C(2)C(12) are higher than those of gelatin-DTAB. At high concentration of C(12)C(2)C(12) or DTAB, the dilational modulus of gelatin-surfactant system becomes close to that corresponding to pure surfactant, suggesting gelatin at interface is replaced by surfactant. This replacement is also observed by surface tension measurement. However, it is found that gelatin-C(12)C(2)C(12) system has two obvious breaks but gelatin-DTAB has not in surface tension isotherms. These phenomena are ascribed to the double charges and strong hydrophobicity of C(12)C(2)C(12). Based on these experimental results, a mechanism of gelatin-surfactant interaction at air/water interface is proposed.

  12. Surface pressure-induced layer growth of a monolayer at the air-water interface

    SciTech Connect

    Fang, J.Y.; Uphaus, R.A. )

    1994-04-01

    Spread monolayers containing a nematic liquid crystal and stearic acid were characterized at various mole fractions by determination of surface pressure-area isotherms at the air-water interface. The surface-composition phase diagrams indicate that compression induces a new phase transition in the films, which changes from a mixed monolayer to a supermonomolecular system. X-ray diffraction and optical absorption spectra demonstrate that the supermolecular array consists of an island liquid crystal monolayer and a uniform stearic acid monolayer. 12 refs., 7 figs.

  13. Ligand interaction with the purified serotonin transporter in solution and at the air/water interface

    SciTech Connect

    Faivre, V.; Manivet, P.; Callaway, J.C.; Morimoto, H.; Airaksinen, M.M.; Baszkin, A.; Launay, J.M.; Rosilio, V.

    2000-06-01

    The purified serotonin transporter (SERT) was spread at the air/water interface and the effects both of its surface density and of the temperature on its interfacial behavior were studied. The recorded isotherms evidenced the existence of a stable monolayer undergoing a lengthy rearrangement. SERT/ligand interactions appeared to be dependent on the nature of the studied molecules. Whereas an unrelated drug (chlorcyclizine) did not bind to the spread SERT, it interacted with its specific ligands. Compared to heterocyclic drugs, for which binding appeared to be concentration-dependent, a 'two-site' mechanism was evidenced for pinoline and imipramine.

  14. Formation of H-type liquid crystal dimer at air-water interface

    SciTech Connect

    Karthik, C. Gupta, Adbhut Joshi, Aditya Manjuladevi, V. Gupta, Raj Kumar; Varia, Mahesh C.; Kumar, Sandeep

    2014-04-24

    We have formed the Langmuir monolayer of H-shaped Azo linked liquid crystal dimer molecule at the air-water interface. Isocycles of the molecule showed hysteresis suggesting the ir-reversible nature of the monolayer formed. The thin film deposited on the silicon wafer was characterized using Atomic Force Microscopy (AFM) and Field Emission Scanning Electron Microscopy (FESEM). The images showed uniform domains of the dimer molecule. We propose that these molecules tend to take book shelf configuration in the liquid phase.

  15. Organization of tethered polyoxazoline polymer brushes at the air/water interface

    NASA Astrophysics Data System (ADS)

    Gutberlet, T.; Wurlitzer, A.; Dietrich, U.; Politsch, E.; Cevc, G.; Steitz, R.; Lösche, M.

    2000-06-01

    Surface monolayers of short chain poly(methyl oxazoline) (PMeOx) attached to diacylglycerol have been investigated by X-ray and neutron reflectivity in pure systems and in binary mixtures with the unmodified phospholipid DMPC at the air/water interface. Reflectivity curves of pure PMeOx and its mixtures with DMPC indicate an extended conformation of the polymer independent of the available lateral area and pressure. An almost linear increase in the thickness of the polymer layer is found with increasing lateral pressure π. The thickness of the hydrophobic slab within the surface monolayers decreases continuously upon addition of PMeOx to DMPC.

  16. Biogenic amine – surfactant interactions at the air-water interface.

    PubMed

    Penfold, J; Thomas, R K; Li, P X

    2015-07-01

    The strong interaction between polyamines and anionic surfactants results in pronounced adsorption at the air-water interface and can lead to the formation of layered surface structures. The transition from monolayer adsorption to more complex surface structures depends upon solution pH, and the structure and molecular weight of the polyamine. The effects of manipulating the polyamine molecular weight and structure on the adsorption of the anionic surfactant sodium dodecyl sulphate at the air-water interface are investigated using neutron reflectivity and surface tension, for the biogenic amines putrescine, spermidine and spermine. The results show how changing the number of amine groups and the spacing between the amine groups impacts upon the surface adsorption. At lower pH, 3-7, and for the higher molecular weight polyamines, spermidine and spermine, ordered multilayer structures are observed. For putrescine at all pH and for spermidine and spermine at high pH, monolayer adsorption with enhanced surfactant adsorption compared to the pure surfactant is observed. The data for the biogenic amines, when compared with similar data for the polyamines ethylenediamine, diethylenetriamine and triethylenetetramine, indicate that the spacing between amines groups is more optimal for the formation of ordered surface multilayer structures.

  17. Mechanisms of Polyelectrolyte Enhanced Surfactant Adsorption at the Air-Water Interface

    PubMed Central

    Stenger, Patrick C.; Palazoglu, Omer A.; Zasadzinski, Joseph A.

    2009-01-01

    Chitosan, a naturally occurring cationic polyelectrolyte, restores the adsorption of the clinical lung surfactant Survanta to the air-water interface in the presence of albumin at much lower concentrations than uncharged polymers such as polyethylene glycol. This is consistent with the positively charged chitosan forming ion pairs with negative charges on the albumin and lung surfactant particles, reducing the net charge in the double-layer, and decreasing the electrostatic energy barrier to adsorption to the air-water interface. However, chitosan, like other polyelectrolytes, cannot perfectly match the charge distribution on the surfactant, which leads to patches of positive and negative charge at net neutrality. Increasing the chitosan concentration further leads to a reduction in the rate of surfactant adsorption consistent with an over-compensation of the negative charge on the surfactant and albumin surfaces, which creates a new repulsive electrostatic potential between the now cationic surfaces. This charge neutralization followed by charge inversion explains the window of polyelectrolyte concentration that enhances surfactant adsorption; the same physical mechanism is observed in flocculation and re-stabilization of anionic colloids by chitosan and in alternate layer deposition of anionic and cationic polyelectrolytes on charged colloids. PMID:19366599

  18. Atmospheric photochemistry at a fatty acid–coated air-water interface

    NASA Astrophysics Data System (ADS)

    Rossignol, Stéphanie; Tinel, Liselotte; Bianco, Angelica; Passananti, Monica; Brigante, Marcello; Donaldson, D. James; George, Christian

    2016-08-01

    Although fatty acids are believed to be photochemically inert in the actinic region, complex volatile organic compounds are produced during illumination of an air-water interface coated solely with a monolayer of carboxylic acid. When aqueous solutions containing nonanoic acid (NA) at bulk concentrations that give rise to just over a monolayer of NA coverage are illuminated with actinic radiation, saturated and unsaturated aldehydes are seen in the gas phase, and more highly oxygenated products appear in the aqueous phase. This chemistry is probably initiated by triplet-state NA molecules excited by direct absorption of actinic light at the water surface. Because fatty acids–covered interfaces are ubiquitous in the environment, such photochemical processing will have a substantial impact on local ozone and particle formation.

  19. Mechanical Stability of Polystyrene and Janus Particle Monolayers at the Air/Water Interface.

    PubMed

    Lenis, Jessica; Razavi, Sepideh; Cao, Kathleen D; Lin, Binhua; Lee, Ka Yee C; Tu, Raymond S; Kretzschmar, Ilona

    2015-12-16

    The compressional instability of particle-laden air/water interfaces is investigated with plain and surface-anisotropic (Janus) particles. We hypothesize that the amphiphilic nature of Janus particles leads to both anisotropic particle-particle and particle-interface interactions that can yield particle films with unique collapse mechanisms. Analysis of Langmuir isotherms and microstructural characterization of the homogeneous polystyrene particle films during compression reveal an interfacial buckling instability followed by folding, which is in good agreement with predictions from classical elasticity theory. In contrast, Janus particle films exhibit a different behavior during compression, where the collapse mode occurs through the subduction of the Janus particle film. Our results suggest that particle-laden films comprised of surface-anisotropic particles can be engineered to evolve new material properties. PMID:26588066

  20. Trapping of Sodium Dodecyl Sulfate at the Air-Water Interface of Oscillating Bubbles.

    PubMed

    Corti, Mario; Pannuzzo, Martina; Raudino, Antonio

    2015-06-16

    We report that at very low initial bulk concentrations, a couple of hundred times below the critical micellar concentration (CMC), anionic surfactant sodium dodecyl sulfate (SDS) adsorbed at the air-water interface of a gas bubble cannot be removed, on the time scale of the experiment (hours), when the surrounding solution is gently replaced by pure water. Extremely sensitive interferometric measurements of the resonance frequency of the bubble-forced oscillations give precise access to the concentration of the surfactant monolayer. The bulk-interface dynamic exchange of SDS molecules is shown to be inhibited below a concentration which we believe refers to a kind of gas-liquid phase transition of the surface monolayer. Above this threshold we recover the expected concentration-dependent desorption. The experimental observations are interpreted within simple energetic considerations supported by molecular dynamics (MD) calculations. PMID:26039913

  1. Atmospheric photochemistry at a fatty acid-coated air-water interface

    NASA Astrophysics Data System (ADS)

    Rossignol, Stéphanie; Tinel, Liselotte; Bianco, Angelica; Passananti, Monica; Brigante, Marcello; Donaldson, D. James; George, Christian

    2016-08-01

    Although fatty acids are believed to be photochemically inert in the actinic region, complex volatile organic compounds are produced during illumination of an air-water interface coated solely with a monolayer of carboxylic acid. When aqueous solutions containing nonanoic acid (NA) at bulk concentrations that give rise to just over a monolayer of NA coverage are illuminated with actinic radiation, saturated and unsaturated aldehydes are seen in the gas phase, and more highly oxygenated products appear in the aqueous phase. This chemistry is probably initiated by triplet-state NA molecules excited by direct absorption of actinic light at the water surface. Because fatty acids-covered interfaces are ubiquitous in the environment, such photochemical processing will have a substantial impact on local ozone and particle formation.

  2. Atmospheric photochemistry at a fatty acid-coated air-water interface.

    PubMed

    Rossignol, Stéphanie; Tinel, Liselotte; Bianco, Angelica; Passananti, Monica; Brigante, Marcello; Donaldson, D James; George, Christian

    2016-08-12

    Although fatty acids are believed to be photochemically inert in the actinic region, complex volatile organic compounds are produced during illumination of an air-water interface coated solely with a monolayer of carboxylic acid. When aqueous solutions containing nonanoic acid (NA) at bulk concentrations that give rise to just over a monolayer of NA coverage are illuminated with actinic radiation, saturated and unsaturated aldehydes are seen in the gas phase, and more highly oxygenated products appear in the aqueous phase. This chemistry is probably initiated by triplet-state NA molecules excited by direct absorption of actinic light at the water surface. Because fatty acids-covered interfaces are ubiquitous in the environment, such photochemical processing will have a substantial impact on local ozone and particle formation. PMID:27516601

  3. Dynamic mechanical properties of a polyelectrolyte adsorbed insoluble lipid monolayer at the air-water interface.

    PubMed

    Park, Chang Young; Kim, Mahn Won

    2015-04-23

    Polymers have been used to stabilize interfaces or to tune the mechanical properties of interfaces in various contexts, such as in oil emulsions or biological membranes. Although the structural properties of these systems are relatively well-studied, instrumental limitations continue to make it difficult to understand how the addition of polymer affects the dynamic mechanical properties of thin and soft films. We have solved this challenge by developing a new instrument, an optical-tweezer-based interface shear microrheometer (ISMR). With this technique, we observed that the interface shear modulus, G*, of a dioctadecyldimethylammonium chloride (DODAC) monolayer at the air-water interface significantly increased with adsorption of polystyrenesulfonate (PSS). In addition, the viscous film (DODAC monolayer) became a viscoelastic film with PSS adsorption. At a low salt concentration, 10 mM of NaCl in the subphase, the viscoelasticity of the DODAC/PSS composite was predominantly determined by a particular property of PSS, that is, it behaves as a Gaussian chain in a θ-solvent. At a high salt concentration, 316 mM of NaCl, the thin film behaved as a polymer melt excluding water molecules. PMID:25826703

  4. Mechanistic Insights on the Photosensitized Chemistry of a Fatty Acid at the Air/Water Interface

    PubMed Central

    2016-01-01

    Interfaces are ubiquitous in the environment and many atmospheric key processes, such as gas deposition, aerosol, and cloud formation are, at one stage or another, strongly impacted by physical and chemical processes occurring at interfaces. Here, the photoinduced chemistry of an air/water interface coated with nonanoic acid—a fatty acid surfactant we use as a proxy for chemically complex natural aqueous surface microlayers—was investigated as a source of volatile and semivolatile reactive organic species. The carboxylic acid coating significantly increased the propensity of photosensitizers, chosen to mimic those observed in real environmental waters, to partition to the interface and enhance reactivity there. Photochemical formation of functionalized and unsaturated compounds was systematically observed upon irradiation of these coated surfaces. The role of a coated interface appears to be critical in providing a concentrated medium allowing radical–radical reactions to occur in parallel with molecular oxygen additions. Mechanistic insights are provided from extensive analysis of products observed in both gas and aqueous phases by online switchable reagent ion-time of flight-mass spectrometry and by off-line ultraperformance liquid chromatography coupled to a Q Exactive high resolution mass spectrometer through heated electrospray ionization, respectively. PMID:27611489

  5. Catechol oxidation by ozone and hydroxyl radicals at the air-water interface.

    PubMed

    Pillar, Elizabeth A; Camm, Robert C; Guzman, Marcelo I

    2014-12-16

    Anthropogenic emissions of aromatic hydrocarbons promptly react with hydroxyl radicals undergoing oxidation to form phenols and polyphenols (e.g., catechol) typically identified in the complex mixture of humic-like substances (HULIS). Because further processing of polyphenols in secondary organic aerosols (SOA) can continue mediated by a mechanism of ozonolysis at interfaces, a better understanding about how these reactions proceed at the air-water interface is needed. This work shows how catechol, a molecular probe of the oxygenated aromatic hydrocarbons present in SOA, can contribute interfacial reactive species that enhance the production of HULIS under atmospheric conditions. Reactive semiquinone radicals are quickly produced upon the encounter of 40 ppbv-6.0 ppmv O3(g) with microdroplets containing [catechol] = 1-150 μM. While the previous pathway results in the instantaneous formation of mono- and polyhydroxylated aromatic rings (PHA) and chromophoric mono- and polyhydroxylated quinones (PHQ), a different channel produces oxo- and dicarboxylic acids of low molecular weight (LMW). The cleavage of catechol occurs at the 1,2 carbon-carbon bond at the air-water interface through the formation of (1) an ozonide intermediate, (2) a hydroperoxide, and (3) cis,cis-muconic acid. However, variable [catechol] and [O3(g)] can affect the ratio of the primary products (cis,cis-muconic acid and trihydroxybenzenes) and higher order products observed (PHA, PHQ, and LMW oxo- and dicarboxylic acids). Secondary processing is confirmed by mass spectrometry, showing the production of crotonic, maleinaldehydic, maleic, glyoxylic, and oxalic acids. The proposed pathway can contribute precursors to aqueous SOA (AqSOA) formation, converting aromatic hydrocarbons into polyfunctional species widely found in tropospheric aerosols with light-absorbing brown carbon.

  6. Catechol oxidation by ozone and hydroxyl radicals at the air-water interface.

    PubMed

    Pillar, Elizabeth A; Camm, Robert C; Guzman, Marcelo I

    2014-12-16

    Anthropogenic emissions of aromatic hydrocarbons promptly react with hydroxyl radicals undergoing oxidation to form phenols and polyphenols (e.g., catechol) typically identified in the complex mixture of humic-like substances (HULIS). Because further processing of polyphenols in secondary organic aerosols (SOA) can continue mediated by a mechanism of ozonolysis at interfaces, a better understanding about how these reactions proceed at the air-water interface is needed. This work shows how catechol, a molecular probe of the oxygenated aromatic hydrocarbons present in SOA, can contribute interfacial reactive species that enhance the production of HULIS under atmospheric conditions. Reactive semiquinone radicals are quickly produced upon the encounter of 40 ppbv-6.0 ppmv O3(g) with microdroplets containing [catechol] = 1-150 μM. While the previous pathway results in the instantaneous formation of mono- and polyhydroxylated aromatic rings (PHA) and chromophoric mono- and polyhydroxylated quinones (PHQ), a different channel produces oxo- and dicarboxylic acids of low molecular weight (LMW). The cleavage of catechol occurs at the 1,2 carbon-carbon bond at the air-water interface through the formation of (1) an ozonide intermediate, (2) a hydroperoxide, and (3) cis,cis-muconic acid. However, variable [catechol] and [O3(g)] can affect the ratio of the primary products (cis,cis-muconic acid and trihydroxybenzenes) and higher order products observed (PHA, PHQ, and LMW oxo- and dicarboxylic acids). Secondary processing is confirmed by mass spectrometry, showing the production of crotonic, maleinaldehydic, maleic, glyoxylic, and oxalic acids. The proposed pathway can contribute precursors to aqueous SOA (AqSOA) formation, converting aromatic hydrocarbons into polyfunctional species widely found in tropospheric aerosols with light-absorbing brown carbon. PMID:25423038

  7. Equation of state and adsorption dynamics of soft microgel particles at an air-water interface.

    PubMed

    Deshmukh, Omkar S; Maestro, Armando; Duits, Michel H G; van den Ende, Dirk; Stuart, Martien Cohen; Mugele, Frieder

    2014-09-28

    Understanding the adsorption dynamics of soft microgel particles is a key step in designing such particles for potential applications as stimuli-responsive Pickering stabilizers for foams or emulsions. In this study we experimentally determine an equation of state (EOS) for poly (N-isopropylacrylamide) (PNIPAM) microgel particles adsorbed onto an air-water interface using a Langmuir film balance. We detect a finite surface pressure at very low surface concentration of particles, for which standard theories based on hard disk models predict negligible pressures, implying that the particles must deform strongly upon adsorption to the interface. Furthermore, we study the evolution of the surface pressure due to the adsorption of PNIPAM particles as a function of time using pendant drop tensiometry. The equation of state determined in the equilibrium measurements allows us to extract the adsorbed amount as a function of time. We find a mixed-kinetic adsorption that is initially controlled by the diffusion of particles towards the interface. At later stages, a slow exponential relaxation indicates the presence of a coverage-dependent adsorption barrier related to crowding of particles at the interface. PMID:24954112

  8. Entropy of adsorption of mixed surfactants from solutions onto the air/water interface

    USGS Publications Warehouse

    Chen, L.-W.; Chen, J.-H.; Zhou, N.-F.

    1995-01-01

    The partial molar entropy change for mixed surfactant molecules adsorbed from solution at the air/water interface has been investigated by surface thermodynamics based upon the experimental surface tension isotherms at various temperatures. Results for different surfactant mixtures of sodium dodecyl sulfate and sodium tetradecyl sulfate, decylpyridinium chloride and sodium alkylsulfonates have shown that the partial molar entropy changes for adsorption of the mixed surfactants were generally negative and decreased with increasing adsorption to a minimum near the maximum adsorption and then increased abruptly. The entropy decrease can be explained by the adsorption-orientation of surfactant molecules in the adsorbed monolayer and the abrupt entropy increase at the maximum adsorption is possible due to the strong repulsion between the adsorbed molecules.

  9. Turbulent heat and mass transfers across a thermally stratified air-water interface

    NASA Technical Reports Server (NTRS)

    Papadimitrakis, Y. A.; Hsu, Y.-H. L.; Wu, J.

    1986-01-01

    Rates of heat and mass transfer across an air-water interface were measured in a wind-wave research facility, under various wind and thermal stability conditions (unless otherwise noted, mass refers to water vapor). Heat fluxes were obtained from both the eddy correlation and the profile method, under unstable, neutral, and stable conditions. Mass fluxes were obtained only under unstable stratification from the profile and global method. Under unstable conditions the turbulent Prandtl and Schmidt numbers remain fairly constant and equal to 0.74, whereas the rate of mass transfer varies linearly with bulk Richardson number. Under stable conditions the turbulent Prandtl number rises steadily to a value of 1.4 for a bulk Richardson number of about 0.016. Results of heat and mass transfer, expressed in the form of bulk aerodynamic coefficients with friction velocity as a parameter, are also compared with field data.

  10. Reversible monolayer-to-crystalline phase transition in amphiphilic silsesquioxane at the air-water interface

    DOE PAGES

    Banerjee, R.; Sanyal, M. K.; Bera, M. K.; Gibaud, A.; Lin, B.; Meron, M.

    2015-02-17

    We report on the counter intuitive reversible crystallisation of two-dimensional monolayer of Trisilanolisobutyl Polyhedral Oligomeric SilSesquioxane (TBPOSS) on water surface using synchrotron x-ray scattering measurements. Amphiphilic TBPOSS form rugged monolayers and Grazing Incidence X-ray Scattering (GIXS) measurements reveal that the in-plane inter-particle correlation peaks, characteristic of two-dimensional system, observed before transition is replaced by intense localized spots after transition. The measured x-ray scattering data of the non-equilibrium crystalline phase on the air-water interface could be explained with a model that assumes periodic stacking of the TBPOSS dimers. These crystalline stacking relaxes upon decompression and the TBPOSS layer retains its initialmore » monolayer state. The existence of these crystals in compressed phase is confirmed by atomic force microscopy measurements by lifting the materials on a solid substrate.« less

  11. Reversible monolayer-to-crystalline phase transition in amphiphilic silsesquioxane at the air-water interface

    SciTech Connect

    Banerjee, R.; Sanyal, M. K.; Bera, M. K.; Gibaud, A.; Lin, B.; Meron, M.

    2015-02-17

    We report on the counter intuitive reversible crystallisation of two-dimensional monolayer of Trisilanolisobutyl Polyhedral Oligomeric SilSesquioxane (TBPOSS) on water surface using synchrotron x-ray scattering measurements. Amphiphilic TBPOSS form rugged monolayers and Grazing Incidence X-ray Scattering (GIXS) measurements reveal that the in-plane inter-particle correlation peaks, characteristic of two-dimensional system, observed before transition is replaced by intense localized spots after transition. The measured x-ray scattering data of the non-equilibrium crystalline phase on the air-water interface could be explained with a model that assumes periodic stacking of the TBPOSS dimers. These crystalline stacking relaxes upon decompression and the TBPOSS layer retains its initial monolayer state. The existence of these crystals in compressed phase is confirmed by atomic force microscopy measurements by lifting the materials on a solid substrate.

  12. Conformational changes of a calix[8]arene derivative at the air-water interface.

    PubMed

    de Miguel, Gustavo; Pedrosa, José M; Martín-Romero, María T; Muñoz, Eulogia; Richardson, Tim H; Camacho, Luis

    2005-03-10

    The particular behavior of a p-tert-butyl calix[8]arene derivative (C8A) has been studied at the air-water interface using surface pressure-area isotherms, surface potential-area isotherms, film relaxation measurements, Brewster angle microscopy (BAM), and infrared spectroscopy for Langmuir-Blodgett films. Thus, it is observed that the properties of the film, for example, isotherms, domain formation, and FTIR spectra, recorded during the first compression cycle differ appreciably from those during the second compression and following cycles. The results obtained are interpreted on the basis of the conformational changes of the C8A molecules by surface pressure, allowing us to inquire into the inter- and intramolecular interactions (hydrogen bonds) of those molecules. Thus, the compression induces changes in the kind of hydrogen bonds from intra- and intermolecular with other C8A molecules to hydrogen bonds with water molecules. PMID:16851456

  13. Conformational changes of a calix[8]arene derivative at the air-water interface.

    PubMed

    de Miguel, Gustavo; Pedrosa, José M; Martín-Romero, María T; Muñoz, Eulogia; Richardson, Tim H; Camacho, Luis

    2005-03-10

    The particular behavior of a p-tert-butyl calix[8]arene derivative (C8A) has been studied at the air-water interface using surface pressure-area isotherms, surface potential-area isotherms, film relaxation measurements, Brewster angle microscopy (BAM), and infrared spectroscopy for Langmuir-Blodgett films. Thus, it is observed that the properties of the film, for example, isotherms, domain formation, and FTIR spectra, recorded during the first compression cycle differ appreciably from those during the second compression and following cycles. The results obtained are interpreted on the basis of the conformational changes of the C8A molecules by surface pressure, allowing us to inquire into the inter- and intramolecular interactions (hydrogen bonds) of those molecules. Thus, the compression induces changes in the kind of hydrogen bonds from intra- and intermolecular with other C8A molecules to hydrogen bonds with water molecules.

  14. Real-time imaging of crystallization in polylactide enantiomeric monolayers at the air-water interface.

    PubMed

    Kim, Young Shin; Snively, Christopher M; Liu, Yujuan; Rabolt, John F; Chase, D Bruce

    2008-10-01

    A newly developed planar array infrared reflection-absorption spectrograph (PA-IRRAS) offers significant advantages over conventional approaches including fast acquisition speed, excellent compensation for water vapor, and an excellent capacity for large infrared accessories, e.g., a water trough. In this study, the origin of stereocomplexation in a polylactide enantiomeric monolayer at the air-water interface was investigated using PA-IRRAS. PA-IRRAS was used as a probe to follow the real-time conformational changes associated with intermolecular interactions of polymer chains during the compression of the monolayers. It was found that a mixture of poly(D-lactic acid) (PDLA) and poly(L-lactic acid) (PLLA) (D/L) formed a stereocomplex when the two-dimensional monolayer developed at the air-water interface before film compression, indicating that there is no direct correlation between film compression and stereocomplexation. PA-IRRAS spectra of the stereocomplex exhibited distinct band shifts in crystalline sensitive components, e.g., the vas(C-O-C, h) mode, as well as amorphous-dependent components, e.g., the vs(C-O-C) mode, when compared with the spectra of PLLA alone. On the other hand, time-resolved PA-IRRAS spectra, which were obtained as the films were being compressed, revealed that both monolayers of PLLA and mixed PLLA/PDLA stereocomplex were crystallized into a 10(3)-helix and a 3(1)-helix, respectively, with a distinct band shift in crystalline sensitive components only. Fourier self-deconvolution of the spectra demonstrated that the band shift in crystalline sensitive components is correlated with the intermolecular interaction of polymer chains. PMID:18781784

  15. Hydration, Orientation, and Conformation of Methylglyoxal at the Air-Water Interface.

    PubMed

    Wren, Sumi N; Gordon, Brittany P; Valley, Nicholas A; McWilliams, Laura E; Richmond, Geraldine L

    2015-06-18

    Aqueous-phase processing of methylglyoxal (MG) has been suggested to constitute an important source of secondary organic aerosol (SOA). The uptake of MG to aqueous particles is higher than expected because its carbonyl moieties can hydrate to form geminal diols, as well as because MG and its hydration products can undergo aldol condensation reactions to form larger oligomers in solution. MG is known to be surface active, but an improved description of its surface behavior is crucial to understanding MG-SOA formation. These studies investigate MG adsorption, focusing on its hydration state at the air-water interface, using a combined experimental and theoretical approach that involves vibrational sum frequency spectroscopy, molecular dynamics simulations, and density functional theory calculations. Together, the experimental and theoretical data show that MG exists predominantly in a singly hydrated state (diol) at the interface, with a diol-tetrol ratio at the surface higher than that for the bulk. In addition to exhibiting a strong surface activity, we find that MG significantly perturbs the water structure at the interface. The results have implications for understanding the atmospheric fate of methylglyoxal.

  16. Amyloid fibril formation at a uniformly sheared air/water interface

    NASA Astrophysics Data System (ADS)

    Posada, David; Hirsa, Amir

    2013-11-01

    Amyloid fibril formation is a process by which protein molecules in solution form nuclei and aggregate into fibrils. Amyloid fibrils have long been associated with several common diseases such as Parkinson's disease and Alzheimer's. More recently, fibril protein deposition has been implicated in uncommon disorders leading to the failure of various organs including the kidneys, heart, and liver. Fibrillization can also play a detrimental role in biotherapeutic production. Results from previous studies show that a hydrophobic interface, such air/water, can accelerate fibrillization. Studies also show that agitation accelerates fibrillization. When attempting to elucidate fundamental mechanisms of fibrillization and distinguish the effects of interfaces and flow, it can be helpful to experiment with uniformly sheared interfaces. A new Taylor-Couette device is introduced for in situ, real-time high resolution microscopy. With a sub-millimeter annular gap, surface tension acts as the channel floor, permitting a stable meniscus to be placed arbitrarily close to a microscope to study amyloid fibril formation over long periods.

  17. Ultrafast Reorientational Dynamics of Leucine at the Air-Water Interface.

    PubMed

    Donovan, Michael A; Yimer, Yeneneh Y; Pfaendtner, Jim; Backus, Ellen H G; Bonn, Mischa; Weidner, Tobias

    2016-04-27

    Ultrafast dynamics of protein side chains are involved in important biological processes such as ligand binding, protein folding, and hydration. In addition, the dynamics of a side chain can report on local environments within proteins. While protein side chain dynamics have been probed for proteins in solution with nuclear magnetic resonance and infrared methods for decades, information about side chain dynamics at interfaces is lacking. At the same time, the dynamics and motions of side chains can be particularly important for interfacial binding and protein-driven surface manipulation. We here demonstrate that ultrafast reorientation dynamics of leucine amino acids at interfaces can be recorded in situ and in real time using polarization- and time-resolved pump-probe sum frequency generation (SFG). Combined with molecular dynamics simulations, time-resolved SFG was used to probe the reorientation of the isopropyl methyl groups of l-leucine at the air-water interface. The data show that the methyl units reorient diffusively at an in plane rate of Dφ = 0.07 rad(2)/ps and an out of plane rate of Dθ = 0.05 rad(2)/ps. PMID:27057584

  18. Mechanism of vibrational energy dissipation of free OH groups at the air-water interface.

    PubMed

    Hsieh, Cho-Shuen; Campen, R Kramer; Okuno, Masanari; Backus, Ellen H G; Nagata, Yuki; Bonn, Mischa

    2013-11-19

    Interfaces of liquid water play a critical role in a wide variety of processes that occur in biology, a variety of technologies, and the environment. Many macroscopic observations clarify that the properties of liquid water interfaces significantly differ from those of the bulk liquid. In addition to interfacial molecular structure, knowledge of the rates and mechanisms of the relaxation of excess vibrational energy is indispensable to fully understand physical and chemical processes of water and aqueous solutions, such as chemical reaction rates and pathways, proton transfer, and hydrogen bond dynamics. Here we elucidate the rate and mechanism of vibrational energy dissipation of water molecules at the air-water interface using femtosecond two-color IR-pump/vibrational sum-frequency probe spectroscopy. Vibrational relaxation of nonhydrogen-bonded OH groups occurs at a subpicosecond timescale in a manner fundamentally different from hydrogen-bonded OH groups in bulk, through two competing mechanisms: intramolecular energy transfer and ultrafast reorientational motion that leads to free OH groups becoming hydrogen bonded. Both pathways effectively lead to the transfer of the excited vibrational modes from free to hydrogen-bonded OH groups, from which relaxation readily occurs. Of the overall relaxation rate of interfacial free OH groups at the air-H2O interface, two-thirds are accounted for by intramolecular energy transfer, whereas the remaining one-third is dominated by the reorientational motion. These findings not only shed light on vibrational energy dynamics of interfacial water, but also contribute to our understanding of the impact of structural and vibrational dynamics on the vibrational sum-frequency line shapes of aqueous interfaces.

  19. Surface shear rheology of WPI-monoglyceride mixed films spread at the air-water interface.

    PubMed

    Carrera Sánchez, Cecilio; Rodríguez Patino, Juan M

    2004-07-01

    Surface shear viscosity of food emulsifiers may contribute appreciably to the long-term stability of food dispersions (emulsions and foams). In this work we have analyzed the structural, topographical, and shear characteristics of a whey protein isolate (WPI) and monoglyceride (monopalmitin and monoolein) mixed films spread on the air-water interface at pH 7 and at 20 degrees C. The surface shear viscosity (etas) depend on the surface pressure and on the composition of the mixed film. The surface shear viscosity varies greatly with the surface pressure. In general, the greater the surface pressure, the greater are the values of etas. The values of etas for the mixed WPI-monoolein monolayer were more than one order of magnitude lower than those for a WPI-monopalmitin mixed film, especially at the higher surface pressures. At higher surface pressures, collapsed WPI residues may be displaced from the interface by monoglyceride molecules with important repercussions on the shear characteristics of the mixed films. A shear-induced change in the topography and a segregation between domains of the film forming components were also observed. The displacement of the WPI by the monoglycerides is facilitates under shear conditions, especially for WPI-monoolein mixed films.

  20. Field observations of turbulent dissipation rate profiles immediately below the air-water interface

    NASA Astrophysics Data System (ADS)

    Wang, Binbin; Liao, Qian

    2016-06-01

    Near surface profiles of turbulence immediately below the air-water interface were measured with a free-floating Particle Image Velocimetry (PIV) system on Lake Michigan. The surface-following configuration allowed the system to measure the statistics of the aqueous-side turbulence in the topmost layer immediately below the water surface (z≈0˜15 cm, z points downward with 0 at the interface). Profiles of turbulent dissipation rate (ɛ) were investigated under a variety of wind and wave conditions. Various methods were applied to estimate the dissipation rate. Results suggest that these methods yield consistent dissipation rate profiles with reasonable scattering. In general, the dissipation rate decreases from the water surface following a power law relation in the top layer, ɛ˜z-0.7, i.e., the slope of the decrease was lower than that predicted by the wall turbulence theory, and the dissipation was considerably higher in the top layer for cases with higher wave ages. The measured dissipation rate profiles collapse when they were normalized with the wave speed, wave height, water-side friction velocity, and the wave age. This scaling suggests that the enhanced turbulence may be attributed to the additional source of turbulent kinetic energy (TKE) at the "skin layer" (likely due to micro-breaking), and its downward transport in the water column.

  1. Spread Films of Human Serum Albumin at the Air-Water Interface: Optimization, Morphology, and Durability.

    PubMed

    Campbell, Richard A; Ang, Joo Chuan; Sebastiani, Federica; Tummino, Andrea; White, John W

    2015-12-22

    It has been known for almost one hundred years that a lower surface tension can be achieved at the air-water interface by spreading protein from a concentrated solution than by adsorption from an equivalent total bulk concentration. Nevertheless, the factors that control this nonequilibrium process have not been fully understood. In the present work, we apply ellipsometry, neutron reflectometry, X-ray reflectometry, and Brewster angle microscopy to elaborate the surface loading of human serum albumin in terms of both the macroscopic film morphology and the spreading dynamics. We show that the dominant contribution to the surface loading mechanism is the Marangoni spreading of protein from the bulk of the droplets rather than the direct transfer of their surface films. The films can be spread on a dilute subphase if the concentration of the spreading solution is sufficient; if not, dissolution of the protein occurs, and only a textured adsorbed layer slowly forms. The morphology of the spread protein films comprises an extended network with regions of less textured material or gaps. Further, mechanical cycling of the surface area of the spread films anneals the network into a membrane that approach constant compressibility and has increased durability. Our work provides a new perspective on an old problem in colloid and interface science. The scope for optimization of the surface loading mechanism in a range of systems leading to its exploitation in deposition-based technologies in the future is discussed.

  2. Effect of grafted polymer species on particle monolayer structure at the air-water interface.

    PubMed

    Mouri, Emiko; Okazaki, Yoshitaka; Komune, Seishu; Yoshinaga, Kohji

    2011-03-01

    We have studied poly(methyl methacrylate)-grafted(PMMA) particle monolayer systems at the air-water interface. In previous papers, we reported that PMMA chains grafted from particles (silica particle and polystyrene latex) were extended on water surfaces. Through observing deposited particle monolayers on substrates using SEM, we have confirmed that PMMA of large molecular weights were either dispersed or arrayed in structure with long inter-particle distances approximately 500 nm. In contrast, low molecular weight PMMA were observed to aggregate upon deposition. We speculated that the difference in morphology in deposited particle monolayers would be attributed to the affinity between the grafted polymer and the substrate. To examine the effect of this affinity three new polymer-grafted silica particles were synthesized with a fairly high graft density of about 0.14 approximately 0.43 nm(-2). As well as PMMA-grafted silica particles (SiO2-PMMA), poly(2-hydroxyethyl methacrylate) and poly(t-butyl methacrylate)--grafted silica particles (SiO2-PHEMA and SiO2-PtBuMA) were also prepared and subjected to pi-A isotherm measurements and SEM observations. These pi-A isotherms indicated that polymer-grafted silica formed monolayer at the air-water interface, and the onset area of increasing surface pressure suggests that the polymer chains are extended on a water surface. However, the morphology of the deposited monolayer is highly dependent on polymer species: SiO2-PHEMA showed that the dispersed particle monolayer structure was independent of grafted molecular weight while SiO2-tBuMA showed an aggregated structure that was also independent of grafted moleculer weight. SiO2-PMMA showed intermediate tendencies: dispersed structure was observed with high grafted molecular weight and aggregated structure was observed with low grafted molecule weight. The morphology on glass substrate would be explaiened by hydrophilic interaction between grafted polymer and hydrophilic glass

  3. Bromine and heavy halide chemistry at the air/water and air/ice interfaces: a computational approach

    NASA Astrophysics Data System (ADS)

    Gladich, I.; Shepson, P. B.; Szleifer, I.; Carignano, M.

    2010-12-01

    The air-water and air-ice interfaces are critically important surfaces, with respect to the physical and chemical properties of the Earth's atmosphere. In particular chloride, bromide and iodide ions are strongly involved in the reactions occurring at aerosol surfaces that are hydrated and at the air-ice interface in the polar boundary layer. Unfortunately, experimental access to these interfaces are quite problematic and the computational approach, based on molecular dynamic simulations and quantum mechanic calculations, is an interesting alternative approach. In this work, molecular dynamic (MD) simulations are used to study the halide enhancements at the air-water interface in the case of a dilute mixture of iodide, bromide and chloride ions. The MD results show how the air- water halide enhancement is different in the case of mixtures from the case of binary solutions (i.e. anions plus counter-positive ions) and how the presence of these halides at the interfaces depends from their relative concentrations in solution. In detail, heavy halides are strongly enhanced at the interfaces even if they are minor constituents in the bulk. Furthermore the enhancement of the larger halide ions, like bromide, at the surface is greater if lighter halides, like chloride, are in greater excess in the bulk. The applications of this last result on some real system, like sea-water, and the importance of bromide ions in the polar chemistry of ozone depletion events suggest a combined approach, MD and quantum mechanism (QM) calculation, to investigate the ozonation reaction of bromide (Br-+O3 → BrO-+O2 ) in the ice-QLL and in bulk water. The study of the reaction constants suggests how the different environments can affect the kinetics of such reaction. These results can help to understand the complex chemistry occurring at the air-water interface of hydrated aerosol and at the air-ice interface in the polar boundary layer.

  4. Structural properties and organization of hexadecanol isomers at the air/water interface

    NASA Astrophysics Data System (ADS)

    Walker, Robert; Can, Süleyman; Mago, Deesha

    2006-03-01

    A wealth of experimental data and theoretical modeling has led to well-honed intuition about the surface properties and structure of symmetric amphiphiles adsorbed to liquid surfaces. Less clear is how asymmetric amphiphiles organize in two dimensions at different surface coverages. We have studied the structure and two dimensional phase behavior of hexadecanol isomers adsorbed to the air/water interface. These isomers include the linear, n-hexadecanol as well structures with the alcohol functional group in the 2-, 3-, and 4- positions. Surface pressure methods are employed to study thermodynamic behavior of these insoluble monolayers, and vibrational sum frequency generation -- a vibrational spectroscopy with surface specificity -- is used to probe the molecular conformation and orientation of molecules within films. At their equilibrium spreading pressures, both 1- and 2- hexadecanol form very compact films having a high degree of conformational order and molecular areas of 19 and 28 sq. Angstroms/molecule in the tightly packed limit. In contrast, monolayers formed by 3-hexadecanol and 4-hexadecanol are much more disordered - but very similar to each other - and occupy much larger areas/molecule (75 sq. Angstroms/molec) in the tightly packed limit.

  5. Orientation-controlled parallel assembly at the air-water interface

    NASA Astrophysics Data System (ADS)

    Park, Kwang Soon; Hao Hoo, Ji; Baskaran, Rajashree; Böhringer, Karl F.

    2012-10-01

    This paper presents an experimental and theoretical study with statistical analysis of a high-yield, orientation-specific fluidic self-assembly process on a preprogrammed template. We demonstrate self-assembly of thin (less than few hundred microns in thickness) parts, which is vital for many applications in miniaturized platforms but problematic for today's pick-and-place robots. The assembly proceeds row-by-row as the substrate is pulled up through an air-water interface. Experiments and analysis are presented with an emphasis on the combined effect of controlled surface waves and magnetic force. For various gap values between a magnet and Ni-patterned parts, magnetic force distributions are generated using Monte Carlo simulation and employed to predict assembly yield. An analysis of these distributions shows that a gradual decline in yield following the probability density function can be expected with degrading conditions. The experimentally determined critical magnetic force is in good agreement with a derived value from a model of competing forces acting on a part. A general set of design guidelines is also presented from the developed model and experimental data.

  6. Influence of the air-water interface on hydrosol lidar operation.

    PubMed

    Kokhanenko, Grigorii P; Krekova, Margarita M; Penner, Loganes E; Shamanaev, Vitalii S

    2005-06-10

    The results of seawater sensing by use of an airborne lidar with a changeable field of view (FOV) are presented, together with the results of numerical simulation of lidar operation by the Monte Carlo method. It is demonstrated that multiple scattering and wind-driven sea waves have opposite effects on the measured attenuation coefficient. At small FOVs the wind-driven sea waves cause the lidar signal decay rate to increase compared with the size of the plane surface and hence result in an overestimation of the retrieved attenuation coefficient. Inefficient operation of lidars with small FOVs is caused by strong fluctuations of lidar signal power that cannot be described by a normal distribution. Specific features of the fluctuations can be interpreted as manifestations of the well-known effect of backscattered signal amplification caused by the double passage of radiation through the same inhomogeneities. As for the plane air-water interface, multiple scattering is significant for large FOVs and compensates for the effect of wind-driven sea waves. The applicability of simple sea-surface models to a description of lidar signal power fluctuations is discussed.

  7. Duolayers at the Air/Water Interface: Improved Lifetime through Ionic Interactions.

    PubMed

    Prime, Emma L; Solomon, David H; Dagley, Ian J; Qiao, Greg G

    2016-08-01

    Ionic interactions to stabilize Langmuir films at the air/water interface have been used to develop improved duolayer films. Two-component mixtures of octadecanoic (stearic) acid and poly(diallyldimethylammonium chloride) (polyDADMAC) with different ratios were prepared and applied to the water surface. Surface pressure isotherm cycles demonstrated a significant improvement in film stability with the inclusion of the polymer. Viscoelastic properties were measured using canal viscometry and oscillating barriers, with both methods showing that the optimum ratio for improved properties was four octadecanoic acid molecules to one DADMAC unit (1:0.25). At this ratio it is expected multiple strong ionic interactions are formed along each polymer chain. Brewster angle microscopy showed decreased domain size with increased ratios of polyDADMAC, indicating that the polymer is interspersed across the surface. This new method to stabilize and increase the viscoelastic properties of charged monolayer films, using a premixed composition, will have application in areas such as water evaporation mitigation, optical devices, and foaming. PMID:27420341

  8. Substrateless Welding of Self-Assembled Silver Nanowires at Air/Water Interface.

    PubMed

    Hu, Hang; Wang, Zhongyong; Ye, Qinxian; He, Jiaqing; Nie, Xiao; He, Gufeng; Song, Chengyi; Shang, Wen; Wu, Jianbo; Tao, Peng; Deng, Tao

    2016-08-10

    Integrating connected silver nanowire networks with flexible polymers has appeared as a popular way to prepare flexible electronics. To reduce the contact resistance and enhance the connectivity between silver nanowires, various welding techniques have been developed. Herein, rather than welding on solid supporting substrates, which often requires complicated transferring operations and also may pose damage to heat-sensitive substrates, we report an alternative approach to prepare easily transferrable conductive networks through welding of self-assembled silver nanowires at the air/water interface using plasmonic heating. The intriguing welding behavior of partially aligned silver nanowires was analyzed with combined experimental observation and theoretical modeling. The underlying water not only physically supports the assembled silver nanowires but also buffers potential overheating during the welding process, thereby enabling effective welding within a broad range of illumination power density and illumination duration. The welded networks could be directly integrated with PDMS substrates to prepare high-performance stable flexible heaters that are stretchable, bendable, and can be easily patterned to explore selective heating applications. PMID:27437907

  9. Dipolar interactions between domains in lipid monolayers at the air-water interface.

    PubMed

    Rufeil-Fiori, Elena; Wilke, Natalia; Banchio, Adolfo J

    2016-05-25

    A great variety of biologically relevant monolayers present phase coexistence characterized by domains formed by lipids in an ordered phase state dispersed in a continuous, disordered phase. From the difference in surface densities between these phases, inter-domain dipolar interactions arise. These interactions are relevant for the determination of the spacial distribution of domains as well as their dynamics. In this work, we propose a novel way of estimating the dipolar repulsion using a passive method that involves the analysis of images of the monolayer with phase coexistence. This method is based on the comparison of the pair correlation function obtained from experiments with that obtained from Brownian dynamics simulations of a model system. As an example, we determined the difference in dipolar density of a binary monolayer of DSPC/DMPC at the air-water interface from the analysis of the radial distribution of domains, and the results are compared with those obtained by surface potential determinations. A systematic analysis for the experimentally relevant parameter range is given, which may be used as a working curve for obtaining the dipolar repulsion in different systems. PMID:27139819

  10. Substrateless Welding of Self-Assembled Silver Nanowires at Air/Water Interface.

    PubMed

    Hu, Hang; Wang, Zhongyong; Ye, Qinxian; He, Jiaqing; Nie, Xiao; He, Gufeng; Song, Chengyi; Shang, Wen; Wu, Jianbo; Tao, Peng; Deng, Tao

    2016-08-10

    Integrating connected silver nanowire networks with flexible polymers has appeared as a popular way to prepare flexible electronics. To reduce the contact resistance and enhance the connectivity between silver nanowires, various welding techniques have been developed. Herein, rather than welding on solid supporting substrates, which often requires complicated transferring operations and also may pose damage to heat-sensitive substrates, we report an alternative approach to prepare easily transferrable conductive networks through welding of self-assembled silver nanowires at the air/water interface using plasmonic heating. The intriguing welding behavior of partially aligned silver nanowires was analyzed with combined experimental observation and theoretical modeling. The underlying water not only physically supports the assembled silver nanowires but also buffers potential overheating during the welding process, thereby enabling effective welding within a broad range of illumination power density and illumination duration. The welded networks could be directly integrated with PDMS substrates to prepare high-performance stable flexible heaters that are stretchable, bendable, and can be easily patterned to explore selective heating applications.

  11. Impact of artificial monolayer application on stored water quality at the air-water interface.

    PubMed

    Pittaway, P; Martínez-Alvarez, V; Hancock, N; Gallego-Elvira, B

    2015-01-01

    Evaporation mitigation has the potential to significantly improve water use efficiency, with repeat applications of artificial monolayer formulations the most cost-effective strategy for large water storages. Field investigations of the impact of artificial monolayers on water quality have been limited by wind and wave turbulence, and beaching. Two suspended covers differing in permeability to wind and light were used to attenuate wind turbulence, to favour the maintenance of a condensed monolayer at the air/water interface of a 10 m diameter tank. An octadecanol formulation was applied twice-weekly to one of two covered tanks, while a third clean water tank remained uncovered for the 14-week duration of the trial. Microlayer and subsurface water samples were extracted once a week to distinguish impacts associated with the installation of covers, from the impact of prolonged monolayer application. The monolayer was selectively toxic to some phytoplankton, but the toxicity of hydrocarbons leaching from a replacement liner had a greater impact. Monolayer application did not increase water temperature, humified dissolved organic matter, or the biochemical oxygen demand, and did not reduce dissolved oxygen. The impact of an octadecanol monolayer on water quality and the microlayer may not be as detrimental as previously considered. PMID:26398042

  12. Gaseous exchange of polycyclic aromatic hydrocarbons across the air-water interface of lower Chesapeake Bay

    SciTech Connect

    Gustafson, K.E.; Dickhut, R.M.

    1995-12-31

    The gaseous exchange fluxes of polycyclic aromatic hydrocarbons (PAHs) across the air-water interface of lower Chesapeake Bay were determined using a modified two-film exchange model. Sampling covered the period January 1994 to June 1995 for five sites on lower Chesapeake Bay ranging from rural to urban and highly industrialized. Simultaneous air and water samples were collected and the atmospheric gas phase and water column dissolved phase analyzed via GC/MS for 17 PAHs. The direction and magnitude of flux for each PAH was calculated using Henry`s law constants, hydrological and meteorological parameters, Temperature was observed to be an important environmental factor in determining both the direction and magnitude of PAH gas exchange. Nonetheless, wind speed significantly impacts mass transfer coefficients, and therefore was found to control the magnitude of flux. Spatial and temporal variation of PAH gaseous exchange fluxes were examined. Fluxes were determined to be both into and out of Chesapeake Bay. The range of gas exchange fluxes ({minus}560 to 600{micro}g/M{sup 2}*Mo) is of the same order to 10X greater than atmospheric wet and dry depositional fluxes to lower Chesapeake Bay. The results of this study support the hypothesis that gas exchange is a major transport process affecting the net loadings of PAHs in lower Chesapeake Bay.

  13. Surface modification of gold nanoparticles and their monolayer behavior at the air/water interface

    NASA Astrophysics Data System (ADS)

    Hsu, Chaio-Ling; Wang, Ke-Hsuan; Chang, Chien-Hsiang; Hsu, Wen-Ping; Lee, Yuh-Lang

    2011-01-01

    Gold nanoparticles were prepared by two different methods. The first method was chemically grafting the particles with different lengths of alkylthiol (C6SH, C12SH and C18SH). For the second method, the Au particles were surface modified first by mercaptosuccinic acid (MSA) to render a surface with carboxylic acid groups which play a role to physically adsorb cationic surfactant in chloroform. This method was termed physical/chemical method. In the first method, the effects of alkyl chain length and dispersion solvent on the monolayer behavior of surface modified gold nanoparticles was evaluated. The gold nanoparticles prepared by 1-hexanthiol demonstrated the narrowest size distribution. Most of them showed narrower particle size distributions in chloroform than in hexane. For the physical/chemical method, the particles can spread more uniformly on the water surface which is attributed to the amphiphilic character of the particles at the air/water interface. However, the particles cannot pack closely due to the relatively weak particle-particle interaction. The effect of alkyl chain length was also assessed for the second method.

  14. Kinetics of trans-cis isomerization in azobenzene dimers at an air-water interface

    SciTech Connect

    Kumar, Bharat; Suresh, K. A.

    2009-08-15

    We have studied the kinetics of trans to cis isomerization under the illumination of ultraviolet light, in the Langmuir monolayer of mesogenic azobenzene dimer, bis-[5-(4{sup '}-n-dodecyloxy benzoyloxy)-2-(4{sup ''}-methylphenylazo)phenyl] adipate, at an air-water interface. We find that the trans to cis isomerization reaction of the molecules in the monolayer shows deviation from the first-order kinetics unlike those reported on Langmuir monolayers of azobenzene molecules. We attribute the deviation from first-order kinetics to the simultaneous photoisomerization of trans isomers to form cis isomers and the reverse thermal isomerization of cis isomers to form trans isomers. Our analysis of the rate of change of mole fraction of trans isomers to form cis isomers indicates a first-order kinetics for trans to cis photoisomerization reaction and a second-order kinetics for cis to trans thermal isomerization reaction. This second-order kinetics mechanism is similar to the Lindemann-Hinshelwood mechanism for the unimolecular reactions at low concentration of reactants. The formation of the activated cis isomer by collisions is a slow process as compared to the decay of the activated cis isomer to trans isomer in the liquid expanded phase. This results in the second-order kinetics for the thermal isomerization of cis isomers.

  15. Dipolar interactions between domains in lipid monolayers at the air-water interface.

    PubMed

    Rufeil-Fiori, Elena; Wilke, Natalia; Banchio, Adolfo J

    2016-05-25

    A great variety of biologically relevant monolayers present phase coexistence characterized by domains formed by lipids in an ordered phase state dispersed in a continuous, disordered phase. From the difference in surface densities between these phases, inter-domain dipolar interactions arise. These interactions are relevant for the determination of the spacial distribution of domains as well as their dynamics. In this work, we propose a novel way of estimating the dipolar repulsion using a passive method that involves the analysis of images of the monolayer with phase coexistence. This method is based on the comparison of the pair correlation function obtained from experiments with that obtained from Brownian dynamics simulations of a model system. As an example, we determined the difference in dipolar density of a binary monolayer of DSPC/DMPC at the air-water interface from the analysis of the radial distribution of domains, and the results are compared with those obtained by surface potential determinations. A systematic analysis for the experimentally relevant parameter range is given, which may be used as a working curve for obtaining the dipolar repulsion in different systems.

  16. Characterization of composite phthalocyanine-fatty acid films from the air/water interface to solid supports.

    PubMed

    Giancane, G; Manno, D; Serra, A; Sgobba, V; Valli, L

    2011-12-22

    A commercial vanadyl 2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine (VOPc) was dissolved in chloroform and spread on ultrapure water subphase in a Langmuir trough. The floating film was thoroughly characterized at the air-water interface by means of the Langmuir isotherm, Brewster angle microscopy, UV-vis reflection spectroscopy, and infrared measurements carried out directly at the air-water interface. All the results showed the formation of a non-uniform and aggregated floating layer, too rigid to be transferred by the Langmuir-Blodgett (LB) method. For this reason, a mixture of arachidic acid and VOPc was realized, characterized, and transferred by the LB technique on solid substrates. Interface measurements and atomic force microscopy analysis suggested the formation of a uniform arachidic acid film and a superimposed VOPc placed in prone configuration.

  17. Measurement and computation of hydrodynamic coupling at an air/water interface with an insoluble monolayer

    NASA Astrophysics Data System (ADS)

    Hirsa, Amir H.; Lopez, Juan M.; Miraghaie, Reza

    2001-09-01

    The coupling between a bulk vortical flow and a surfactant-influenced air/water interface has been examined in a canonical flow geometry through experiments and computations. The flow in an annular region bounded by stationary inner and outer cylinders is driven by the constant rotation of the floor and the free surface is initially covered by a uniformly distributed insoluble monolayer. When driven slowly, this geometry is referred to as the deep-channel surface viscometer and the flow is essentially azimuthal. The only interfacial property that affects the flow in this regime is the surface shear viscosity, [mu]s, which is uniform on the surface due to the vanishingly small concentration gradient. However, when operated at higher Reynolds number, secondary flow drives the surfactant film towards the inner cylinder until the Marangoni stress balances the shear stress on the bulk fluid. In general, the flow can be influenced by the surface tension, [sigma], and the surface dilatational viscosity, [kappa]s, as well as [mu]s. However, because of the small capillary number of the present flow, the effects of surface tension gradients dominate the surface viscosities in the radial stress balance, and the effect of [mu]s can only come through the azimuthal stress. Vitamin K1 was chosen for this study since it forms a well-behaved insoluble monolayer on water and [mu]s is essentially zero in the range of concentration on the surface, c, encountered. Thus the effect of Marangoni elasticity on the interfacial stress could be isolated. The flow near the interface was measured in an optical channel using digital particle image velocimetry. Steady axisymmetric flow was observed at the nominal Reynolds number of 8500. A numerical model has been developed using the axisymmetric Navier Stokes equations to examine the details of the coupling between the bulk and the interface. The nonlinear equation of state, [sigma](c), for the vitamin K1 monolayer was measured and utilized in

  18. Advances in simulating radiance signatures for dynamic air/water interfaces

    NASA Astrophysics Data System (ADS)

    Goodenough, Adam A.; Brown, Scott D.; Gerace, Aaron

    2015-05-01

    The air-water interface poses a number of problems for both collecting and simulating imagery. At the surface, the magnitude of observed radiance can change by multiple orders of magnitude at high spatiotemporal frequency due to glinting effects. In the volume, similarly high frequency focusing of photons by a dynamic wave surface significantly changes the reflected radiance of in-water objects and the scattered return of the volume itself. These phenomena are often manifest as saturated pixels and artifacts in collected imagery (often enhanced by time delays between neighboring pixels or interpolation between adjacent filters) and as noise and greater required computation times in simulated imagery. This paper describes recent advances made to the Digital Image and Remote Sensing Image Generation (DIRSIG) model to address the simulation issues to better facilitate an understanding of a multi/hyper-spectral collection. Glint effects are simulated using a dynamic height field that can be driven by wave frequency models and generates a sea state at arbitrary time scales. The volume scattering problem is handled by coupling the geometry representing the surface (facetization by the height field) with the single scattering contribution at any point in the water. The problem is constrained somewhat by assuming that contributions come from a Snell's window above the scattering point and by assuming a direct source (sun). Diffuse single scattered and multiple scattered energy contributions are handled by Monte Carlo techniques employed previously. The model is compared to existing radiative transfer codes where possible, with the objective of providing a robust movel of time-dependent absolute radiance at many wavelengths.

  19. Effect of glycyrrhetinic acid on lipid raft model at the air/water interface.

    PubMed

    Sakamoto, Seiichi; Uto, Takuhiro; Shoyama, Yukihiro

    2015-02-01

    To investigate an interfacial behavior of the aglycon of glycyrrhizin (GC), glycyrrhetinic acid (GA), with a lipid raft model consisting of equimolar ternary mixtures of N-palmitoyl sphingomyelin (PSM), dioleoylphosphatidylcholine (DOPC), and cholesterol (CHOL), Langmuir monolayer techniques were systematically conducted. Surface pressure (π)-molecular area (A) and surface potential (ΔV)-A isotherms showed that the adsorbed GA at the air/water interface was desorbed into the bulk upon compression of the lipid monolayer. In situ morphological analysis by Brewster angle microscopy and fluorescence microscopy revealed that the raft domains became smaller as the concentrations of GA in the subphase (CGA) increased, suggesting that GA promotes the formation of fluid networks related to various cellular processes via lipid rafts. In addition, ex situ morphological analysis by atomic force microscopy revealed that GA interacts with lipid raft by lying down at the surface. Interestingly, the distinctive striped regions were formed at CGA=5.0 μM. This phenomenon was observed to be induced by the interaction of CHOL with adsorbed GA and is involved in the membrane-disrupting activity of saponin and its aglycon. A quantitative comparison of GA with GC (Sakamoto et al., 2013) revealed that GA interacts more strongly with the raft model than GC in the monolayer state. Various biological activities of GA are known to be stronger than those of GC. This fact allows us to hypothesize that differences in the interactions of GA/GC with the model monolayer correlate to their degree of exertion for numerous activities.

  20. Langmuir nanoarchitectonics: one-touch fabrication of regularly sized nanodisks at the air-water interface.

    PubMed

    Mori, Taizo; Sakakibara, Keita; Endo, Hiroshi; Akada, Misaho; Okamoto, Ken; Shundo, Atsuomi; Lee, Michael V; Ji, Qingmin; Fujisawa, Takuya; Oka, Kenichiro; Matsumoto, Mutsuyoshi; Sakai, Hideki; Abe, Masahiko; Hill, Jonathan P; Ariga, Katsuhiko

    2013-06-18

    In this article, we propose a novel methodology for the formation of monodisperse regularly sized disks of several nanometer thickness and with diameters of less than 100 nm using Langmuir monolayers as fabrication media. An amphiphilic triimide, tri-n-dodecylmellitic triimide (1), was spread as a monolayer at the air-water interface with a water-soluble macrocyclic oligoamine, 1,4,7,10-tetraazacyclododecane (cyclen), in the subphase. The imide moieties of 1 act as hydrogen bond acceptors and can interact weakly with the secondary amine moieties of cyclen as hydrogen bond donors. The monolayer behavior of 1 was investigated through π-A isotherm measurements and Brewster angle microscopy (BAM). The presence of cyclen in the subphase significantly shifted isotherms and induced the formation of starfish-like microstructures. Transferred monolayers on solid supports were analyzed by reflection absorption FT-IR (FT-IR-RAS) spectroscopy and atomic force microscopy (AFM). The Langmuir monolayer transferred onto freshly cleaved mica by a surface touching (i.e., Langmuir-Schaefer) method contained disk-shaped objects with a defined height of ca. 3 nm and tunable diameter in the tens of nanometers range. Several structural parameters such as the disk height, molecular aggregation numbers in disk units, and 2D disk density per unit surface area are further discussed on the basis of AFM observations together with aggregate structure estimation and thermodynamic calculations. It should be emphasized that these well-defined structures are produced through simple routine procedures such as solution spreading, mechanical compression, and touching a substrate at the surface. The controlled formation of defined nanostructures through easy macroscopic processes should lead to unique approaches for economical, energy-efficient nanofabrication.

  1. AWiFS Radiometric Assessment

    NASA Technical Reports Server (NTRS)

    Thome, Kurt; Aaron, David; Pagnutti, Mary

    2007-01-01

    An assessment of the Advanced Wide Field Sensor (AWiFS) is presented. The contents include: 1) Overview of AWiFS sensor; 2) Description of University of Arizona approach; 3) Description of South Dakota State approach and results; 4) Description of Stennis Space Center approach and results; 5) Summary of results for all groups.

  2. Capillarity-induced directed self-assembly of patchy hexagram particles at the air-water interface.

    PubMed

    Kang, Sung-Min; Choi, Chang-Hyung; Kim, Jongmin; Yeom, Su-Jin; Lee, Daeyeon; Park, Bum Jun; Lee, Chang-Soo

    2016-07-01

    Directed self-assembly can produce ordered or organized superstructures from pre-existing building blocks through pre-programmed interactions. Encoding desired information into building blocks with specific directionality and strength, however, poses a significant challenge for the development of self-assembled superstructures. Here, we demonstrate that controlling the shape and patchiness of particles trapped at the air-water interface can represent a powerful approach for forming ordered macroscopic complex structures through capillary interactions. We designed hexagram particles using a micromolding method that allowed for precise control over the shape and, more importantly, the chemical patchiness of the particles. The assembly behaviors of these hexagram particles at the air-water interface were strongly affected by chemical patchiness. In particular, two-dimensional millimeter-scale ordered structures could be formed by varying the patchiness of the hexagram particles, and we attribute this effect to the delicate balance between the attractive and repulsive interactions among the patchy hexagram particles. Our results provide important clues for encoding information into patchy particles to achieve macroscopic assemblies via a simple molding technique and potentially pave a new pathway for the programmable assembly of particles at the air-water interface.

  3. Capillarity-induced directed self-assembly of patchy hexagram particles at the air-water interface.

    PubMed

    Kang, Sung-Min; Choi, Chang-Hyung; Kim, Jongmin; Yeom, Su-Jin; Lee, Daeyeon; Park, Bum Jun; Lee, Chang-Soo

    2016-07-01

    Directed self-assembly can produce ordered or organized superstructures from pre-existing building blocks through pre-programmed interactions. Encoding desired information into building blocks with specific directionality and strength, however, poses a significant challenge for the development of self-assembled superstructures. Here, we demonstrate that controlling the shape and patchiness of particles trapped at the air-water interface can represent a powerful approach for forming ordered macroscopic complex structures through capillary interactions. We designed hexagram particles using a micromolding method that allowed for precise control over the shape and, more importantly, the chemical patchiness of the particles. The assembly behaviors of these hexagram particles at the air-water interface were strongly affected by chemical patchiness. In particular, two-dimensional millimeter-scale ordered structures could be formed by varying the patchiness of the hexagram particles, and we attribute this effect to the delicate balance between the attractive and repulsive interactions among the patchy hexagram particles. Our results provide important clues for encoding information into patchy particles to achieve macroscopic assemblies via a simple molding technique and potentially pave a new pathway for the programmable assembly of particles at the air-water interface. PMID:27328067

  4. Formation of a Rigid Hydrophobin Film and Disruption by an Anionic Surfactant at an Air/Water Interface.

    PubMed

    Kirby, Stephanie M; Zhang, Xujun; Russo, Paul S; Anna, Shelley L; Walker, Lynn M

    2016-06-01

    Hydrophobins are amphiphilic proteins produced by fungi. Cerato-ulmin (CU) is a hydrophobin that has been associated with Dutch elm disease. Like other hydrophobins, CU stabilizes air bubbles and oil droplets through the formation of a persistent protein film at the interface. The behavior of hydrophobins at surfaces has raised interest in their potential applications, including use in surface coatings, food foams, and emulsions and as dispersants. The practical use of hydrophobins requires an improved understanding of the interfacial behavior of these proteins, alone and in the presence of added surfactants. In this study, the adsorption behavior of CU at air/water interfaces is characterized by measuring the surface tension and interfacial rheology as a function of adsorption time. CU is found to adsorb irreversibly at air/water interfaces. The magnitude of the dilatational modulus increases with adsorption time and surface pressure until CU eventually forms a rigid film. The persistence of this film is tested through the sequential addition of strong surfactant sodium dodecyl sulfate (SDS) to the bulk liquid adjacent to the interface. SDS is found to coadsorb to interfaces precoated with a CU film. At high concentrations, the addition of SDS significantly decreases the dilatational modulus, indicating disruption and displacement of CU by SDS. Sequential adsorption results in mixed layers with properties not observed in interfaces generated from complexes formed in the bulk. These results lend insight to the complex interfacial interactions between hydrophobins and surfactants. PMID:27164189

  5. Surface activity of saponin from Quillaja bark at the air/water and oil/water interfaces.

    PubMed

    Wojciechowski, Kamil

    2013-08-01

    Surface activity of Sigma's Quillaja bark saponin (QBS) was studied by means of dynamic interfacial tension and surface dilational rheology at three fluid/fluid interfaces with the polarity of the non-aqueous phase increasing in the order: air/water, tetradecane/water and olive oil/water. The equilibrium interfacial tension isotherms were fitted to the generalized Frumkin model with surface compressibility for the air/water and tetradecane/water interfaces, whereas the isotherm for the third interface displays a more complex shape. Upon fast compression of a drop of concentrated "Sigma" QBS solution immersed in olive oil, a clearly visible and durable skin was formed. On the other hand, no skin formation was noticed at the air/water interface, and only a little at the tetradecane/water interface. Addition of a fatty acid, however, improved slightly the skin-formation ability of the QBS at the latter interface. The surface behavior of the QBS from Sigma was compared with that from Desert King, Int. ("Supersap"), employed in a recent study by Stanimirova et al. [22]. The two products exhibit different areas per molecule in the saturated adsorbed layer (0.37nm(2) vs. 1.19nm(2) for "Sigma" and "Supersap", respectively). Also their surface rheology is different: although both QBSs form predominantly elastic layers, for "Sigma" the surface storage modulus, εr=103mNm(-1), while for "Supersap" εr=73mNm(-1) at 10(-3)moll(-1) (i.e., around their cmc). The two saponin products exhibit also different ionic character, as proven by the acid-base titration of their aqueous solutions: QBS from Sigma is an ionic surfactant, while the "Supersap" from Desert King is a non-ionic one. PMID:23524082

  6. Surface activity of saponin from Quillaja bark at the air/water and oil/water interfaces.

    PubMed

    Wojciechowski, Kamil

    2013-08-01

    Surface activity of Sigma's Quillaja bark saponin (QBS) was studied by means of dynamic interfacial tension and surface dilational rheology at three fluid/fluid interfaces with the polarity of the non-aqueous phase increasing in the order: air/water, tetradecane/water and olive oil/water. The equilibrium interfacial tension isotherms were fitted to the generalized Frumkin model with surface compressibility for the air/water and tetradecane/water interfaces, whereas the isotherm for the third interface displays a more complex shape. Upon fast compression of a drop of concentrated "Sigma" QBS solution immersed in olive oil, a clearly visible and durable skin was formed. On the other hand, no skin formation was noticed at the air/water interface, and only a little at the tetradecane/water interface. Addition of a fatty acid, however, improved slightly the skin-formation ability of the QBS at the latter interface. The surface behavior of the QBS from Sigma was compared with that from Desert King, Int. ("Supersap"), employed in a recent study by Stanimirova et al. [22]. The two products exhibit different areas per molecule in the saturated adsorbed layer (0.37nm(2) vs. 1.19nm(2) for "Sigma" and "Supersap", respectively). Also their surface rheology is different: although both QBSs form predominantly elastic layers, for "Sigma" the surface storage modulus, εr=103mNm(-1), while for "Supersap" εr=73mNm(-1) at 10(-3)moll(-1) (i.e., around their cmc). The two saponin products exhibit also different ionic character, as proven by the acid-base titration of their aqueous solutions: QBS from Sigma is an ionic surfactant, while the "Supersap" from Desert King is a non-ionic one.

  7. Multi-scale modeling of mycosubtilin lipopeptides at the air/water interface: structure and optical second harmonic generation.

    PubMed

    Loison, Claire; Nasir, Mehmet Nail; Benichou, Emmanuel; Besson, Françoise; Brevet, Pierre-François

    2014-02-01

    Monolayers of the lipopeptide mycosubtilin are studied at the air/water interface. Their structure is investigated using molecular dynamics simulations. All-atom models suggest that the lipopeptide is flexible and aggregates at the interface. To achieve simulation times of several microseconds, a coarse-grained (CG) model based on the MARTINI force field was also used. These CG simulations describe the formation of half-micelles at the interface for surface densities up to 1 lipopeptide per nm(2). In these aggregates, the tyrosine side chain orientation is found to be constrained: on average, its main axis, as defined along the C-OH bond, aligns along the interface normal and points towards the air side. The origin of the optical second harmonic generation (SHG) from mycosubtilin monolayers at the air/water interface is also investigated. The molecular hyperpolarizability of the lipopeptide is obtained from quantum chemistry calculations. The tyrosine side chain contribution to the hyperpolarizability is found to be dominant. The orientation distribution of tyrosine, associated with a dominant hyperpolarizability component along the C-OH bond of the tyrosine, yields a ratio of the susceptibility elements χ((2))(ZZZ)/χ((2))(ZXX) consistent with the experimental measurements recently reported by M. N. Nasir et al. [Phys. Chem. Chem. Phys., 2013, 15, 19919].

  8. Multi-scale modeling of mycosubtilin lipopeptides at the air/water interface: structure and optical second harmonic generation.

    PubMed

    Loison, Claire; Nasir, Mehmet Nail; Benichou, Emmanuel; Besson, Françoise; Brevet, Pierre-François

    2014-02-01

    Monolayers of the lipopeptide mycosubtilin are studied at the air/water interface. Their structure is investigated using molecular dynamics simulations. All-atom models suggest that the lipopeptide is flexible and aggregates at the interface. To achieve simulation times of several microseconds, a coarse-grained (CG) model based on the MARTINI force field was also used. These CG simulations describe the formation of half-micelles at the interface for surface densities up to 1 lipopeptide per nm(2). In these aggregates, the tyrosine side chain orientation is found to be constrained: on average, its main axis, as defined along the C-OH bond, aligns along the interface normal and points towards the air side. The origin of the optical second harmonic generation (SHG) from mycosubtilin monolayers at the air/water interface is also investigated. The molecular hyperpolarizability of the lipopeptide is obtained from quantum chemistry calculations. The tyrosine side chain contribution to the hyperpolarizability is found to be dominant. The orientation distribution of tyrosine, associated with a dominant hyperpolarizability component along the C-OH bond of the tyrosine, yields a ratio of the susceptibility elements χ((2))(ZZZ)/χ((2))(ZXX) consistent with the experimental measurements recently reported by M. N. Nasir et al. [Phys. Chem. Chem. Phys., 2013, 15, 19919]. PMID:24346061

  9. Dissecting the Molecular Structure of the Air/Water Interface from Quantum Simulations of the Sum-Frequency Generation Spectrum.

    PubMed

    Medders, Gregory R; Paesani, Francesco

    2016-03-23

    The molecular characterization of the air/water interface is a key step in understanding fundamental multiphase phenomena ranging from heterogeneous chemical processes in the atmosphere to the hydration of biomolecules. The apparent simplicity of the air/water interface, however, masks an underlying complexity associated with the dynamic nature of the water hydrogen-bond network that has so far hindered an unambiguous characterization of its microscopic properties. Here, we demonstrate that the application of quantum many-body molecular dynamics, which enables spectroscopically accurate simulations of water from the gas to the condensed phase, leads to a definitive molecular-level picture of the interface region. For the first time, excellent agreement is obtained between the simulated vibrational sum-frequency generation spectrum and the most recent state-of-the-art measurements, without requiring any empirical frequency shift or ad hoc scaling of the spectral intensity. A systematic dissection of the spectral features demonstrates that a rigorous representation of nuclear quantum effects as well as of many-body energy and electrostatic contributions is necessary for a quantitative reproduction of the experimental data. The unprecedented accuracy of the simulations presented here indicates that quantum many-body molecular dynamics can enable predictive studies of aqueous interfaces, which by complementing analogous experimental measurements will provide unique molecular insights into multiphase and heterogeneous processes of relevance in chemistry, biology, materials science, and environmental research. PMID:26943730

  10. Revised parameters for modeling the transport of PCB components across an air water interface

    SciTech Connect

    Bopp, R.F.

    1983-03-20

    A number of revisions of the data base and conceptualizations utilized in air-water transport models for PCB components are suggested. The most significant of these involves the assignment of physical chemical properties on the basis of degree of chlorination. the effect of temperature on the rate of transport is also discussed. The revised model is tested on a number of natural situations and compared with available data.

  11. OH-Radical Oxidation of Surface-Active cis-Pinonic Acid at the Air-Water Interface.

    PubMed

    Enami, Shinichi; Sakamoto, Yosuke

    2016-05-26

    Gaseous biogenic volatile organic compounds (BVOCs) are immediately oxidized by gaseous oxidants to form BVOC-acids that rapidly condense onto aqueous aerosol phase and thus contribute to the growth of atmospheric particles. Because BVOC-acids are highly hydrophobic and hence surface-active in nature, it seems critical to study the oxidation by gaseous hydroxyl radical (·OH(g)) at the air-water interface. Here we report on the fast (≤10 μs) oxidation of aqueous cis-pinonic acid (C10H16O3, CPA, cis-pinonate anion's m/z = 183), a representative BVOC-acid, by ·OH(g) at the air-water interface for the first time. We find that cis-pinonate anion is more enriched at the air-water interface by ∼4 and ∼14 times than n-octanoate anion at 10 and 100 μM, respectively, as revealed by an interface-specific mass spectrometry of the equimolar mixture of microjets. Exposure of aqueous CPA microjets to ·OH(g) pulses from the 266 nm laser photolysis of O3(g)/O2(g)/H2O(g)/N2(g) mixtures yields pinonic peroxyl radicals (m/z = 214) that lead to the functionalization products carbonyls (m/z = 197), alcohols (m/z = 199), and pinonic hydroperoxides (m/z = 215) in addition to smaller-mass products including carbonyls (m/z = 155 and 157). We confirmed the formation of the corresponding alcohols, aldehydes, and hydroperoxides in experiments performed in D2O solvent. The analysis of total mass balance implies a significant amount (>70%) of products would be emitted into the gas-phase during the heterogeneous ·OH-oxidations. Our results suggest ·OH-oxidations of amphiphilic BVOC-acids at the air-water interface may play a far more significant role in photochemical aging process of aqueous aerosols than previously assumed. PMID:27098046

  12. Towards Organized Hybrid Nanomaterials at the Air/Water Interface Based on Liquid-Crystal/ZnO Nanocrystals.

    PubMed

    Paczesny, Jan; Wolska-Pietkiewicz, Małgorzata; Binkiewicz, Ilona; Wróbel, Zbigniew; Wadowska, Monika; Matuła, Kinga; Dzięcielewski, Igor; Pociecha, Damian; Smalc-Koziorowska, Julita; Lewiński, Janusz; Hołyst, Robert

    2015-11-16

    The ability to self-assemble nanosized ligand-stabilized metal oxide or semiconductor materials offers an intriguing route to engineer nanomaterials with new tailored properties from the disparate components. We describe a novel one-pot two-step organometallic approach to prepare ZnO nanocrystals (NCs) coated with deprotonated 4-(dodecyloxy)benzoic acid (i.e., an X-type liquid-crystalline ligand) as a model LC system (termed ZnO-LC1 NCs). Langmuir and Langmuir-Blodgett films of the resulting hybrids are investigated. The observed behavior of the ZnO NCs at the air/water interface is rationalized by invoking a ZnO-interdigitation process mediated by the anchored liquid-crystalline shell. The ordered superstructures form according to mechanism based on a ZnO-interdigitation process mediated by liquid crystals (termed ZIP-LC). The external and directed force applied upon compression at the air/water interface and the packing of the ligands that stabilize the ZnO cores drives the formation of nanorods of ordered internal structure. To study the process in detail, we follow a nontraditional protocol of thin-film investigation. We collect the films from the air/water interface in powder form (ZnO-LC1 LB), resuspend the powder in organic solvents and utilize otherwise unavailable experimental techniques. The structural and physical properties of the resulting superlattices were studied by using electron microscopy, atomic force microscopy, X-ray studies, dynamic light scattering, thermogravimetric analysis, UV/Vis absorption, and photoluminescence spectroscopy.

  13. Adsorption, Ordering, and Local Environments of Surfactant-Encapsulated Polyoxometalate Ions Probed at the Air-Water Interface.

    PubMed

    Doughty, Benjamin; Yin, Panchao; Ma, Ying-Zhong

    2016-08-16

    The continued development and application of surfactant-encapsulated polyoxometalates (SEPs) relies on understanding the ordering and organization of species at their interface and how these are impacted by the various local environments to which they are exposed. Here, we report on the equilibrium properties of two common SEPs adsorbed to the air-water interface and probed with surface-specific vibrational sum-frequency generation (SFG) spectroscopy. These results reveal clear shifts in vibrational band positions, the magnitude of which scales with the charge of the SEP core, which is indicative of a static field effect on the surfactant coating and the associated local chemical environment. This static field also induces ordering in surrounding water molecules that is mediated by charge screening via the surface-bound surfactants. From these SFG measurements, we are able to show that Mo132-based SEPs are more polar than Mo72V30 SEPs. Disorder in the surfactant chain packing at the highly curved SEP surfaces is attributed to large conic volumes that can be sampled without interactions with neighboring chains. Measurements of adsorption isotherms yield free energies of adsorption to the air-water interface of -46.8 ± 0.4 and -44.8 ± 1.2 kJ/mol for the Mo132 and Mo72V30 SEPs, respectively, indicating a strong propensity for the fluid surface. The influence of intermolecular interactions on the surface adsorption energies is discussed. PMID:27452922

  14. Application of LIF to investigate gas transfer near the air-water interface in a grid-stirred tank

    NASA Astrophysics Data System (ADS)

    Herlina; Jirka, G. H.

    The interaction between oxygen absorption into liquids and bottom shear-induced turbulence was investigated in a grid-stirred tank using a laser-induced fluorescence (LIF) technique. The LIF technique enabled visualization as well as quantification of planar concentration fields of the dissolved oxygen (DO) near the air-water interface. Qualitative observation of the images provided more insight into the physical mechanism controlling the gas transfer process. The high data resolution is an advantage for revealing the concentration distribution within the boundary layer, which is a few hundreds of a micrometer thick. Mean and turbulent fluctuation characteristics were obtained and compared with previous results.

  15. Thermodynamic, morphological and structural properties of dissociated fatty acid monolayers at the air-water interface

    NASA Astrophysics Data System (ADS)

    Johann, Robert

    2001-10-01

    Research on monolayers of amphiphilic lipids on aqueous solution is of basic importance in surface science. Due to the applicability of a variety of surface sensitive techniques, floating insoluble monolayers are very suitable model systems for the study of order, structure formation and material transport in two dimensions or the interactions of molecules at the interface with ions or molecules in the bulk (headword 'molecular recognition'). From the behavior of monolayers conclusions can be drawn on the properties of lipid layers on solid substrates or in biological membranes. This work deals with specific and fundamental interactions in monolayers both on the molecular and on the microscopic scale and with their relation to the lattice structure, morphology and thermodynamic behavior of monolayers at the air-water interface. As model system especially monolayers of long chain fatty acids are used, since there the molecular interactions can be gradually adjusted by varying the degree of dissociation by means of the suphase pH value. For manipulating the molecular interactions besides the subphase composition also temperature and monolayer composition are systematically varied. The change in the monolayer properties as a function of an external parameter is analyzed by means of isotherm and surface potential measurements, Brewster-angle microscopy, X-ray diffraction at grazing incidence and polarization modulated infrared reflection absorption spectroscopy. For this a quantitative measure for the molecular interactions and for the chain conformational order is derived from the X-ray data. The most interesting results of this work are the elucidation of the origin of regular polygonal and dendritic domain shapes, the various effects of cholesterol on molecular packing and lattice order of long chain amphiphiles, as well as the detection of an abrupt change in the head group bonding interactions, the chain conformational order and the phase transition pressure

  16. Interfacial dynamic and dilational rheology of polyelectrolyte/surfactant two-component nanoparticle systems at air-water interface

    NASA Astrophysics Data System (ADS)

    Tong, L. J.; Bao, M. T.; Li, Y. M.; Gong, H. Y.

    2014-10-01

    The interfacial characteristics of nanoparticles and consequent inter-particle interactions at the interface are poorly understood. In this work, the interfacial dynamic and corresponding dilational surface rheology of self-assembled polyelectrolyte/surfactant nanoparticles at the air-water interface are characterized. The nanoparticles are prepared from dodecyltrimethylammonium (DTAB) and poly (sodium 4-styrene-sulfonate) (PSS) by mixing them in aqueous solution. The interfacial dynamic characteristics have been carried out by comparing the surface pressure with the dilational rheological response of these nanoparticles at interface. The results indicate that this type of nanoparticles can adsorb at the interface forming a nanoparticle monolayer, which leads to the surface tension decreased markedly. The dependence of surface pressure on time shows the instability and disassembly process of nanoparticles at the interface. On the basis of these observations, it is proposed that the nanoparticles undergo a dynamic process that interface induced nanoparticles disassembly into DTAB/PSS complexes. The presence of PSS in the subphase can promote the process of nanoparticles disassembly. A transition point in dilational elasticity and viscosity response of the nanoparticles versus oscillation frequency further validate the micro dynamic process of nanoparticles and the formation of polyelectrolyte/surfactant complex monolayer at the interface.

  17. Degradation and rearrangement of a lung surfactant lipid at the air-water interface during exposure to the pollutant gas ozone.

    PubMed

    Thompson, Katherine C; Jones, Stephanie H; Rennie, Adrian R; King, Martin D; Ward, Andrew D; Hughes, Brian R; Lucas, Claire O M; Campbell, Richard A; Hughes, Arwel V

    2013-04-01

    The presence of unsaturated lipids in lung surfactant is important for proper respiratory function. In this work, we have used neutron reflection and surface pressure measurements to study the reaction of the ubiquitous pollutant gas-phase ozone, O3, with pure and mixed phospholipid monolayers at the air-water interface. The results reveal that the reaction of the unsaturated lipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, POPC, with ozone leads to the rapid loss of the terminal C9 portion of the oleoyl strand of POPC from the air-water interface. The loss of the C9 portion from the interface is accompanied by an increase in the surface pressure (decrease in surface tension) of the film at the air-water interface. The results suggest that the portion of the oxidized oleoyl strand that is still attached to the lipid headgroup rapidly reverses its orientation and penetrates the air-water interface alongside the original headgroup, thus increasing the surface pressure. The reaction of POPC with ozone also leads to a loss of material from the palmitoyl strand, but the loss of palmitoyl material occurs after the loss of the terminal C9 portion from the oleoyl strand of the molecule, suggesting that the palmitoyl material is lost in a secondary reaction step. Further experiments studying the reaction of mixed monolayers composed of unsaturated lipid POPC and saturated lipid dipalmitoyl-sn-glycero-3-phosphocholine, DPPC, revealed that no loss of DPPC from the air-water interface occurs, eliminating the possibility that a reactive species such as an OH radical is formed and is able to attack nearby lipid chains. The reaction of ozone with the mixed films does cause a significant change in the surface pressure of the air-water interface. Thus, the reaction of unsaturated lipids in lung surfactant changes and impairs the physical properties of the film at the air-water interface.

  18. Reactivity of aldehydes at the air-water interface. Insights from molecular dynamics simulations and ab initio calculations.

    PubMed

    Martins-Costa, Marilia T C; García-Prieto, Francisco F; Ruiz-López, Manuel F

    2015-02-14

    Understanding the influence of solute-solvent interactions on chemical reactivity has been a subject of intense research in the last few decades. Theoretical studies have focused on bulk solvation phenomena and a variety of models and methods have been developed that are now widely used by both theoreticians and experimentalists. Much less attention has been paid, however, to processes that occur at liquid interfaces despite the important role such interfaces play in chemistry and biology. In this study, we have carried out sequential molecular dynamics simulations and quantum mechanical calculations to analyse the influence of the air-water interface on the reactivity of formaldehyde, acetaldehyde and benzaldehyde, three simple aldehydes of atmospheric interest. The calculated free-energy profiles exhibit a minimum at the interface, where the average reactivity indices may display large solvation effects. The study emphasizes the role of solvation dynamics, which are responsible for large fluctuations of some molecular properties. We also show that the photolysis rate constant of benzaldehyde in the range 290-308 nm increases by one order of magnitude at the surface of a water droplet, from 2.7 × 10(-5) s(-1) in the gas phase to 2.8 × 10(-4) s(-1) at the air-water interface, and we discuss the potential impact of this result on the chemistry of the troposphere. Experimental data in this domain are still scarce and computer simulations like those presented in this work may provide some insights that can be useful to design new experiments.

  19. Polystyrene-poly(ethylene oxide) diblock copolymer: the effect of polystyrene and spreading concentration at the air/water interface.

    PubMed

    Glagola, Cameron P; Miceli, Lia M; Milchak, Marissa A; Halle, Emily H; Logan, Jennifer L

    2012-03-20

    Polystyrene-block-poly(ethylene oxide) (PS-PEO) is an amphiphilic diblock copolymer that undergoes microphase separation when spread at the air/water interface, forming nanosized domains. In this study, we investigate the impact of PS by examining a series of PS-PEO samples containing constant PEO (~17,000 g·mol(-1)) and variable PS (from 3600 to 200,000 g·mol(-1)) through isothermal characterization and atomic force microscopy (AFM). The polymers separated into two categories: predominantly hydrophobic and predominantly hydrophilic with a weight percent of PEO of ~20% providing the boundary between the two. AFM results indicated that predominantly hydrophilic PS-PEO forms dots while more hydrophobic samples yield a mixture of dots and spaghetti with continent-like structures appearing at ~7% PEO or less. These structures reflect a blend of polymer spreading, entanglement, and vitrification as the solvent evaporates. Changing the spreading concentration provides insight into this process with higher concentrations representing earlier kinetic stages and lower concentrations demonstrating later ones. Comparison of isothermal results and AFM analysis shows how polymer behavior at the air/water interface correlates with the observed nanostructures. Understanding the impact of polymer composition and spreading concentration is significant in leading to greater control over the nanostructures obtained through PS-PEO self-assembly and their eventual application as polymer templates.

  20. Surface Partitioning and Stability of Mixed Films of Fluorinated Alcohols and Acids at the Air- Water Interface

    NASA Astrophysics Data System (ADS)

    Rontu, N. A.; Vaida, V.

    2007-05-01

    The production of fluorinated compounds over the past 50 years has had numerous industrial applications. For example, perfluorinated carboxylic acids are used in the synthesis of polymers and fire retardants, perfluoroalkyl sulfonates act as surface protectors, and fluorotelomer alcohols are incorporated into products such as paints, coatings, polymers, and adhesives. Fluorotelomer alcohols (FTOHs) are linear polyfluorinated alcohols with the formula CF3(CF2)nCH2CH2OH (n=1,3,5,...). They have been suggested as possible precursors for perfluorinated carboxylic acids and detected in the troposphere over several North American sites. Perfluorocarboxylic acids have even been detected in the arctic food chain, human blood, tissues of animals and environmental waters. We report the surface activity of fluorotelomer alcohols and perfluorinated carboxylic acids at the air-water interface by using a Langmuir trough. Isotherms of the pure compounds along with mixed films with other organic carboxylic acids were collected. The main objective of these experiments was to understand their heterogeneous chemistry by characterizing the pure and mixed films, which serves as a representative model for organic films on atmospheric surfaces such as those found on oceans and aqueous aerosols. Film properties and behavior, notably stabilization, evaporation from the subphase, and miscibility in the single-component mixtures as well as in the mixed films will be discussed. An important consequence of FTOHs and perfluorocarboxylic acids being found to partition to the air-water interface is the possibility of their transport and widespread distribution and deposition using atmospheric aerosols.

  1. Interpreting Vibrational Sum-frequency Spectra of Sulfur Dioxide at the Air/Water Interface: A Comprehensive Molecular Dynamics Study

    SciTech Connect

    Baer, Marcel; Mundy, Christopher J.; Chang, Tsun-Mei; Tao, Fu-Ming; Dang, Liem X.

    2010-06-01

    We investigated the solvation and spectroscopic properties of SO2 at the air/water interface using molecular simulation techniques. Molecular interactions from both Kohn-Sham (KS) density functional theory (DFT) and classical polarizable models were utilized to understand the properties of SO2:(H2O)x complexes in the vicinity of the air/water interface. The KS-DFT was included to allow comparisons with sum-frequency generation spectroscopy through the identification of surface SO2:(H2O)x complexes. Using our simulation results, we were able to develop a much more detailed picture for the surface structure of SO2 that is consistent with the spectroscopic data obtained Richmond and coworkers (J. Am. Chem. Soc. 127, 16806 (2005)). We also found many similarities and differences between to the two interaction potentials, including a noticeable weakness of the classical potential model in reproducing the asymmetric hydrogen bonding of water with SO2 due to its inability to account for SO2 resonance structures. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  2. Electrochemical Surface Potential due to Classical Point Charge Models Drives Anion Adsorption to the Air-Water Interface

    SciTech Connect

    Baer, Marcel D.; Stern, Abraham C.; Levin, Yan; Tobias, Douglas J.; Mundy, Christopher J.

    2012-06-07

    Herein, we present research that suggests that the underlying physics that drive simple empirical models of anions (e.g. point charge, no polarization) to the air-water interface, with water described by SPC/E, or related partial charge models is different than when both ions and water are modeled with quantum mechanical based interactions. Specifically, we will show that the driving force of ions to the air-water interface for point charge models results from both cavitation and the negative electrochemical surface potential. We will demonstrate that we can fully characterize the role of the free energy due to the electrochemical surface potential computed from simple empirical models and its role in ionic adsorption within the context of dielectric continuum theory (DCT). Our research suggests that a significant part of the electrochemical surface potential in empirical models appears to be an artifact of the failure of point charge models in the vicinity of a broken symmetry. This work was supported by the U.S. Department of Energy‘s (DOE) Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is operated for the Department of Energy by Battelle.

  3. Ellipsometric characterization of ethylene oxide-butylene oxide diblock copolymer adsorption at the air-water interface.

    PubMed

    Blomqvist, B Rippner; Benjamins, J-W; Nylander, T; Arnebrant, T

    2005-05-24

    Ellipsometry was used to determine the adsorbed layer thickness (d) and the surface excess (adsorbed amount, Gamma) of a nonionic diblock copolymer, E(106)B(16), of poly(ethylene oxide) (E) and poly(butylene oxide) (B) at the air-water interface. The results were obtained (i) by the conventional ellipsometric evaluation procedure using the change of both ellipsometric angles Psi and Delta and (ii) by using the change of Delta only and assuming values of the layer thickness. It was demonstrated that the calculated surface excesses from the different methods were in close agreement, independent of the evaluation procedure, with a plateau adsorption of about 2.5 mg/m(2) (400 A(2)/molecule). Furthermore, the amount of E(106)B(16) adsorbed at the air-water interface was found to be almost identical to that adsorbed from aqueous solution onto a hydrophobic solid surface. In addition, the possibility to use combined measurements with H(2)O or D(2)O as substrates to calculate values of d and Gamma was investigated and discussed. We also briefly discuss within which limits the Gibbs equation can be used to determine the surface excess of polydisperse block copolymers. PMID:15896051

  4. Reversible self-association of ovalbumin at air-water interfaces and the consequences for the exerted surface pressure.

    PubMed

    Kudryashova, Elena V; Visser, Antonie J W G; De Jongh, Harmen H J

    2005-02-01

    In this study the relation between the ability of protein self-association and the surface properties at air-water interfaces is investigated using a combination of spectroscopic techniques. Three forms of chicken egg ovalbumin were obtained with different self-associating behavior: native ovalbumin, heat-treated ov-albumin-being a cluster of 12-16 predominantly noncovalently bound proteins, and succinylated ovalbumin, as a form with diminished aggregation properties due to increased electrostatic repulsion. While the bulk diffusion of aggregated protein is clearly slower compared to monomeric protein, the efficiency of transport to the interface is increased, just like the efficiency of sticking to rather than bouncing from the interface. On a timescale of hours, the aggregated protein dissociates and adopts a conformation comparable to that of native protein adsorbed to the interface. The exerted surface pressure is higher for aggregated material, most probably because the deformability of the particle is smaller. Aggregated protein has a lower ability to desorb from the interface upon compression of the surface layer, resulting in a steadily increasing surface pressure upon reducing the available area for the surface layer. This observation is opposite to what is observed for succinylated protein that may desorb more easily and thereby suppresses the buildup of a surface pressure. Generally, this work demonstrates that modulating the ability of proteins to self-associate offers a tool to control the rheological properties of interfaces.

  5. Phospholipid surface bilayers at the air-water interface. II. Water permeability of dimyristoylphosphatidylcholine surface bilayers.

    PubMed Central

    Ginsberg, L; Gershfeld, N L

    1985-01-01

    Dispersions of dimyristoylphosphatidylcholine (DMPC) in water have been reported to form a structure at 29 degrees C at the equilibrium air/water surface with a molecular density equal to that of a typical bilayer. In this study, the water permeability of this structure has been evaluated by measuring the rate of water evaporation from DMPC dispersions in water in the temperature range where the surface film density exceeds that of a monolayer. Evaporation rates for the lipid dispersions did not deviate from those for lipid-free systems throughout the entire temperature range examined (20-35 degrees C) except at 29 degrees C, where a barrier to evaporation was detected. This strengthens the view that the structure that forms at this temperature has the properties of a typical bilayer. PMID:3978199

  6. Surface pressure affects B-hordein network formation at the air-water interface in relation to gastric digestibility.

    PubMed

    Yang, Jingqi; Huang, Jun; Zeng, Hongbo; Chen, Lingyun

    2015-11-01

    Protein interfacial network formation under mechanical pressure and its influence on degradation was investigated at molecular level using Langmuir-Blodgett B-hordein monolayer as a 2D model. Surface properties, such as surface pressure, dilatational and shear rheology and the surface pressure--area (π-A) isotherm, of B-hordein at air-water interface were analyzed by tensiometer, rheometer and a Langmuir-Blodgett trough respectively. B-Hordein conformation and orientation under different surface pressures were determined by polarization modulation-infrared reflection absorption spectroscopy (PM-IRRAS). The interfacial network morphology was observed by atomic force microscopy (AFM). B-Hordein could reduce the air-water surface tension rapidly to ∼ 45 mN/m and form a solid-like network with high rheological elasticity and compressibility at interface, which could be a result of interactions developed by intermolecular β-sheets. The results also revealed that B-hordein interfacial network switched from an expanded liquid phase to a solid-like film with increasing compression pressure. The orientation of B-hordein was parallel to the surface when in expended liquid phase, whereas upon compression, the hydrophobic repetitive region tilted away from water phase. When compressed to 30 mN/m, a strong elastic network was formed at the interface, and it was resistant to a harsh gastric-like environment of low pH and pepsin. This work generated fundamental knowledge, which suggested the potential to design B-hordein stabilized emulsions and encapsulations with controllable digestibility for small intestine targeted delivery of bioactive compounds.

  7. DNS and measurements of scalar transfer across an air-water interface during inception and growth of Langmuir circulation

    NASA Astrophysics Data System (ADS)

    Hafsi, A.; Ma, Y.; Buckley, M.; Tejada-Martinez, A. E.; Veron, F.

    2016-05-01

    Direct numerical simulations (DNS) of an initially quiescent coupled air-water interface driven by an air flow with free stream speed of 5 m/s have been conducted and scalar transfer from the air side to the water side and subsequent vertical transport in the water column have been analysed. Two simulations are compared: one with a freely deforming interface, giving rise to gravity-capillary waves and aqueous Langmuir turbulence (LT) characterized by small-scale (centimeter-scale) Langmuir cells (LC), and the other with the interface intentionally held flat, i.e., without LC. It is concluded that LT serves to enhance vertical transport of the scalar in the water side and in the process increases scalar transfer efficiency from the air side to the water side relative to the shear-dominated turbulence in the flat interface case. Furthermore, transition to LT was observed to be accompanied by a spike in scalar flux characterized by an order of magnitude increase. These episodic flux increases, if linked to gusts and overall unsteadiness in the wind field, are expected to be an important contributor in determining the long-term average of the air-sea gas fluxes.

  8. DNS of scalar transfer across an air-water interface during inception and growth of Langmuir circulation

    NASA Astrophysics Data System (ADS)

    Hafsi, Amine; Tejada-Martinez, Andres; Veron, Fabrice; Ma, Yi; USF/UDEL Collaboration

    2015-11-01

    Upon a blowing of a wind over an initially quiescent air-sea interface, first short capillary waves are generated which in time coexist with longer waves as part of a broad spectrum of waves. The interaction between the Stokes drift velocity induced by surface gravity waves and the mean current induced by surface wind stress leads to Langmuir turbulence (LT) characterized by Langmuir circulation (LC) consisting of parallel downwind-elongated, counter rotating vortices roughly aligned in the direction of the wind. The typical length scale of LC ranges from several centimeters when short capillary waves first appear up to tens of meters when the spectrum of waves broadens. Results are presented from direct numerical simulation (DNS) of an initially quiescent coupled air-water interface driven by an air flow with free stream speed of 5 m/s. Cases with a freely deforming interface (characterized by gravity-capillary waves giving rise to small-scale LC) and with the interface intentionally held fixed (i.e. without LC) will be compared to understand the mechanisms by which the LT enhances scalar transfer from the airside to the waterside and bulk concentration throughout the water column. Time-permitting, we will compare our results with available laboratory physical experiments.

  9. Bacterial Swimming at Air/Water and Oil/Water Interfaces

    NASA Astrophysics Data System (ADS)

    Morse, Michael; Huang, Athena; Li, Guanglai; Tang, Jay

    2012-02-01

    The microbes inhabiting the planet over billions of years have adapted to diverse physical environments of water, soil, and interfaces between water and either solid or air. Following recent studies on bacterial swimming and accumulation near solid surfaces, we turn our attention to the behavior of Caulobacter crescentus, a singly flagellated bacterium, at water/air and water/oil interfaces. The latter is motivated by relevance to microbial degradation of crude oil in light of the recent oil spill in the Gulf of Mexico. Our ongoing study suggests that Caulobacter swarmer cells tend to get physically trapped at both water/air and water/oil interfaces, accumulating at the surface to a greater degree than boundary confinement properties like that of solid surfaces would predict. At the water/air interface, swimmers move in tight circles at half the speed of swimmers in the bulk fluid. At the water/oil interface, swimming circles are even tighter with further reduced swimming speed. We report experimental data and present preliminary analysis of the findings based on low Reynolds number hydrodynamics, the known surface tension, and surface viscosity at the interface. The analysis will help determine properties of the bacterium such as their surface charge and hydrophobicity.

  10. Behaviors of bovine serum albumin and rapeseed proteins at the air/water interface after grafting aliphatic or aromatic chains.

    PubMed

    Gerbanowski, Alice; Rabiller, Claude; Guéguen, Jacques

    2003-06-15

    The influence of grafting aliphatic or aromatic groups on the behaviors of bovine serum albumin (BSA) and rapeseed proteins (napin and cruciferin) at the air/water interface is studied. From compression isotherms, it is shown that the chemical modification induces an increase in the interfacial molecular areas of the three proteins. The more hydrophobic the groups grafted, the more important this increase is. The dilatational modulus clearly emphasized that the grafting of hydrophobic groups also leads to an increase of the collapse pressure, demonstrating a higher cohesiveness and resistance to pressure of the interfacial films. These results are discussed on the basis of the physicochemical changes due to these chemical modifications, especially the conformation, the surface hydrophobicity, and the flexibility of the modified proteins. The improvement of surface properties obtained by grafting aliphatic or aromatic chains onto these proteins looks very promising in regard to emulsifying and foaming properties.

  11. The Equilibria of Diosgenin-Phosphatidylcholine and Diosgenin-Cholesterol in Monolayers at the Air/Water Interface.

    PubMed

    Janicka, Katarzyna; Jastrzebska, Izabella; Petelska, Aneta Dorota

    2016-08-01

    Diosgenin (Dio) has shown many treatment properties, but the most important property is cytotoxic activity in cancer cells. In this study, we investigated monolayers of Dio, cholesterol (Ch), and phosphatidylcholine (PC) at the air/water interface. The measurements were carried with a Langmuir Teflon trough and a Nima 9000 tensiometer program. The surface tension values of pure and mixed monolayers were used to calculate π-A isotherms and determine molecular surface areas. We were able to demonstrate the formation of complexes between Dio and PC and Dio and Ch molecules also. We considered the equilibrium between individual components and the formed complexes. In addition, we established that diosgenin and the lipids formed highly stable 1:1 complexes. PMID:27350149

  12. Characerization of photosynthetic reaction centres from Rhodobacter sphaeroides at the air-water interface and in Langmuir-Blodgett films

    SciTech Connect

    Fang, J.Y.; Gaul, D.F.; Chumanov, G.; Cotton, T.M.; Uphaus, R.A. |

    1995-11-01

    Monolayers of the reaction center complex from Rhodobacter sphaeroides were prepared from dodecyl {Beta}-maltoside suspensions at an air-water interface. The stability of these monolayers was determined. A value of 28 nm{sup 2} per complex was obtained for the cross-sectional area from the equilibrium surface pressure-area isotherms. Multilayer films of alternating arachidic acid-reaction center monolayers were constructed on quartz slides by the Langmuir-Blodgett technique. Absorption spectroscopy was used to confirm the structural integrity of the complex and to determine the transfer ratio. Low-angle X-ray diffraction measurements were performed on these multilayers. A value of 64 A was obtained for the thickness of the reaction center monolayer in the multilayer film. This novel approach can be used to study multilayers of other membrane-bound proteins. 20 refs., 9 figs.

  13. Synthesis of a Two-Dimensional Covalent Organic Monolayer through Dynamic Imine Chemistry at the Air/Water Interface.

    PubMed

    Dai, Wenyang; Shao, Feng; Szczerbiński, Jacek; McCaffrey, Ryan; Zenobi, Renato; Jin, Yinghua; Schlüter, A Dieter; Zhang, Wei

    2016-01-01

    A two-dimensional covalent organic monolayer was synthesized from simple aromatic triamine and dialdehyde building blocks by dynamic imine chemistry at the air/water interface (Langmuir-Blodgett method). The obtained monolayer was characterized by optical microscopy, scanning electron microscopy, and atomic force microscopy, which unambiguously confirmed the formation of a large (millimeter range), unimolecularly thin aromatic polyimine sheet. The imine-linked chemical structure of the obtained monolayer was characterized by tip-enhanced Raman spectroscopy, and the peak assignment was supported by spectra simulated by density functional theory. Given the modular nature and broad substrate scope of imine formation, the work reported herein opens up many new possibilities for the synthesis of customizable 2D polymers and systematic studies of their structure-property relationships.

  14. Supramolecular 1-D polymerization of DNA origami through a dynamic process at the 2-dimensionally confined air-water interface.

    PubMed

    Yonamine, Yusuke; Cervantes-Salguero, Keitel; Minami, Kosuke; Kawamata, Ibuki; Nakanishi, Waka; Hill, Jonathan P; Murata, Satoshi; Ariga, Katsuhiko

    2016-05-14

    In this study, a Langmuir-Blodgett (LB) system has been utilized for the regulation of polymerization of a DNA origami structure at the air-water interface as a two-dimensionally confined medium, which enables dynamic condensation of DNA origami units through variation of the film area at the macroscopic level (ca. 10-100 cm(2)). DNA origami sheets were conjugated with a cationic lipid (dioctadecyldimethylammonium bromide, 2C18N(+)) by electrostatic interaction and the corresponding LB-film was prepared. By applying dynamic pressure variation through compression-expansion processes, the lipid-modified DNA origami sheets underwent anisotropic polymerization forming a one-dimensionally assembled belt-shaped structure of a high aspect ratio although the thickness of the polymerized DNA origami was maintained at the unimolecular level. This approach opens up a new field of mechanical induction of the self-assembly of DNA origami structures. PMID:27091668

  15. Introducing high-quality planar defects into colloidal crystals via self-assembly at the air/water interface

    NASA Astrophysics Data System (ADS)

    Zhong, Kuo; Demeyer, Pieter-Jan; Zhou, Xingping; Kruglova, Olga; Verellen, Niels; Moshchalkov, Victor V.; Song, Kai; Clays, Koen

    2015-02-01

    We demonstrate a facile method for fabrication of colloidal crystals containing a planar defect by using PS@SiO2 core-shell spheres as building blocks. A monolayer of solid spheres was embedded in core-shell colloidal crystals serving as the defect layer, which formed by means of self-assembly at the air/water interface. Compared with previous methods, this fabrication method results in pronounced passbands in the band gaps of the colloidal photonic crystal. The FWHM of the obtained passband is only ~16nm, which is narrower than the previously reported results. The influence of the defect layer thickness on the optical properties of these sandwiched structures was also investigated. No high-cost processes or specific equipment is needed in our approach. Inverse opals with planar defects can be obtained via calcination of the PS cores, without the need of infiltration. The experimental results are in good agreement with simulations performed using the FDTD method.

  16. Turbulence at the Air-Water Interface in Lakes of Different Sizes: Consequences for Gas Transfer Coefficients

    NASA Astrophysics Data System (ADS)

    MacIntyre, S.; Crowe, A. T.; Amaral, J. H.; Arneborg, L.; Bastviken, D.; Forsberg, B. R.; Melack, J. M.; Tota, J.; Tedford, E. W.; Karlsson, J.; Podgrajsek, E.; Andersson, A.; Rutgersson, A.

    2014-12-01

    Similarity scaling predicts that wind induced shear will be the dominant source of turbulence near the air-water interface in lakes with low to moderate wind forcing. Turbulence is expected to be enhanced with wave activity; results are conflicting on the effects of heating and cooling. We measured turbulence with an acoustic Doppler velocimeter (ADV) and / or a temperature-gradient microstructure profiler and obtained correlative time series measurements of meteorology and water column temperature in a 800 m2 arctic pond, a 1 ha boreal lake, and a large tropical reservoir. Turbulence measurements with both instruments corroborated those calculated from similarity scaling in the boreal lake. Within the arctic pond, dissipation rates obtained with the ADV were in agreement with those from similarity scaling when winds exceeded ~1.5 m/s with a greater frequency of measurable dissipation rates when surface waves were present. Dissipation rates in the tropical reservoir reached and often exceeded 10-6 m2 s-3 in the upper meter under light winds and decreased by an order of magnitude with cooling or rainfall. Under cooling, dissipation rates were at least an order of magnitude higher in the uppermost 25 cm bin than in the water column below. Gas transfer coefficients calculated from concurrent measurements of greenhouse gas fluxes with floating chambers and the surface renewal model using the estimates of turbulence were in agreement. These results support the predictions of Monin-Obuhov similarity scaling in that shear dominates turbulence production near the air-water interface under heating and cooling, illustrate spatial variability in turbulence production in small water bodies due to the intermittency of wind interacting with the water's surface, are in agreement with prior oceanic observations that shear and associated turbulence can be intensified in shallow mixing layers under heating with light winds, and illustrate the utility of similarity scaling for

  17. Gas exchange rates across the sediment-water and air-water interfaces in south San Francisco Bay

    USGS Publications Warehouse

    Hartman, Blayne; Hammond, Douglas E.

    1984-01-01

    Radon 222 concentrations in the water and sedimentary columns and radon exchange rates across the sediment-water and air-water interfaces have been measured in a section of south San Francisco Bay. Two independent methods have been used to determine sediment-water exchange rates, and the annual averages of these methods agree within the uncertainty of the determinations, about 20%. The annual average of benthic fluxes from shoal areas is nearly a factor of 2 greater than fluxes from the channel areas. Fluxes from the shoal and channel areas exceed those expected from simple molecular diffusion by factors of 4 and 2, respectively, apparently due to macrofaunal irrigation. Values of the gas transfer coefficient for radon exchange across the air-water interface were determined by constructing a radon mass balance for the water column and by direct measurement using floating chambers. The chamber method appears to yield results which are too high. Transfer coefficients computed using the mass balance method range from 0.4 m/day to 1.8 m/day, with a 6-year average of 1.0 m/day. Gas exchange is linearly dependent upon wind speed over a wind speed range of 3.2–6.4 m/s, but shows no dependence upon current velocity. Gas transfer coefficients predicted from an empirical relationship between gas exchange rates and wind speed observed in lakes and the oceans are within 30% of the coefficients determined from the radon mass balance and are considerably more accurate than coefficients predicted from theoretical gas exchange models.

  18. Static and dynamic evanescent wave light scattering studies of diblock copolymers adsorbed at the air/water interface

    NASA Astrophysics Data System (ADS)

    Lin, Binhua; Rice, Stuart A.; Weitz, D. A.

    1993-11-01

    We report the results of static and dynamic evanescent wave light scattering studies of a monolayer of a diblock copolymer, polystyrene-b-polymethylmethacrylate (PS-b-PMMA) with weight averaged molecular weights (Mw) of 880 000:290 000 supported at the air/water interface. Our studies probe the interfacial structural and dynamic properties of the monolayer on a length scale which is a fraction of the wavelength of light. The static light scattering studies were carried out as a function of polymer surface coverage and temperature; we also report some preliminary data for the dependence of the static structure function on the relative molecular weights of the PS and PMMA blocks. The complementary dynamic light scattering studies were carried out only as a function of surface coverage. Our data suggest that, upon spreading in the air/water interface, PS-b-PMMA (880:290 K) copolymers form thin disklike aggregates containing about 240 molecules. These data are consistent with a model in which each such aggregate is a ``furry disk'' with a dense core consisting of a layer of collapsed PS blocks atop a thin layer of extended PMMA blocks on the water surface and a brushlike boundary of extended PMMA blocks. The data show that the furry disks diffuse freely when the surface coverage is small, but when the surface coverage is large, they are immobile. Our data also suggest that the furry disks can aggregate to form even larger ``islands'' of disks with an extension greater than 20 μm. The static structure function of the assembly of furry disks is well described, over a wide range of surface coverage, by the structure factor of a two-dimensional hard disk fluid modulated by a two-dimensional hard disk form factor.

  19. Probing Shear Thinning Behaviors of IgG Molecules at the Air-Water Interface via Rheological Methods.

    PubMed

    Gleason, Camille; Yee, Chanel; Masatani, Peter; Middaugh, C Russell; Vance, Aylin

    2016-01-19

    Shear thinning behavior, often observed in shear viscosity tests of IgG therapeutic molecules, could lead to significant disparities in the projections for the viscosity profile of a molecule. Despite its importance, molecular determinants of sheer thinning in protein suspensions are largely unknown. To better understand the factors influencing sheer thinning, viscosity profiles of IgG1 and IgG2 molecules were monitored over a wide range of bulk concentrations (0.007-70 mg/mL). The degree of shear-thinning of 70 and 0.007 mg/mL samples was minimal in comparison to the 0.7 mg/mL solution for both IgG molecules. These observations suggest that bulk concentration alone does not determine the degree of sheer thinning, and additional factors play a role. Additional data reveals, within a threshold range of concentrations, that a strong correlation exists between the degree of shear thinning and the surface area to volume (SA:V) ratio of an IgG sample exposed to the interface. The influence of the interface, however, diminishes when the bulk concentration falls outside this concentration window. Also revealed by interfacial oscillatory rheological testing, both IgG molecules showed solid-like behavior (G'i) at the air-water interface at 0.7 mg/mL, whereas liquid-like behavior (G″i) was dominant at 0.007 and 70 mg/mL concentrations. These observations imply that the lack of solid-like behavior was due to the absence of a network structure. Likewise the addition of polysorbate 20 (PS20) to the 0.7 mg/mL solutions decreased the degree of shear thinning by disrupting the network structure at the interface. Taken together, the results presented here suggest that, although shear thinning behavior is a manifestation of an interfacial, rather than a bulk, phenomenon, the extent of it depends on how susceptible the surface molecules are to the air-water interface, where the surface molecular structures are influenced by the bulk properties.

  20. Surface Tension Drives the Orientation of Crystals at the Air-Water Interface.

    PubMed

    Chevalier, Nicolas R; Guenoun, Patrick

    2016-07-21

    The fabrication of oriented crystalline thin films is essential for a range of applications ranging from semiconductors to optical components, sensors, and catalysis. Here we show by depositing micrometric crystal particles on a liquid interface from an aerosol phase that the surface tension of the liquid alone can drive the crystallographic orientation of initially randomly oriented particles. The X-ray diffraction patterns of the particles at the interface are identical to those of a monocrystalline sample cleaved along the {104} (CaCO3) or {111} (CaF2) face. We show how this orientation effect can be used to produce thin coatings of oriented crystals on a solid substrate. These results also have important implications for our understanding of heterogeneous crystal growth beneath amphiphile monolayers and for 2D self-assembly processes at the air-liquid interface. PMID:27389283

  1. Surface Tension Drives the Orientation of Crystals at the Air-Water Interface.

    PubMed

    Chevalier, Nicolas R; Guenoun, Patrick

    2016-07-21

    The fabrication of oriented crystalline thin films is essential for a range of applications ranging from semiconductors to optical components, sensors, and catalysis. Here we show by depositing micrometric crystal particles on a liquid interface from an aerosol phase that the surface tension of the liquid alone can drive the crystallographic orientation of initially randomly oriented particles. The X-ray diffraction patterns of the particles at the interface are identical to those of a monocrystalline sample cleaved along the {104} (CaCO3) or {111} (CaF2) face. We show how this orientation effect can be used to produce thin coatings of oriented crystals on a solid substrate. These results also have important implications for our understanding of heterogeneous crystal growth beneath amphiphile monolayers and for 2D self-assembly processes at the air-liquid interface.

  2. Dynamic performance of duolayers at the air/water interface. 2. Mechanistic insights from all-atom simulations.

    PubMed

    Christofferson, Andrew J; Yiapanis, George; Leung, Andy H M; Prime, Emma L; Tran, Diana N H; Qiao, Greg G; Solomon, David H; Yarovsky, Irene

    2014-09-18

    The novel duolayer system, comprising a monolayer of ethylene glycol monooctadecyl ether (C18E1) and the water-soluble polymer poly(vinylpyrrolidone) (PVP), has been shown to resist forces such as wind stress to a greater degree than the C18E1 monolayer alone. This paper reports all-atom molecular dynamics simulations comparing the monolayer (C18E1 alone) and duolayer systems under an applied force parallel to the air/water interface. The simulations show that, due to the presence of PVP at the interface, the duolayer film exhibits an increase in chain tilt, ordering, and density, as well as a lower lateral velocity compared to the monolayer. These results provide a molecular rationale for the improved performance of the duolayer system under wind conditions, as well as an atomic-level explanation for the observed efficacy of the duolayer system as an evaporation suppressant, which may serve as a useful guide for future development for thin films where resistance to external perturbation is desirable.

  3. Ozonolysis of methyl oleate monolayers at the air-water interface: oxidation kinetics, reaction products and atmospheric implications.

    PubMed

    Pfrang, Christian; Sebastiani, Federica; Lucas, Claire O M; King, Martin D; Hoare, Ioan D; Chang, Debby; Campbell, Richard A

    2014-07-14

    Ozonolysis of methyl oleate monolayers at the air-water interface results in surprisingly rapid loss of material through cleavage of the C=C bond and evaporation/dissolution of reaction products. We determine using neutron reflectometry a rate coefficient of (5.7 ± 0.9) × 10(-10) cm(2) molecule(-1) s(-1) and an uptake coefficient of ∼3 × 10(-5) for the oxidation of a methyl ester monolayer: the atmospheric lifetime is ∼10 min. We obtained direct experimental evidence that <2% of organic material remains at the surface on atmospheric timescales. Therefore known long atmospheric residence times of unsaturated fatty acids suggest that these molecules cannot be present at the interface throughout their ageing cycle, i.e. the reported atmospheric longevity is likely to be attributed to presence in the bulk and viscosity-limited reactive loss. Possible reaction products were characterized by ellipsometry and uncertainties in the atmospheric fate of organic surfactants such as oleic acid and its methyl ester are discussed. Our results suggest that a minor change to the structure of the molecule (fatty acid vs. its methyl ester) considerably impacts on reactivity and fate of the organic film. PMID:24870051

  4. Impact of biogenic amine molecular weight and structure on surfactant adsorption at the air-water interface.

    PubMed

    Penfold, Jeffrey; Thomas, Robert K; Li, Peixun

    2016-02-01

    The oligoamines, such as ethylenediamine to pentaethylenetetramine, and the aliphatic biogenic amines, such as putrescine, spermidine and spermine, strongly interact with anionic surfactants, such as sodium dodecylsulfate, SDS. It has been shown that this results in pronounced surfactant adsorption at the air-water interface and the transition from monolayer to multilayer adsorption which depends upon solution pH and oligoamine structure. In the neutron reflectivity, NR, and surface tension, ST, results presented here the role of the oligoamine structure on the adsorption of SDS is investigated more fully using a range of different biogenic amines. The effect of the extent of the intra-molecular spacing between amine groups on the adsorption has been extended by comparing results for cadavarine with putrescine and ethylenediamine. The impact of more complex biogenic amine structures on the adsorption has been investigated with the aromatic phenethylamine, and the heterocyclic amines histamine and melamine. The results provide an important insight into how surfactant adsorption at interfaces can be manipulated by the addition of biogenic amines, and into the role of solution pH and oligoamine structure in modifying the interaction between the surfactant and oligoamine. The results impact greatly upon potential applications and in understanding some of the important biological functions of biogenic amines.

  5. Tuning the Structure and Rheology of Polystyrene Particles at the Air-Water Interface by Varying the pH.

    PubMed

    Truzzolillo, Domenico; Sharaf, Hossameldeen; Jonas, Ulrich; Loppinet, Benoit; Vlassopoulos, Dimitris

    2016-07-12

    We form films of carboxylated polystyrene particles (C-PS) at the air-water interface and investigate the effect of subphase pH on their structure and rheology by using a suite of complementary experimental techniques. Our results suggest that electrostatic interactions drive the stability and the structural order of the films. In particular, we show that by increasing the pH of the subphase from 9 up to 13, the films exhibit a gradual transition from solid to liquidlike, which is accompanied by a loss of the long-range order (that characterizes them at lower values of pH). Direct optical visualization of the layers, scanning electron microscopy, and surface pressure isotherms indicate that the particles deposited at the interface form three-dimensional structures involving clusters, with the latter being suppressed and a quasi-2D particle configuration eventually reached at the highest pH values. Evidently, the properties of colloidal films can be tailored significantly by altering the pH of the subphase.

  6. Effects of surface pressure on the properties of Langmuir monolayers and interfacial water at the air-water interface.

    PubMed

    Lin, Wei; Clark, Anthony J; Paesani, Francesco

    2015-02-24

    The effects of surface pressure on the physical properties of Langmuir monolayers of palmitic acid (PA) and dipalmitoylphosphatidic acid (DPPA) at the air/water interface are investigated through molecular dynamics simulations with atomistic force fields. The structure and dynamics of both monolayers and interfacial water are compared across the range of surface pressures at which stable monolayers can form. For PA monolayers at T = 300 K, the untilted condensed phase with a hexagonal lattice structure is found at high surface pressure, while the uniformly tilted condensed phase with a centered rectangular lattice structure is observed at low surface pressure, in agreement with the available experimental data. A state with uniform chain tilt but no periodic spatial ordering is observed for DPPA monolayers on a Na(+)/water subphase at both high and low surface pressures. The hydrophobic acyl chains of both monolayers pack efficiently at all surface pressures, resulting in a very small number of gauche defects. The analysis of the hydrogen-bonding structure/dynamics at the monolayer/water interface indicates that water molecules hydrogen-bonded to the DPPA head groups reorient more slowly than those hydrogen-bonded to the PA head groups, with the orientational dynamics becoming significantly slower at high surface pressure. Possible implications for physicochemical processes taking place on marine aerosols in the atmosphere are discussed.

  7. Relative Order of Sulfuric Acid, Bisulfate, Hydronium, and Cations at the Air-Water Interface.

    PubMed

    Hua, Wei; Verreault, Dominique; Allen, Heather C

    2015-11-01

    Sulfuric acid (H2SO4), bisulfate (HSO4(-)), and sulfate (SO4(2-)) are among the most abundant species in tropospheric and stratospheric aerosols due to high levels of atmospheric SO2 emitted from biomass burning and volcanic eruptions. The air/aqueous interfaces of sulfuric acid and bisulfate solutions play key roles in heterogeneous reactions, acid rain, radiative balance, and polar stratospheric cloud nucleation. Molecular-level knowledge about the interfacial distribution of these inorganic species and their perturbation of water organization facilitates a better understanding of the reactivity and growth of atmospheric aerosols and of the aerosol surface charge, thus shedding light on topics of air pollution, climate change, and thundercloud electrification. Here, the air/aqueous interface of NaHSO4, NH4HSO4, and Mg(HSO4)2 salt solutions as well as H2SO4 and HCl acid solutions are investigated by means of vibrational sum frequency generation (VSFG) and heterodyne-detected (HD) VSFG spectroscopy. VSFG spectra of all acid solutions show higher SFG response in the OH-bonded region relative to neat water, with 1.1 M H2SO4 being more enhanced than 1.1 M HCl. In addition, VSFG spectra of bisulfate salt solutions highly resemble that of the dilute H2SO4 solution (0.26 M) at a comparable pH. HD-VSFG (Im χ((2))) spectra of acid and bisulfate salt solutions further reveal that hydrogen-bonded water molecules are oriented preferentially toward the bulk liquid phase. General agreement between Im χ((2)) spectra of 1.1 M H2SO4 and 1.1 M HCl acid solutions indicate that HSO4(-) ions have a similar surface preference as that of chloride (Cl(-)) ions. By comparing the direction and magnitude of the electric fields arising from the interfacial ion distributions and the concentration of each species, the most reasonable relative surface preference that can be deduced from a simplified model follows the order H3O(+) > HSO4(-) > Na(+), NH4(+), Mg(2+) > SO4(2-). Interestingly

  8. Relative Order of Sulfuric Acid, Bisulfate, Hydronium, and Cations at the Air-Water Interface.

    PubMed

    Hua, Wei; Verreault, Dominique; Allen, Heather C

    2015-11-01

    Sulfuric acid (H2SO4), bisulfate (HSO4(-)), and sulfate (SO4(2-)) are among the most abundant species in tropospheric and stratospheric aerosols due to high levels of atmospheric SO2 emitted from biomass burning and volcanic eruptions. The air/aqueous interfaces of sulfuric acid and bisulfate solutions play key roles in heterogeneous reactions, acid rain, radiative balance, and polar stratospheric cloud nucleation. Molecular-level knowledge about the interfacial distribution of these inorganic species and their perturbation of water organization facilitates a better understanding of the reactivity and growth of atmospheric aerosols and of the aerosol surface charge, thus shedding light on topics of air pollution, climate change, and thundercloud electrification. Here, the air/aqueous interface of NaHSO4, NH4HSO4, and Mg(HSO4)2 salt solutions as well as H2SO4 and HCl acid solutions are investigated by means of vibrational sum frequency generation (VSFG) and heterodyne-detected (HD) VSFG spectroscopy. VSFG spectra of all acid solutions show higher SFG response in the OH-bonded region relative to neat water, with 1.1 M H2SO4 being more enhanced than 1.1 M HCl. In addition, VSFG spectra of bisulfate salt solutions highly resemble that of the dilute H2SO4 solution (0.26 M) at a comparable pH. HD-VSFG (Im χ((2))) spectra of acid and bisulfate salt solutions further reveal that hydrogen-bonded water molecules are oriented preferentially toward the bulk liquid phase. General agreement between Im χ((2)) spectra of 1.1 M H2SO4 and 1.1 M HCl acid solutions indicate that HSO4(-) ions have a similar surface preference as that of chloride (Cl(-)) ions. By comparing the direction and magnitude of the electric fields arising from the interfacial ion distributions and the concentration of each species, the most reasonable relative surface preference that can be deduced from a simplified model follows the order H3O(+) > HSO4(-) > Na(+), NH4(+), Mg(2+) > SO4(2-). Interestingly

  9. Methane flux across the air-water interface - Air velocity effects

    NASA Technical Reports Server (NTRS)

    Sebacher, D. I.; Harriss, R. C.; Bartlett, K. B.

    1983-01-01

    Methane loss to the atmosphere from flooded wetlands is influenced by the degree of supersaturation and wind stress at the water surface. Measurements in freshwater ponds in the St. Marks Wildlife Refuge, Florida, demonstrated that for the combined variability of CH4 concentrations in surface water and air velocity over the water surface, CH4 flux varied from 0.01 to 1.22 g/sq m/day. The liquid exchange coefficient for a two-layer model of the gas-liquid interface was calculated as 1.7 cm/h for CH4 at air velocity of zero and as 1.1 + 1.2 v to the 1.96th power cm/h for air velocities from 1.4 to 3.5 m/s and water temperatures of 20 C.

  10. Toward a simple molecular understanding of sum frequency generation at air-water interfaces

    SciTech Connect

    Noah-Vanhoucke, Joyce; Smith, Jared D.; Geissler, Phillip L.

    2009-01-13

    Second-order vibrational spectroscopies successfully isolate signals from interfaces, but they report on intermolecular structure in a complicated and indirect way. Here we adapt a perspective on vibrational response developed for bulk spectroscopies to explore the microscopic fluctuations to which sum frequency generation (SFG), a popular surface-specific measurement, is most sensitive. We focus exclusively on inhomogeneous broadening of spectral susceptibilities for OH stretching of HOD as a dilute solute in D{sub 2}O. Exploiting a simple connection between vibrational frequency shifts and an electric field variable, we identify several functions of molecular orientation whose averages govern SFG. The frequency-dependence of these quantities is well captured by a pair of averages, involving alignment of OH and OD bonds with the surface normal at corresponding values of the electric field. The approximate form we obtain for SFG susceptibility highlights a dramatic sensitivity to the way a simulated liquid slab is partitioned for calculating second-order response.

  11. Surface Pressure Study of Lipid Aggregates at the Air Water Interface

    NASA Astrophysics Data System (ADS)

    Shew, Woody; Ploplis Andrews, Anna

    1996-11-01

    Qualitative and quantitative descriptions of the growth of fatty acid aggregates on a water/air interface were made by analyzing surface pressure measurements taken with a Langmuir Balance. High concentrations of palmitic acid, lauric acid, myristic acid, and also phosphatidylethanolamine in solution with chloroform were applied with a syringe to the surface of the Langmuir Balance and surface pressure was monitored as aggregates assembled spontaneously. The aggregation process for palmitic acid was determined to consist of three distinct parts. Exponential curves were fit to the individual regions of the data and growth and decay constants were determined. Surface pressure varied in very complex ways for lauric acid, myristic acid, and phosphatidylethanolamine yet kinetic measurements yield qualitative information about assembly of those aggregates. This research was supported by NSF Grant No. DMR-93-22301.

  12. Hydrogen bonding and orientation effects on the accommodation of methylamine at the air-water interface

    NASA Astrophysics Data System (ADS)

    Hoehn, Ross D.; Carignano, Marcelo A.; Kais, Sabre; Zhu, Chongjing; Zhong, Jie; Zeng, Xiao C.; Francisco, Joseph S.; Gladich, Ivan

    2016-06-01

    Methylamine is an abundant amine compound detected in the atmosphere which can affect the nature of atmospheric aerosol surfaces, changing their chemical and optical properties. Molecular dynamics simulation results show that methylamine accommodation on water is close to unity with the hydrophilic head group solvated in the interfacial environment and the methyl group pointing into the air phase. A detailed analysis of the hydrogen bond network indicates stronger hydrogen bonds between water and the primary amine group at the interface, suggesting that atmospheric trace gases will likely react with the methyl group instead of the solvated amine site. These findings suggest new chemical pathways for methylamine acting on atmospheric aerosols in which the methyl group is the site of orientation specific chemistry involving its conversion into a carbonyl site providing hydrophilic groups for uptake of additional water. This conversion may explain the tendency of aged organic aerosols to form cloud condensation nuclei. At the same time, formation of NH2 radical and formaldehyde is suggested to be a new source for NH2 radicals at aerosol surfaces, other than by reaction of absorbed NH3. The results have general implications for the chemistry of other amphiphilic organics, amines in particular, at the surface of atmospherically relevant aerosols.

  13. Structural and topographical characteristics of adsorbed WPI and monoglyceride mixed monolayers at the air-water interface.

    PubMed

    Patino, Juan M Rodríguez; Fernández, Marta Cejudo

    2004-05-25

    In this work we have analyzed the structural and topographical characteristics of mixed monolayers formed by an adsorbed whey protein isolate (WPI) and a spread monoglyceride monolayer (monopalmitin or monoolein) on the previously adsorbed protein film. Measurements of the surface pressure (pi)-area (A) isotherm were obtained at 20 degrees C and at pH 7 for protein-adsorbed films from water in a Wilhelmy-type film balance. Since the surface concentration (1/A) is actually unknown for the adsorbed monolayer, the values were derived by assuming that the A values for adsorbed and spread monolayers were equal at the collapse point of the mixed film. The pi-A isotherm deduced for adsorbed WPI monolayer in this work is practically the same as that obtained directly by spreading. For WPI-monoglyceride mixed films, the pi-A isotherms for adsorbed and spread monolayers at pi higher than the equilibrium surface pressure of WPI are practically coincident, a phenomenon which may be attributed to the protein displacement by the monoglyceride from the interface. At lower surface pressures, WPI and monoglyceride coexist at the interface and the adsorbed and spread pi-A isotherms (i.e., the monolayer structure of the mixed films) are different. Monopalmitin has a higher capacity than monoolein for the displacement of protein from the air-water interface. However, some degree of interactions exists between proteins and monoglycerides and these interactions are higher for adsorbed than for spread films. The topography of the monolayer corroborates these conclusions.

  14. Adsorption of β-casein-surfactant mixed layers at the air-water interface evaluated by interfacial rheology.

    PubMed

    Maestro, Armando; Kotsmar, Csaba; Javadi, Aliyar; Miller, Reinhard; Ortega, Francisco; Rubio, Ramón G

    2012-04-26

    This work presents a detailed study of the dilational viscoelastic moduli of the adsorption layers of the milk protein β-casein (BCS) and a surfactant at the liquid/air interface, over a broad frequency range. Two complementary techniques have been used: a drop profile tensiometry technique and an excited capillary wave method, ECW. Two different surfactants were studied: the nonionic dodecyldimethylphosphine oxide (C12DMPO) and the cationic dodecyltrimethylammonium bromide (DoTAB). The interfacial dilational elasticity and viscosity are very sensitive to the composition of protein-surfactant mixed adsorption layers at the air/water interface. Two different dynamic processes have been observed for the two systems studied, whose characteristic frequencies are close to 0.01 and 100 Hz. In both systems, the surface elasticity was found to show a maximum when plotted versus the surfactant concentration. However, at frequencies above 50 Hz the surface elasticity of BCS + C12DMPO is higher than the one of the aqueous BCS solution over most of the surfactant concentration range, whereas for the BCS + DoTAB it is smaller for high surfactant concentrations and higher at low concentrations. The BCS-surfactant interaction modifies the BCS random coil structure via electrostatic and/or hydrophobic interactions, leading to a competitive adsorption of the BCS-surfactant complexes with the free, unbound surfactant molecules. Increasing the surfactant concentration decreases the adsorbed proteins. However, the BCS molecules are rather strongly bound to the interface due to their large adsorption energy. The results have been fitted to the model proposed by C. Kotsmar et al. ( J. Phys. Chem. B 2009 , 113 , 103 ). Even though the model describes well the concentration dependence of the limiting elasticity, it does not properly describe its frequency dependence.

  15. Quantifying the effect of the air/water interface in marine active source EM

    NASA Astrophysics Data System (ADS)

    Wright, David

    2015-07-01

    The marine controlled source EM surveying method has become an accepted tool for deep water exploration for oil and gas reserves. In shallow water (< 500 m) data are complicated by the signal which interacts with the water-air interface which can dominate the response at the receiver. By decomposing the 1-D response to an impulsive current dipole source in the time domain and frequency domain I separate the response into: (1) an earth response, (2) a direct arrival, (3) a coupled airwave which travels through the air and (4) a surface coupling term which travels through the earth. The last two terms are coupled to the sea surface as well as to the earth resistivity structure but one travels through the air between source and receiver and the other only through the earth. Using a range of simple models I quantify the effect of these four terms in the time domain and the frequency domain. The results show that in shallow water the total response is significantly larger than in very deep water and that a large part of this extra energy comes from surface coupling, which is reflected at the sea surface and does not propagate through the air but through the earth. As a result, this term is highly sensitive to the resistivity of the earth. This means that the sea surface in shallow water not only significantly increases the signal strength of CSEM data but also enhances the sensitivity to subsurface resistivity structure. Compared with the surface coupling term, the coupled part of the airwave contains very little information about the earth, and is limited to the near surface. Time domain separation of the airwave from the surface coupling response results in greater sensitivity to a deep resistive target than frequency domain separation although there is also reasonable sensitivity in the frequency domain.

  16. Exchange of polycyclic aromatic hydrocarbons across the air-water interface in the Bohai and Yellow Seas

    NASA Astrophysics Data System (ADS)

    Chen, Yingjun; Lin, Tian; Tang, Jianhui; Xie, Zhiyong; Tian, Chongguo; Li, Jun; Zhang, Gan

    2016-09-01

    In this study, air and surface seawater samples collected from the Bohai (BS) and Yellow Seas (YS) in May 2012 were determined exchange of PAHs, especially of low-molecular-weight (LMW) PAHs (three- and four-ring PAHs) at the air-water interface. Net volatilization fluxes of LMW PAHs were 266-1454 ng/m2/d and decreased with distance from the coast, indicating that these PAHs transported from coastal runoff were potential contributors to the atmosphere in the BS and YS. Moreover, LMW PAHs were enriched in the dissolved phase compared with those in the particulate phase in the water column, possibly suggesting that the volatilized LMW PAHs were directly derived from wastewater discharge or petroleum pollution rather than released from contaminated sediments. The air-sea exchange fluxes of the three-ring PAHs were 2- to 20-fold higher than their atmospheric deposition fluxes in the BS and YS. The input to and output from the water reached equilibrium for four-ring PAHs. Differently, five- and six-ring PAHs were introduced into the marine environment primarily through dry and wet deposition, indicating that the water column was still a sink of these PAHs from the surrounding atmosphere.

  17. Carbon dioxide fluxes across the air-water interface and its impact on carbon availability in aquatic systems

    SciTech Connect

    Portielje, R.; Lijklema, L.

    1995-06-01

    Diffusion of CO{sub 2} across the air-water interface was analyzed with a model that simulates both transport and reaction of CO{sub 2} in a stagnant boundary layer. The atmospheric C influx was determined in relation to several environmental variables: pH, total dissolved inorganic C, temperature, and the thickness of the stagnant boundary layer in relation to ambient windspeed. We used the model to calculate the atmospheric CO{sub 2} influx into experimental ditches for a period of 6 to 8 months, starting in early spring. Three of the six ditches were dominated by aquatic macrophytes and three by benthic algae. Each series received three levels of external N and P input. A comparison with net C assimilation during the same period, as estimated from continuous oxygen measurements, showed that, especially in the ditches dominated by submersed macrophytes, a sizable fraction of the C requirements during this period could have been obtained from atmospheric CO{sub 2}. In the ditches dominated by benthic algae, this fraction was considerably less, but nonetheless substantial, and was related to the level of N and P loading. Increased primary production due to enhanced external N and P loading increased the atmospheric C input due to the resultant higher pH values. The trophic state with respect to N and P and the availability of C are therefore interrelated. 25 refs., 8 figs., 5 tabs.

  18. Self-Assembly and Lipid Interactions of Diacylglycerol Lactone Derivatives Studied at the Air/Water Interface

    PubMed Central

    Philosof-Mazor, Liron; Volinsky, Roman; Comin, Maria J.; Lewin, Nancy E.; Kedei, Noemi; Blumberg, Peter M.; Marquez, Victor E.; Jelinek, Raz

    2009-01-01

    Synthetic diacylglycerol lactones (DAG-lactones) have been shown to be effective modulators of critical cellular signaling pathways. The biological activity of these amphiphilic molecules depends in part upon their lipid interactions within the cellular plasma membrane. This study explores the thermodynamic and structural features of DAG-lactone derivatives and their lipid interactions at the air/water interface. Surface-pressure/area isotherms and Brewster angle microscopy revealed the significance of specific side-groups attached to the terminus of a very rigid 4-(2-phenylethynyl) benzoyl chain of the DAG-lactones, which affected both the self-assembly of the molecules and their interactions with phospholipids. The experimental data highlight the formation of different phases within mixed DAG-lactone/phospholipid monolayers and underscore the relationship between the two components in binary mixtures of different mole ratios. Importantly, the results suggest that DAG-lactones are predominantly incorporated within fluid phospholipid phases rather than in the condensed phases that form, for example, by cholesterol. Moreover, the size and charge of the phospholipid headgroups do not seem to affect DAG-lactone interactions with lipids. PMID:18788772

  19. Exchange of polycyclic aromatic hydrocarbons across the air-water interface in the Bohai and Yellow Seas

    NASA Astrophysics Data System (ADS)

    Chen, Yingjun; Lin, Tian; Tang, Jianhui; Xie, Zhiyong; Tian, Chongguo; Li, Jun; Zhang, Gan

    2016-09-01

    In this study, air and surface seawater samples collected from the Bohai (BS) and Yellow Seas (YS) in May 2012 were determined exchange of PAHs, especially of low-molecular-weight (LMW) PAHs (three- and four-ring PAHs) at the air-water interface. Net volatilization fluxes of LMW PAHs were 266-1454 ng/m2/d and decreased with distance from the coast, indicating that these PAHs transported from coastal runoff were potential contributors to the atmosphere in the BS and YS. Moreover, LMW PAHs were enriched in the dissolved phase compared with those in the particulate phase in the water column, possibly suggesting that the volatilized LMW PAHs were directly derived from wastewater discharge or petroleum pollution rather than released from contaminated sediments. The air-sea exchange fluxes of the three-ring PAHs were 2- to 20-fold higher than their atmospheric deposition fluxes in the BS and YS. The input to and output from the water reached equilibrium for four-ring PAHs. Differently, five- and six-ring PAHs were introduced into the marine environment primarily through dry and wet deposition, indicating that the water column was still a sink of these PAHs from the surrounding atmosphere.

  20. Disruption of viscoelastic beta-lactoglobulin surface layers at the air-water interface by nonionic polymeric surfactants.

    PubMed

    Rippner Blomqvist, B; Ridout, M J; Mackie, A R; Wärnheim, T; Claesson, P M; Wilde, P

    2004-11-01

    Nonequilibrium interfacial layers formed by competitive adsorption of beta-lactoglobulin and the nonionic triblock copolymer PEO99-PPO65-PEO99 (F127) to the air-water interface were investigated in order to explain the influence of polymeric surfactants on protein film surface rheology and foam stability. Surface dilatational and shear rheological methods, surface tension measurements, dynamic thin-film measurements, diffusion measurements (from fluorescence recovery after photo bleaching), and determinations of foam stability were used as methods. The high surface viscoelasticity, both the shear and dilatational, of the protein films was significantly reduced by coadsorption of polymeric surfactant. The drainage rate of single thin films, in the presence of beta-lactoglobulin, increased with the amount of added F127, but equilibrium F127 films were found to be thicker than beta-lactoglobulin films, even at low concentration of the polymeric surfactant. It is concluded that the effect of the nonionic triblock copolymer on the interfacial rheology of beta-lactoglobulin layers is similar to that of low molecular weight surfactants. They differ however in that F127 increases the thickness of thin liquid films. In addition, the significant destabilizing effect of low molecular weight surfactants on protein foams is not found in the investigated system. This is explained as due to long-range steric forces starting to stabilize the foam films at low concentrations of F127. PMID:15518507

  1. Effect of perfluoroalkyl chain length on monolayer behavior of partially fluorinated oleic acid molecules at the air-water interface.

    PubMed

    Baba, Teruhiko; Takai, Katsuki; Takagi, Toshiyuki; Kanamori, Toshiyuki

    2013-01-01

    A series of oleic acid (OA) analogs containing terminal perfluoroalkyl groups (CF3, C2F5, n-C3F7, n-C4F9 or n-C8F17) was synthesized to clarify how the fluorinated chain length affects the stability and molecular packing of liquid-expanded OA monolayers at the air-water interface. Although the substitution of terminal CF3 group for CH3 in OA had no effect on monolayer stability, further fluorination led to a gradual increase in monolayer stability at 25 °C. Surface pressure-area isotherm revealed that partially fluorinated OA analogs form more expanded monolayers than OA at low surface pressures, and that the monolayer behavior of OA analogs with the even-carbon numbered fluorinated chain is almost the same as that of OA upon monolayer compression, whereas the behavior of OA analogs with the odd-carbon numbered fluorinated chain significantly differs from that of OA. These results indicate: (i) the terminal short part (at least C2 residue) in OA predominantly determines the liquid-expanded monolayer stability; (ii) the molecular packing state of OA may be perturbed by the substitution of a short odd-carbon numbered fluorinated chain; (iii) hence, OA analogs with even-carbon numbered chain are considered to be preferable as hydrophobic building blocks for the synthesis of fluorinated phospholipids.

  2. Disruption of viscoelastic beta-lactoglobulin surface layers at the air-water interface by nonionic polymeric surfactants.

    PubMed

    Rippner Blomqvist, B; Ridout, M J; Mackie, A R; Wärnheim, T; Claesson, P M; Wilde, P

    2004-11-01

    Nonequilibrium interfacial layers formed by competitive adsorption of beta-lactoglobulin and the nonionic triblock copolymer PEO99-PPO65-PEO99 (F127) to the air-water interface were investigated in order to explain the influence of polymeric surfactants on protein film surface rheology and foam stability. Surface dilatational and shear rheological methods, surface tension measurements, dynamic thin-film measurements, diffusion measurements (from fluorescence recovery after photo bleaching), and determinations of foam stability were used as methods. The high surface viscoelasticity, both the shear and dilatational, of the protein films was significantly reduced by coadsorption of polymeric surfactant. The drainage rate of single thin films, in the presence of beta-lactoglobulin, increased with the amount of added F127, but equilibrium F127 films were found to be thicker than beta-lactoglobulin films, even at low concentration of the polymeric surfactant. It is concluded that the effect of the nonionic triblock copolymer on the interfacial rheology of beta-lactoglobulin layers is similar to that of low molecular weight surfactants. They differ however in that F127 increases the thickness of thin liquid films. In addition, the significant destabilizing effect of low molecular weight surfactants on protein foams is not found in the investigated system. This is explained as due to long-range steric forces starting to stabilize the foam films at low concentrations of F127.

  3. Modification of beta-lactoglobulin by oligofructose: impact on protein adsorption at the air-water interface.

    PubMed

    Trofimova, Daria; de Jongh, Harmen H J

    2004-06-22

    Maillard products of beta-lactoglobulin (betaLg) and fructose oligosaccharide (FOS) were obtained in different degrees of modification depending on incubation time and pH. By use of a variety of biochemical and spectroscopic tools, it was demonstrated that the modification at limited degrees does not significantly affect the secondary, tertiary, and quaternary structure of betaLg. The consequence of the modification on the thermodynamics of the protein was studied using differential scanning calorimetry, circular dichroism, and by monitoring the fluorescence intensity of protein samples with different concentrations of guanidine-HCl. The modification leads to lowering of the denaturation temperature by 5 degrees C and a reduction of the free energy of stabilization of about 30%. Ellipsometry and drop tensiometry demonstrated that upon adsorption to air-water interfaces in equilibrium modified betaLg exerts a lower surface pressure than native betaLg (16 versus 22 mN/m). Moreover, the surface elastic modulus increased with increasing surface pressure but reached significantly smaller values in the case of FOS-betaLg. Compared to native betaLg, modification of the protein with oligofructose moieties results in higher surface loads and thicker surface layers. The consequences of these altered surface rheological properties are discussed in view of the functional behavior in technological applications.

  4. Adsorption of Hydrophobin-Protein Mixtures at the Air-Water Interface: The Impact of pH and Electrolyte.

    PubMed

    Tucker, Ian M; Petkov, Jordan T; Penfold, Jeffrey; Thomas, Robert K; Cox, Andrew R; Hedges, Nick

    2015-09-15

    The adsorption of the proteins β-casein, β-lactoglobulin, and hydrophobin, and the protein mixtures of β-casein/hydrophobin and β-lactoglobulin/hydrophobin have been studied at the air-water interface by neutron reflectivity, NR. Changing the solution pH from 7 to 2.6 has relatively little impact on the adsorption of hydrophobin or β-lactoglobulin, but results in a substantial change in the structure of the adsorbed layer of β-casein. In β-lactoglobulin/hydrophobin mixtures, the adsorption is dominated by the hydrophobin adsorption, and is independent of the hydrophobin or β-lactoglobulin concentration and solution pH. At pH 2.6, the adsorption of the β-casein/hydrophobin mixtures is dominated by the hydrophobin adsorption over the range of β-casein concentrations studied. At pH 4 and 7, the adsorption of β-casein/hydrophobin mixtures is dominated by the hydrophobin adsorption at low β-casein concentrations. At higher β-casein concentrations, β-casein is adsorbed onto the surface monolayer of hydrophobin, and some interpenetration between the two proteins occurs. These results illustrate the importance of pH on the intermolecular interactions between the two proteins at the interface. This is further confirmed by the impact of PBS, phosphate buffered saline, buffer and CaCl2 on the coadsorption and surface structure. The results provide an important insight into the adsorption properties of protein mixtures and their application in foam and emulsion stabilization.

  5. Large-scale recrystallization of the S-layer of Bacillus coagulans E38-66 at the air/water interface and on lipid films.

    PubMed Central

    Pum, D; Weinhandl, M; Hödl, C; Sleytr, U B

    1993-01-01

    S-layer protein isolated from Bacillus coagulans E38-66 could be recrystallized into large-scale coherent monolayers at an air/water interface and on phospholipid films spread on a Langmuir-Blodgett trough. Because of the asymmetry in the physiochemical surface properties of the S-layer protein, the subunits were associated with their more hydrophobic outer face with the air/water interface and oriented with their negatively charged inner face to the zwitterionic head groups of the dipalmitoylphosphatidylcholine and dipalmitoylphosphatidylethanolamine (DPPE) monolayer films. The dynamic crystal growth at both types of interfaces was first initiated at several distant nucleation points. The individual monocrystalline areas grew isotropically in all directions until the front edge of neighboring crystals was met. The recrystallized S-layer protein and the S-layer-DPPE layer could be chemically cross-linked from the subphase with glutaraldehyde. Images PMID:8478338

  6. Vibrational sum-frequency generation spectroscopy of ionic liquid 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate at the air-water interface

    NASA Astrophysics Data System (ADS)

    Saha, Ankur; SenGupta, Sumana; Kumar, Awadhesh; Choudhury, Sipra; Naik, Prakash D.

    2016-08-01

    The structure and orientation of room temperature ionic liquid (RTIL) 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate [PF3(C2F5)3], commonly known as [bmim][fap], have been investigated at the air-[bmim][fap] and air-water interfaces, employing vibrational sum-frequency generation (VSFG) spectroscopy. The VSFG spectra in the CH stretch region suggest presence of the [bmim] cation at the interfaces. Studies reveal that the butyl chain protrudes out into air, and the imidazolium ring lies almost planar to the interface. The CH stretch intensities get enhanced at the air-water interface, mainly because of polar orientation of imidazolium cation induced by interfacial water molecules. The OH stretch intensities are also enhanced at the air-water interface due to polar orientation of interfacial water molecules induced by [bmim][fap]. The Brewster angle microscopy suggests self aggregation of [bmim][fap] in the presence of water, and the aggregation becomes extensive showing dense surface domains with time. However, the surface pressure is almost unaffected due to aggregation.

  7. Effect of hydration of sugar groups on adsorption of Quillaja bark saponin at air/water and Si/water interfaces.

    PubMed

    Wojciechowski, Kamil; Orczyk, Marta; Marcinkowski, Kuba; Kobiela, Tomasz; Trapp, Marcus; Gutberlet, Thomas; Geue, Thomas

    2014-05-01

    Adsorption of a natural glycoside surfactant Quillaja bark saponin ("QBS", Sigma Aldrich 84510) was studied at the air/water and Si/water interfaces using a combination of surface pressure (SP), surface dilatational rheology, neutron reflectivity (NR), Infra-Red Attenuated Total Reflection Spectroscopy (IR ATR) and Quartz Crystal Microbalance (QCM). The adsorbed layers formed at the air/water interface are predominantly elastic, with the dilatational surface storage modulus reaching the maximum value of E'=184 mN/m. The NR results point to a strong hydration of the adsorbed layers (about 65% hydration, corresponding to about 60 molecules of water per one QBS molecule), most likely related to the presence of multiple sugar groups constituting the glycone part of the QBS molecules. With a layer thickness of 19 Å, the adsorbed amount obtained from NR seems largely underestimated in comparison to the value obtained from the surface tension isotherm. While this high extent of hydration does not prevent formation of dense and highly elastic layers at the air-water surface, QBS adsorption at the Si/water interface is much weaker. The adsorption isotherm of QBS on Si obtained from the QCM study reflects much lower affinity of highly hydrated and negatively charged saponin molecules to the Si/water interface. We postulate that at the air/water interface, QBS adsorbs through the triterpene aglycone moiety. In contrast, weak hydrogen bonding between the glycone part and the surface silanol groups of Si is responsible for QBS adsorption on more polar Si/water interface.

  8. Mixed layers of β-lactoglobulin and SDS at air-water interfaces with tunable intermolecular interactions.

    PubMed

    Engelhardt, Kathrin; Weichsel, Ulrike; Kraft, Elena; Segets, Doris; Peukert, Wolfgang; Braunschweig, Björn

    2014-04-17

    Mixtures of β-lactoglobulin (BLG) and sodium dodecyl sulfate (SDS) were studied at pH 3.8 and 6.7 under equilibrium conditions. At these pH conditions, BLG carries either a positive or a negative net charge, respectively, which enables tunable electrostatic interactions between anionic SDS surfactants and BLG proteins. For pH 3.8, vibrational sum-frequency generation (SFG) and ellipsometry indicate strong BLG-SDS complex formation at air-water interfaces that is caused by attractive electrostatic interactions. The latter complexes are already formed in the bulk solution which was confirmed by a thermodynamic study of BLG-SDS mixtures using isothermal titration calorimetry (ITC). For acidic conditions we determine from our ITC data an exothermal binding enthalpy of -40 kJ mol(-1). Increasing SDS/BLG molar ratios above 10 leads to a surface excess of SDS and thus to a charge reversal from a positive net charge with BLG as the dominating surface adsorbed species to a negatively charged layer with SDS as the dominating surface species. The latter is evidenced by a pronounced minimum in SFG intensities that is also accompanied by a phase change of O-H stretching bands due to a reorientation of H2O within the local electric field. This phase change which occurs at SDS/BLG molar ratio between 1 and 10 causes a polarity change in SFG intensities from BLG aromatic C-H stretching vibrations. Conclusions from SFG spectra are corroborated by ellipsometry which shows a dramatic increase in layer thicknesses at molar ratios where a charge reversal occurs. The formation of interfacial multilayers comprising SDS-BLG complexes is, thus, caused by cancellation of electrostatic interactions which leads to agglomeration at the interface. In contrast to pH 3.8, behavior of BLG-SDS mixtures at pH 6.7 is different due to repulsive electrostatic interactions between SDS and BLG which lead to a significantly reduced binding enthalpy of -17 kJ mol(-1). Finally, it has to be mentioned that

  9. Spectroscopic analysis of total-internal-reflection stimulated Raman scattering from the air/water interface under the strong focusing condition

    NASA Astrophysics Data System (ADS)

    Yui, Hiroharu; Fujiwara, Hideyuki; Sawada, Tsuguo

    2002-07-01

    Anomalous enhancement of stimulated Raman scattering (SRS) derived from the OH stretching vibration of interfacial water molecules is observed when excess electrons are generated at an air/water interface by focusing an intense pulsed beam under a total internal reflection configuration. The characteristic SRS peak appears at 3200 cm-1 and is attributed to the water molecules being in an ice-like hydrogen-bonding environment at the interface. The mechanism of the SRS enhancement is discussed in terms of the enhancement of the nonlinear polarizability of the interfacial water by the large electrostatic fields induced by the transiently generated excess electrons at the interface.

  10. Urease and hexadecylamine-urease films at the air-water interface: an x-ray reflection and grazing incidence x-ray diffraction study.

    PubMed Central

    Gidalevitz, D; Huang, Z; Rice, S A

    1999-01-01

    We report the results of surface x-ray scattering measurements performed on urease and hexadecylamine-urease films at the air-aqueous solution interface. It is demonstrated that although hexadecylamine does not form a stable monolayer on the pure aqueous surface, it does self-assemble into a stable, well-organized structure when spread on top of a urease film at the air-water interface. It is also likely that protein and hexadecylamine domains coexist at the interface. PMID:10233095

  11. Charge and pressure-tuned surface patterning of surfactant-encapsulated polyoxometalate complexes at the air-water interface.

    PubMed

    Xu, Miao; Li, Haolong; Zhang, Liying; Wang, Yizhan; Yuan, Yuan; Zhang, Jianming; Wu, Lixin

    2012-10-16

    In this paper, four organic-inorganic hybrid complexes were prepared using a cationic surfactant dimethyldioctadecylammonium (DODA) to replace the counter cations of four Keggin-type polyoxometalate (POM) clusters with gradually increased negative charges, PW(12)O(40)(3-), SiW(12)O(40)(4-), BW(12)O(40)(5-), and CoW(12)O(40)(6-). The formed surfactant-encapsulated POM (SEP) complexes showed typical amphiphilic properties and can be spread onto the air-water interface to form Langmuir monolayers. The interfacial behavior of the SEP monolayer films was systemically studied by multiple in situ and ex situ characterization methods including Brewster angle microscopy (BAM), atomic force microscopy (AFM), reflection-absorption infrared (RAIR), and X-ray photoelectron spectroscopy (XPS). We found that the increasing alkyl chain density of SEPs leads to an enhanced stability and a higher collapse pressure of SEP Langmuir monolayers. Moreover, a second layer evolved as patterns from the initial monolayers of all the SEPs, when the surface pressures approached the collapse values. The rational combination of alkyl chain density and surface pressure can precisely control the size and the morphology of SEP patterns transforming from disk-like to leaf-like structures on a micrometer scale. The pattern formation was demonstrated to be driven by the self-optimized surface energy of SEP monolayers. This finding can direct a new strategy for the fabrication of POM-hybrid films with controllable patterns, which should be instructive for designing POM-based thin film devices. PMID:22991980

  12. Liquid Surface X-ray Studies of Gold Nanoparticle-Phospholipid Films at the Air/Water Interface.

    PubMed

    You, Siheng Sean; Heffern, Charles T R; Dai, Yeling; Meron, Mati; Henderson, J Michael; Bu, Wei; Xie, Wenyi; Lee, Ka Yee C; Lin, Binhua

    2016-09-01

    Amphiphilic phospholipids and nanoparticles functionalized with hydrophobic capping ligands have been extensively investigated for their capacity to self-assemble into Langmuir monolayers at the air/water interface. However, understanding of composite films consisting of both nanoparticles and phospholipids, and by extension, the complex interactions arising between nanomaterials and biological membranes, remains limited. In this work, dodecanethiol-capped gold nanoparticles (Au-NPs) with an average core diameter of 6 nm were incorporated into 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) monolayers with surface densities ranging from 0.1 to 20% area coverage at a surface pressure of 30 mN/m. High resolution liquid surface X-ray scattering studies revealed a phase separation of the DPPC and Au-NP components of the composite film, as confirmed with atomic force microscopy after the film was transferred to a substrate. At low Au-NP content, the structural organization of the phase-separated film is best described as a DPPC film containing isolated islands of Au-NPs. However, increasing the Au-NP content beyond 5% area coverage transforms the structural organization of the composite film to a long-range interconnected network of Au-NP strands surrounding small seas of DPPC, where the density of the Au-NP network increases with increasing Au-NP content. The observed phase separation and structural organization of the phospholipid and nanoparticle components in these Langmuir monolayers are useful for understanding interactions of nanoparticles with biological membranes. PMID:27459364

  13. Nanostructure of Poly(N-isopropylacrylamide) Brush at the Air/Water Interface and Its Responsivity to Temperature and Salt.

    PubMed

    Matsuoka, Hideki; Uda, Kyohei

    2016-08-23

    Nanostructure and transition of the poly(N-isopropylacrylamide (PNIPAm) brush at the air/water interface were investigated by π-A isotherm and X-ray reflectivity, and an interesting behavior was observed with the change in temperature and salt. The polymer monolayer of poly(n-butyl acrylate)(PnBA)-b-PNIPAm on the water surface showed a transition between carpet-only/carpet+brush structures as a function of brush density, which was controlled by compression/expansion, as was the case for ionic brush systems. The brush stretching factor was about 50%, which was slightly less than that for a strongly ionic brush. The number of water molecules inside the brush layer was estimated to be 11-13 per repeating unit of PNIPAm chain. This value is very close to the number of hydrated water molecules reported, which means that all the water molecules inside the brush layer were hydrated water. With elevating temperature, the PNIPAm brush shrank, and the number of water molecules in the brush layer was reduced to 3. These observations certainly indicated a dehydration process. Interestingly, a part of the PNIAPm chain formed a "hydrophobic PNIPAm layer" on the carpet layer under the PnBA hydrophobic layer. A similar transition was observed also by the addition of salt to the water subphase. Although the formation of "hydrophobic PNIPAm layer" was not observed in this case, shrinking of the brush was observed with increasing salt concentration, and finally it became a carpet-only structure, which contained no water molecules. This salt effect was found to be ion specific, and its effectiveness was in the order of F(-) > Cl(-) > Br(-), which is in agreement with the Hofmeister series. PMID:27467013

  14. Charge and pressure-tuned surface patterning of surfactant-encapsulated polyoxometalate complexes at the air-water interface.

    PubMed

    Xu, Miao; Li, Haolong; Zhang, Liying; Wang, Yizhan; Yuan, Yuan; Zhang, Jianming; Wu, Lixin

    2012-10-16

    In this paper, four organic-inorganic hybrid complexes were prepared using a cationic surfactant dimethyldioctadecylammonium (DODA) to replace the counter cations of four Keggin-type polyoxometalate (POM) clusters with gradually increased negative charges, PW(12)O(40)(3-), SiW(12)O(40)(4-), BW(12)O(40)(5-), and CoW(12)O(40)(6-). The formed surfactant-encapsulated POM (SEP) complexes showed typical amphiphilic properties and can be spread onto the air-water interface to form Langmuir monolayers. The interfacial behavior of the SEP monolayer films was systemically studied by multiple in situ and ex situ characterization methods including Brewster angle microscopy (BAM), atomic force microscopy (AFM), reflection-absorption infrared (RAIR), and X-ray photoelectron spectroscopy (XPS). We found that the increasing alkyl chain density of SEPs leads to an enhanced stability and a higher collapse pressure of SEP Langmuir monolayers. Moreover, a second layer evolved as patterns from the initial monolayers of all the SEPs, when the surface pressures approached the collapse values. The rational combination of alkyl chain density and surface pressure can precisely control the size and the morphology of SEP patterns transforming from disk-like to leaf-like structures on a micrometer scale. The pattern formation was demonstrated to be driven by the self-optimized surface energy of SEP monolayers. This finding can direct a new strategy for the fabrication of POM-hybrid films with controllable patterns, which should be instructive for designing POM-based thin film devices.

  15. Interaction of N-myristoylethanolamine with cholesterol investigated in a Langmuir film at the air-water interface.

    PubMed

    Kamlekar, Ravi Kanth; Chandra, M Sharath; Radhakrishnan, T P; Swamy, Musti J

    2009-01-01

    The dramatic increase in the content of N-acylethanolamines (NAEs) having different acyl chains in various tissues when subjected to stress has resulted in significant interest in investigations on these molecules. Previous studies suggested that N-myristoylethanolamine (NMEA) and cholesterol interact to form a 1:1 (mol/mol) complex. In studies reported here, pressure-area isotherms of Langmuir films at the air-water interface have shown that at low fractions of cholesterol, the average area per molecule is lower than that predicted for ideal mixing, whereas at high cholesterol content the observed molecular area is higher, with a cross-over point at the equimolar composition. A plausible model that can explain these observations is the following: addition of small amounts of cholesterol to NMEA results in a reorientation of the NMEA molecules from the tilted disposition in the crystalline state to the vertical and stabilization of the intermolecular interactions, leading to the formation of a compact monolayer film, whereas at the other end of the composition diagram, addition of small amounts of NMEA to cholesterol leads to a tilting of the cholesterol molecules resulting in an increase in the average area per molecule. In Brewster angle microscopy experiments, a stable and bright homogeneous condensed phase was observed at a relatively low applied pressure of 2 mN.m(-1) for the NMEA:Chol. (1:1, mol/mol) mixture, whereas all other samples required significantly higher pressures (>10 mN.m(-1)) to form a homogeneous condensed phase. These observations are consistent with the formation of a 1:1 stoichiometric complex between NMEA and cholesterol and suggest that increase in the content of NAEs under stress may modulate the composition and dynamics of lipid rafts in biological membranes, resulting in alterations in signaling events involving them, which may be relevant to the putative cytoprotective and stress-combating ability of NAEs.

  16. The interaction of eugenol with cell membrane models at the air-water interface is modulated by the lipid monolayer composition.

    PubMed

    Gonçalves, Giulia E G; de Souza, Fernanda S; Lago, João Henrique G; Caseli, Luciano

    2015-12-01

    Eugenol, a natural phenylpropanoid derivative with possible action in biological surfaces as microbicide, anesthetic and antioxidant, was incorporated in lipid monolayers of selected lipids at the air-water interface, representing cell membrane models. Interaction of eugenol with the lipids dipalmitoylphosphatidylcholine (DPPC), dioctadecyldimethylammonium bromide (DODAB), and dipalmitoylphosphatidylserine (DPPS) could be inferred by means of surface pressure-area isotherms and Polarization-Modulation Reflection-Absorption Spectroscopy. The interaction showed different effects on the different lipids. A higher monolayer expansion was observed for DPPS and DODAB, while more significant effects on the polar groups of the lipids were observed for DPPS and DPPC. These results pointed to the fact that the interaction of eugenol with lipid monolayers at the air-water interface is modulated by the lipid composition, which may be important to comprehend at the molecular level the interaction of this drug with biological surfaces.

  17. Toward a unified picture of the water self-ions at the air-water interface: a density functional theory perspective.

    PubMed

    Baer, Marcel D; Kuo, I-Feng W; Tobias, Douglas J; Mundy, Christopher J

    2014-07-17

    The propensities of the water self-ions, H3O(+) and OH(-), for the air-water interface have implications for interfacial acid-base chemistry. Despite numerous experimental and computational studies, no consensus has been reached on the question of whether or not H3O(+) and/or OH(-) prefer to be at the water surface or in the bulk. Here we report a molecular dynamics simulation study of the bulk vs interfacial behavior of H3O(+) and OH(-) that employs forces derived from density functional theory with a generalized gradient approximation exchange-correlation functional (specifically, BLYP) and empirical dispersion corrections. We computed the potential of mean force (PMF) for H3O(+) as a function of the position of the ion in the vicinity of an air-water interface. The PMF suggests that H3O(+) has equal propensity for the interface and the bulk. We compare the PMF for H3O(+) to our previously computed PMF for OH(-) adsorption, which contains a shallow minimum at the interface, and we explore how differences in solvation of each ion at the interface vs in the bulk are connected with interfacial propensity. We find that the solvation shell of H3O(+) is only slightly dependent on its position in the water slab, while OH(-) partially desolvates as it approaches the interface, and we examine how this difference in solvation behavior is manifested in the electronic structure and chemistry of the two ions.

  18. Molecular dynamics shows that ion pairing and counterion anchoring control the properties of triflate micelles: a comparison with triflate at the air/water interface.

    PubMed

    Lima, Filipe S; Chaimovich, Hernan; Cuccovia, Iolanda M; Horinek, Dominik

    2014-02-11

    Micellar properties of dodecyltrimethylammonium triflate (DTA-triflate, DTATf) are very different from those of DTA-bromide (DTAB). DTATf aggregates show high aggregation numbers (Nagg), low degree of counterion dissociation (α), disk-like shape, high packing, ordering, and low hydration. These micellar properties and the low surface tension of NaTf aqueous solutions point to a high affinity of Tf(-) to the micellar and air/water interfaces. Although the micellar properties of DTATf are well defined, the source of the Tf(-) effect upon the DTA aggregates is unclear. Molecular dynamics (MD) simulations of Tf(-) (and Br(-)) at the air/water interface and as counterion of a DTA aggregate were performed to clarify the nature of Tf(-) preferences for these interfaces. The effect of NaTf or NaBr on surface tension calculated from MD simulations agreed with the reported experimental values. From the MD simulations a high affinity of Tf(-) toward the interface, which occurred in a specific orientation, was calculated. The micellar properties calculated from the MD simulations for DTATf and DTAB were consistent with experimental data: in MD simulations, the DTATf aggregate was more ordered, packed, and dehydrated than the DTAB aggregate. The Tf(-)/alkyltrimethylammonium interaction energies, calculated from the MD simulations, suggested ion pair formation at the micellar interface, stabilized by the preferential orientation of the adsorbed Tf(-) at the micellar interface.

  19. Intraday evaporation and heat fluxes variation at air-water interface of extremely shallow lakes in Chilean Andean Plateau

    NASA Astrophysics Data System (ADS)

    Vergara, Jaime; de la Fuente, Alberto

    2016-04-01

    Salars are landscapes formed by evapo-concentration of salts that usually have extremely shallow terminal lagoons (de la Fuente & Niño, 2010). They are located in the altiplanic region of the Andes Mountains of Chile, Argentina, Bolivia and Peru, and they sustain highly vulnerable and isolated ecosystems in the Andean Desert. These ecosystems are sustained by benthic primary production, which is directly linked to mass, heat and momentum transfer between the water column and the atmosphere (de la Fuente, 2014). Despite the importance of these transport processes across the air-water interface, there are few studies describing their intraday variation and how they are influenced by the stability of the atmospheric boundary layer in the altiplano. The main objective of this work is to analyze the intraday vertical transport variation of water vapor, temperature and momentum between the atmosphere and a shallow water body on Salar del Huasco located in northern Chile (20°19'40"S, 68°51'25"W). To achieve this goal, we measured atmospheric and water variables in a campaign realized on late October 2015, using high frequency meteorological instruments (a sonic anemometer with an incorporated infrared gas analyzer, and a standard meteorological station) and water sensors. From these data, we characterize the intraday variation of water vapor, temperature and momentum fluxes, we quantify the influence of the atmospheric boundary layer stability on them, and we estimate transfer coefficients associated to latent heat, sensible heat, hydrodynamic drag and vertical transport of water vapor. As first results, we found that latent and sensible heat fluxes are highly influenced by wind speed rather buoyancy, and we can identify four intraday intervals with different thermo-hydrodynamic features: (1) cooling under stable condition with wind speed near 0 from midnight until sunrise; (2) free convection with nearly no wind speed under unstable condition from sunrise until midday

  20. Partially Hydrated Electrons at the Air/Water Interface Observed by UV-Excited Time-Resolved Heterodyne-Detected Vibrational Sum Frequency Generation Spectroscopy.

    PubMed

    Matsuzaki, Korenobu; Kusaka, Ryoji; Nihonyanagi, Satoshi; Yamaguchi, Shoichi; Nagata, Takashi; Tahara, Tahei

    2016-06-22

    Hydrated electrons are the most fundamental anion species, consisting only of electrons and surrounding water molecules. Although hydrated electrons have been extensively studied in the bulk aqueous solutions, even their existence is still controversial at the water surface. Here, we report the observation and characterization of hydrated electrons at the air/water interface using new time-resolved interface-selective nonlinear vibrational spectroscopy. With the generation of electrons at the air/water interface by ultraviolet photoirradiation, we observed the appearance of a strong transient band in the OH stretch region by heterodyne-detected vibrational sum-frequency generation. Through the comparison with the time-resolved spectra at the air/indole solution interface, the transient band was assigned to the vibration of water molecules that solvate electrons at the interface. The analysis of the frequency and decay of the observed transient band indicated that the electrons are only partially hydrated at the water surface, and that they escape into the bulk within 100 ps. PMID:27281547

  1. In situ studies of metal coordinations and molecular orientations in monolayers of amino-acid-derived Schiff bases at the air-water interface.

    PubMed

    Liu, Huijin; Zheng, Haifu; Miao, Wangen; Du, Xuezhong

    2009-03-01

    The surface behaviors of monolayers of amino-acid-derived Schiff bases, namely, 4-(4-(hexadecyloxy)benzylideneamino)benzoic acid (HBA), at the air-water interface on pure water and ion-containing subphases (Cu2+, Ca2+, and Ba2+) have been clarified by a combination of surface pressure-area isotherms and surface plasmon resonance (SPR) technique, and the metal coordinations and molecular orientations in the monolayers have been investigated using in situ infrared reflection absorption spectroscopy (IRRAS). The presence of metal ions gives rise to condensation of the monolayers (Cu2+, pH 6.1; Ca2+, pH 11; Ba2+, pH 10), even leading to the formation of three-dimensional structures of the compressed monolayer in the case of Ba2+ (pH 12). The metal coordinations with the carboxyl groups at the interface depend on the type of metal ions and pH of the aqueous subphase. The orientations of the aromatic Schiff base segments with surface pressure are elaborately described. The spectral behaviors of the Schiff base segments with incidence angle in the case of Ba2+ (pH 12) have so far presented an excellent example for the selection rule of IRRAS at the air-water interface for p-polarization with vibrational transition moments perpendicular to the water surface. The chain orientations in the monolayers are quantitatively determined on the assumption that the thicknesses of the HBA monolayers at the air-water interface are composed of the sublayers of alkyl chains and Schiff base segments. PMID:19437705

  2. Experimentally probing the libration of interfacial water: the rotational potential of water is stiffer at the air/water interface than in bulk liquid.

    PubMed

    Tong, Yujin; Kampfrath, Tobias; Campen, R Kramer

    2016-07-21

    Most properties of liquid water are determined by its hydrogen-bond network. Because forming an aqueous interface requires termination of this network, one might expect the molecular level properties of interfacial water to markedly differ from water in bulk. Intriguingly, much prior experimental and theoretical work has found that, from the perspective of their time-averaged structure and picosecond structural dynamics, hydrogen-bonded OH groups at an air/water interface behave the same as hydrogen-bonded OH groups in bulk liquid water. Here we report the first experimental observation of interfacial water's libration (i.e. frustrated rotation) using the laser-based technique vibrational sum frequency spectroscopy. We find this mode has a frequency of 834 cm(-1), ≈165 cm(-1) higher than in bulk liquid water at the same temperature and similar to bulk ice. Because libration frequency is proportional to the stiffness of water's rotational potential, this increase suggests that one effect of terminating bulk water's hydrogen bonding network at the air/water interface is retarding rotation of water around intact hydrogen bonds. Because in bulk liquid water the libration plays a key role in stabilizing reaction intermediates and dissipating excess vibrational energy, we expect the ability to probe this mode in interfacial water to open new perspectives on the kinetics of heterogeneous reactions at aqueous interfaces. PMID:27339861

  3. Determination and comparison of how the chain number and chain length of a lipid affects its interactions with a phospholipid at an air/water interface.

    PubMed

    Ngyugen, Hang; McNamee, Cathy E

    2014-06-01

    We determined how the number of chains in a lipid and its chain length affects its interactions with a phospholipid model membrane, and whether the number of chains or the chain length of lipids affects their interactions with the phospholipids more. This was achieved by using a Langmuir trough and a fluorescence microscope to study the interactions of mono-, di-, and triglycerides with a phospholipid monolayer at an air/water interface. The effect of the number of chains in a lipid on its interactions with phospholipids at air/water interfaces was shown by surface pressure-area per molecule isotherms and their thermodynamic analysis to worsen as the number of alkyl chains was increased to be greater than one. An increase in the packing density decreased the mixing ability of the lipids with the phospholipids, resulting in the formation of aggregates in the mixed monolayer. The aggregation was explained by the intermolecular hydrophobic and van der Waals attractions between the lipid molecules. Fluorescence microscopy revealed partial mixing without aggregation for monoglycerides, but the presence of lipid aggregation for diglycerides and triglycerides. The effect of decreasing the chain length of triglycerides from a long chain to a medium chain caused the interactions of the lipids with the phospholipid molecules at the air/water interface to significantly improve. Decreasing the chain length of monoglycerides from a long chain to a medium chain worsened their interaction with the phospholipid molecules. The effect of decreasing the triglyceride chain length on their interactions with phospholipids was much greater than the effect of decreasing the number of alkyl chains in the lipid.

  4. Mechanical properties of protein adsorption layers at the air/water and oil/water interface: a comparison in light of the thermodynamical stability of proteins.

    PubMed

    Mitropoulos, Varvara; Mütze, Annekathrin; Fischer, Peter

    2014-04-01

    Over the last decades numerous studies on the interfacial rheological response of protein adsorption layers have been published. The comparison of these studies and the retrieval of a common parameter to compare protein interfacial activity are hampered by the fact that different boundary conditions (e.g. physico-chemical, instrumental, interfacial) were used. In the present work we review previous studies and attempt a unifying approach for the comparison between bulk protein properties and their adsorption films. Among many common food grade proteins we chose bovine serum albumin, β-lactoglobulin and lysozyme for their difference in thermodynamic stability and studied their adsorption at the air/water and limonene/water interface. In order to achieve this we have i) systematically analyzed protein adsorption kinetics in terms of surface pressure rise using a drop profile analysis tensiometer and ii) we addressed the interfacial layer properties under shear stress using an interfacial shear rheometer under the same experimental conditions. We could show that thermodynamically less stable proteins adsorb generally faster and yield films with higher shear rheological properties at air/water interface. The same proteins showed an analog behavior when adsorbing at the limonene/water interface but at slower rates. PMID:24332621

  5. Mechanical properties of protein adsorption layers at the air/water and oil/water interface: a comparison in light of the thermodynamical stability of proteins.

    PubMed

    Mitropoulos, Varvara; Mütze, Annekathrin; Fischer, Peter

    2014-04-01

    Over the last decades numerous studies on the interfacial rheological response of protein adsorption layers have been published. The comparison of these studies and the retrieval of a common parameter to compare protein interfacial activity are hampered by the fact that different boundary conditions (e.g. physico-chemical, instrumental, interfacial) were used. In the present work we review previous studies and attempt a unifying approach for the comparison between bulk protein properties and their adsorption films. Among many common food grade proteins we chose bovine serum albumin, β-lactoglobulin and lysozyme for their difference in thermodynamic stability and studied their adsorption at the air/water and limonene/water interface. In order to achieve this we have i) systematically analyzed protein adsorption kinetics in terms of surface pressure rise using a drop profile analysis tensiometer and ii) we addressed the interfacial layer properties under shear stress using an interfacial shear rheometer under the same experimental conditions. We could show that thermodynamically less stable proteins adsorb generally faster and yield films with higher shear rheological properties at air/water interface. The same proteins showed an analog behavior when adsorbing at the limonene/water interface but at slower rates.

  6. Coadsorption of carbofuran and lead at the air/water interface. Possible occurrence of non-volatile pollutant cotransfer to the atmosphere.

    PubMed

    Acharid, Abdelhaq; Quentel, François; Elléouet, Catherine; Olier, René; Privat, Mireille

    2006-02-01

    The weak solubility of carbofuran allows adsorption at the air/water interface. Carbofuran-rich layers can then induce the coadsorption of metallic salts such as lead nitrate; on the other hand, when carbofuran is missing, no adsorption of this salt takes place. This phenomenon was quantitatively studied through surface tension measurements under concentration conditions close to the environmental ones. Heavy metal salt adsorbed about ten times more than carbofuran. Evidence was then provided that the simultaneous presence of both pollutants in water favours their adsorption and passing from water to the atmosphere through mechanisms such as bubbling.

  7. Photophysical behavior in spread monolayers. Dansyl fluorescence as a probe for polarity at the air-water interface. [N-(5-(dimethylamino)naphthalene-1-sulfonyl)dihexadecylamine

    SciTech Connect

    Grieser, F.; Thistlethwaite, P.; Urquhart, R.; Patterson, L.K.

    1987-09-24

    The emission spectrum of N-(5-(dimethylamino)naphthalene-1-sulfonyl)dihexadecylamine (dansyldihexadecylamine) in monolayers at the air-water interface has been studied. In some cases sudden shifts in the dansyl emission can be correlated with particular features of the surface pressure-area isotherms. These spectral shifts can be explained in terms of a change in the conformation of the head group on the surface and with aggregation of the dansyldihexadecylamine. In other cases the dansyl emission shows a blue shift with increasing compression that can be associated with reduced head-group hydration.

  8. Gas exchange in wetlands with emergent vegetation: The effects of wind and thermal convection at the air-water interface

    NASA Astrophysics Data System (ADS)

    Poindexter, Cristina M.; Variano, Evan A.

    2013-07-01

    Methane, carbon dioxide, and oxygen are exchanged between wetlands and the atmosphere through multiple pathways. One of these pathways, the hydrodynamic transport of dissolved gas through the surface water, is often underestimated in importance. We constructed a model wetland in the laboratory with artificial emergent plants to investigate the mechanisms and magnitude of this transport. We measured gas transfer velocities, which characterize the near-surface stirring driving air-water gas transfer, while varying two stirring processes important to gas exchange in other aquatic environments: wind and thermal convection. To isolate the effects of thermal convection, we identified a semiempirical model for the gas transfer velocity as a function of surface heat loss. The laboratory results indicate that thermal convection will be the dominant mechanism of air-water gas exchange in marshes with emergent vegetation. Thermal convection yielded peak gas transfer velocities of 1 cm h-1. Because of the sheltering of the water surface by emergent vegetation, gas transfer velocities for wind-driven stirring alone are likely to exceed this value only in extreme cases.

  9. Effects of cholesterol component on molecular interactions between paclitaxel and phospholipid within the lipid monolayer at the air-water interface.

    PubMed

    Zhao, Lingyun; Feng, Si-Shen

    2006-08-01

    Cholesterol is a main component of the cell membrane and could have significant effects on drug-cell membrane interactions and thus the therapeutic efficacy of the drug. It also plays an important role in liposomal formulation of drugs for controlled and targeted delivery. In this research, Langmuir film technique, atomic force microscopy (AFM) and Fourier transform infrared spectroscopy (FTIR) are employed for a systematic investigation on the effects of cholesterol component on the molecular interactions between a prototype antineoplastic drug (paclitaxel) and 1,2-dipalmitoyl-sn-glycerol-3-phosphocholine (DPPC) within the cell membrane by using the lipid monolayer at the air-water interface as a model of the lipid bilayer membrane and the biological cell membrane. Analysis of the measured surface pressure (pi) versus molecular area (a) isotherms of the mixed DPPC/paclitaxel/cholesterol monolayers at various molar ratios shows that DPPC, paclitaxel and cholesterol can form a non-ideal miscible system at the air-water interface. Cholesterol enhances the intermolecular forces between paclitaxel and DPPC, produces an area-condensing effect and thus makes the mixed monolayer more stable. Investigation of paclitaxel penetration into the mixed DPPC/cholesterol monolayer shows that the existence of cholesterol in the DPPC monolayer can considerably restrict the drug penetration into the monolayer, which may have clinical significance for diseases of high cholesterol. FTIR and AFM investigation on the mixed monolayer deposited on solid surface confirmed the obtained results.

  10. Phase diagram, design of monolayer binary colloidal crystals, and their fabrication based on ethanol-assisted self-assembly at the air/water interface.

    PubMed

    Dai, Zhengfei; Li, Yue; Duan, Guotao; Jia, Lichao; Cai, Weiping

    2012-08-28

    Flexible structural design and accurate controlled fabrication with structural tunability according to need for binary or multicomponent colloidal crystals have been expected. However, it is still a challenge. In this work, the phase diagram of monolayer binary colloidal crystals (bCCs) is established on the assumption that both large and small polystyrene (PS) colloidal spheres can stay at the air/water interface, and the range diagram for the size ratio and number ratio of small to large colloidal spheres is presented. From this phase diagram, combining the range diagram, we can design and relatively accurately control fabrication of the bCCs with specific structures (or patterns) according to need, including single or mixed patterns with the given relative content. Further, a simple and facile approach is presented to fabricate large-area (more than 10 cm(2)) monolayer bCCs without any surfactants, using differently sized PS spheres, based on ethanol-assisted self-assembly at the air/water interface. bCCs with different patterns and stoichiometries are thus designed from the established phase diagram and then successfully fabricated based on the volume ratios (V(S/L)) of the small to large PS suspensions using the presented colloidal self-assembling method. Interestingly, these monolayer bCCs can be transferred to any desired substrates using water as the medium. This study allows us to design desired patterns of monolayer bCCs and to more accurately control their structures with the used V(S/L).

  11. A semi-analytical calculation of the electrostatic pair interaction between nonuniformly charged colloidal spheres at an air-water interface

    NASA Astrophysics Data System (ADS)

    Lian, Zengju

    2016-07-01

    We study the electrostatic pair interaction between two nonuniformly like-charged colloidal spheres trapped in an air-water interface. Under the linear Poisson-Boltzmann approximation, a general form of the electrostatic potential for the system is shown in terms of multipole expansions. After combining the translation-rotation transform of the coordinates with the numerical multipoint collection, we give a semi-analytical result of the electrostatic pair interaction between the colloids. The pair interaction changes quantitatively or even qualitatively with different distributions of the surface charges on the particles. Because of the anisotropic distribution of the surface charge and the asymmetric dielectric medium, the dipole moment of the ion cloud associating with the particle orients diagonally to the air-water interface with an angle α. When the angle is large, the colloids interact repulsively, while they attract each other when the angle is small. The attractive colloids may be "Janus-like" charged and be arranged with some specific configurations. Whatever the repulsions or the attractions, they all decay asymptotically ∝1/d3 (d is the center-center distance of the particles) which is consistent with our general acknowledge. The calculation results also provide an insight of the effect of the ion concentration, particle size, and the total charge of the particle on the pair interaction between the particles.

  12. A semi-analytical calculation of the electrostatic pair interaction between nonuniformly charged colloidal spheres at an air-water interface.

    PubMed

    Lian, Zengju

    2016-07-01

    We study the electrostatic pair interaction between two nonuniformly like-charged colloidal spheres trapped in an air-water interface. Under the linear Poisson-Boltzmann approximation, a general form of the electrostatic potential for the system is shown in terms of multipole expansions. After combining the translation-rotation transform of the coordinates with the numerical multipoint collection, we give a semi-analytical result of the electrostatic pair interaction between the colloids. The pair interaction changes quantitatively or even qualitatively with different distributions of the surface charges on the particles. Because of the anisotropic distribution of the surface charge and the asymmetric dielectric medium, the dipole moment of the ion cloud associating with the particle orients diagonally to the air-water interface with an angle α. When the angle is large, the colloids interact repulsively, while they attract each other when the angle is small. The attractive colloids may be "Janus-like" charged and be arranged with some specific configurations. Whatever the repulsions or the attractions, they all decay asymptotically ∝1/d(3) (d is the center-center distance of the particles) which is consistent with our general acknowledge. The calculation results also provide an insight of the effect of the ion concentration, particle size, and the total charge of the particle on the pair interaction between the particles. PMID:27394119

  13. Molecular assemblies of 4-(hexadecyloxy)-n-(pyridinylmethylene)anilines at the air-water interface and Cu(II)-promoted vesicle formation via metal coordination.

    PubMed

    Wang, Haibo; Miao, Wangen; Liu, Huijin; Zhang, Xianfeng; Du, Xuezhong

    2010-09-01

    The molecular assemblies of 4-(hexadecyloxy)-N-(pyridinylmethylene)anilines (HPA) at the air-water interface on pure water and aqueous Cu(II) subphases have been investigated using in situ infrared reflection absorption spectroscopy (IRRAS). The Schiff base units were oriented with their long axes almost perpendicular to the water surface, and both imine and pyridinyl nitrogen atoms of the Schiff base units were coordinated to Cu(II) ions together with their geometrical conversions. The alkyl chains in the monolayers were quantitatively determined on the assumption that the HPA monolayers at the air-water interface were composed of sublayers of alkyl chains and Schiff base units, and the chain orientation angle on pure water was 30 +/- 2 degrees and increased to 37 +/- 2 degrees on the aqueous Cu(II) subphase. The HPA amphiphiles could not be dispersed in pure water but could self-organize into vesicles with metal-coordinated headgroups and interdigitated-packed alkyl chains in the presence of Cu(II) ions in aqueous solution. Transmission electron microscopy (TEM), differential scanning calorimetry (DSC), UV-vis spectroscopy, and small-angle X-ray diffraction (XRD) were used to investigate the aggregate structures and specific properties of the coordinated vesicles. PMID:20698514

  14. Reaction of a phospholipid monolayer with gas-phase ozone at the air-water interface: measurement of surface excess and surface pressure in real time.

    PubMed

    Thompson, Katherine C; Rennie, Adrian R; King, Martin D; Hardman, Samantha J O; Lucas, Claire O M; Pfrang, Christian; Hughes, Brian R; Hughes, Arwel V

    2010-11-16

    The reaction between gas-phase ozone and monolayers of the unsaturated lipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, POPC, on aqueous solutions has been studied in real time using neutron reflection and surface pressure measurements. The reaction between ozone and lung surfactant, which contains POPC, leads to decreased pulmonary function, but little is known about the changes that occur to the interfacial material as a result of oxidation. The results reveal that the initial reaction of ozone with POPC leads to a rapid increase in surface pressure followed by a slow decrease to very low values. The neutron reflection measurements, performed on an isotopologue of POPC with a selectively deuterated palmitoyl strand, reveal that the reaction leads to loss of this strand from the air-water interface, suggesting either solubilization of the product lipid or degradation of the palmitoyl strand by a reactive species. Reactions of (1)H-POPC on D(2)O reveal that the headgroup region of the lipids in aqueous solution is not dramatically perturbed by the reaction of POPC monolayers with ozone supporting degradation of the palmitoyl strand rather than solubilization. The results are consistent with the reaction of ozone with the oleoyl strand of POPC at the air-water interface leading to the formation of OH radicals. The highly reactive OH radicals produced can then go on to react with the saturated palmitoyl strands leading to the formation of oxidized lipids with shorter alkyl tails.

  15. Morphological and structural characteristics of diazo dyes at the air-water interface: in situ Brewster angle microscopy and polarized UV/vis analysis.

    PubMed

    Yamaki, Sahori B; Andrade, Acácio A; Mendonça, Cléber R; Oliveira, Osvaldo N; Atvars, Teresa D Z

    2005-03-15

    A morphological analysis is presented for Langmuir films of the diazo dyes Sudan 4 (S4), Sudan 3 (S3), and Sudan red (SR), using Brewster angle microscopy. Stable nonmonomolecular structures are formed at the air-water interface denoted as a plateau in the pressure-area isotherms. Monolayer domains are evident by the contrastless image even before the pressure onset, which grow in size until it reached a condensed monolayer. This behavior resembles that of Langmuir films from simple aromatic fatty acids. Films from all the azo dyes display similar features, according to the surface potential isotherms and in situ polarized UV/vis spectroscopy except for the larger area per molecule occupied by S4 and SR. This is attributed to the presence of CH(3) groups that cause steric hindrance modifying the organization of diazo dye molecules at the air-water interface. UV/vis polarized absorption spectroscopy showed preferential orientation of S4 and S3 on the water surface, while SR molecules lie isotropically. For these three diazo dyes, film absorption was negligible at very large areas per molecule, becoming nonzero only at a critical area coinciding with the onset of surface potential. The critical area is ascribed to the formation of a H-bonded network between water molecules and diazo dye headgroups. PMID:15721920

  16. Mechanism of Action of Thymol on Cell Membranes Investigated through Lipid Langmuir Monolayers at the Air-Water Interface and Molecular Simulation.

    PubMed

    Ferreira, João Victor N; Capello, Tabata M; Siqueira, Leonardo J A; Lago, João Henrique G; Caseli, Luciano

    2016-04-01

    A major challenge in the design of biocidal drugs is to identify compounds with potential action on microorganisms and to understand at the molecular level their mechanism of action. In this study, thymol, a monoterpenoid found in the oil of leaves of Lippia sidoides with possible action in biological surfaces, was incorporated in lipid monolayers at the air-water interface that represented cell membrane models. The interaction of thymol with dipalmitoylphosphatidylcholine (DPPC) at the air-water interface was investigated by means of surface pressure-area isotherms, Brewster angle microscopy (BAM), polarization-modulation reflection-absorption spectroscopy (PM-IRRAS), and molecular dynamics simulation. Thymol expands DPPC monolayers, decreases their surface elasticity, and changes the morphology of the lipid monolayer, which evidence the incorporation of this compound in the lipid Langmuir film. Such incorporation could be corroborated by PM-IRRAS since some specific bands for DPPC were changed upon thymol incorporation. Furthermore, potential of mean force obtained by molecular dynamics simulations indicates that the most stable position of the drug along the lipid film is near the hydrophobic regions of DPPC. These results may be useful to understand the interaction between thymol and cell membranes during biochemical phenomena, which may be associated with its pharmaceutical properties at the molecular level.

  17. Effects of the conjugation of whey proteins with gellan polysaccharides on surfactant-induced competitive displacement from the air-water interface.

    PubMed

    Cai, B; Ikeda, S

    2016-08-01

    Whey proteins can be used to stabilize foams and emulsions against coalescence because of their ability to form viscoelastic films at the interface that resist film rupture on collision between colloidal particles. However, whey proteins are competitively displaced from the interface if small-molecule surfactants are added, leading to destabilization of the entire system. This is because surfactants are more effective in molecular packing at the interface, and they lower interfacial tension to a greater degree than whey proteins do, but their interfacial films are poor in viscoelasticity. We hypothesized that whey proteins would become more resistant to surfactant-induced competitive displacement if they were conjugated with network-forming polysaccharides. The protein moiety of the conjugate would be expected to enable its adsorption to the interface, and the polysaccharide moiety would be expected to form self-assembled networks, strengthening the interfacial film as a whole. In this study, whey proteins were conjugated with gellan polysaccharides using the Maillard reaction. Atomic force microscopy images of interfacial films formed by the whey protein-gellan conjugate at the air-water interface and transferred onto mica sheets using the Langmuir-Blodgett method revealed that gellan did form self-assembled networks at the interface and that interfacial films also contained a large number of unconjugated whey protein molecules. Following the addition of a small-molecule surfactant (Tween 20) to the sub-phase, surface pressure increased, indicating spontaneous adsorption of surfactants to the interface. Atomic force microscopy images showed decreases in interfacial area coverage by whey proteins as surface pressure increased. At a given surface pressure, the interfacial area coverage by whey protein-gellan conjugates was greater than coverage by unconjugated whey proteins, confirming that whey proteins became more resistant to surfactant-induced displacement after

  18. Adsorption at air-water and oil-water interfaces and self-assembly in aqueous solution of ethoxylated polysorbate nonionic surfactants.

    PubMed

    Penfold, Jeffrey; Thomas, Robert K; Li, Peixun X; Petkov, Jordan T; Tucker, Ian; Webster, John R P; Terry, Ann E

    2015-03-17

    The Tween nonionic surfactants are ethoxylated sorbitan esters, which have 20 ethylene oxide groups attached to the sorbitan headgroup and a single alkyl chain, lauryl, palmityl, stearyl, or oleyl. They are an important class of surfactants that are extensively used in emulsion and foam stabilization and in applications associated with foods, cosmetics and pharmaceuticals. A range of ethoxylated polysorbate surfactants, with differing degrees of ethoxylation from 3 to 50 ethylene oxide groups, have been synthesized and characterized by neutron reflection, small-angle neutron scattering, and surface tension. In conjunction with different alkyl chain groups, this provides the opportunity to modify their surface properties, their self-assembly in solution, and their interaction with macromolecules, such as proteins. Adsorption at the air-water and oil-water interfaces and solution self-assembly of the range of ethoxylated polysorbate surfactants synthesized are presented and discussed.

  19. Self-Assembly of Single-Sized and Binary Colloidal Particles at Air/Water Interface by Surface Confinement and Water Discharge.

    PubMed

    Lotito, Valeria; Zambelli, Tomaso

    2016-09-20

    We present an innovative apparatus allowing self-assembly at air/water interface in a smooth and reproducible way. The combination of water discharge and surface confinement of the area over which self-assembly takes place allows transfer of the assembled monolayer without any risk of damage to the colloidal crystal. As we demonstrate, the designed approach offers remarkable advantages in terms of cost and robustness compared to state-of-the art methods and is suitable for the fabrication of highly ordered monolayers even for more challenging assembly experiments such as transfer on rough substrates or assembly of binary colloids. Hence, our apparatus represents a significant headway toward high scale production of large area colloidal crystals. For the binary colloid assembly experiments, we also report the first experimental demonstration of a morphology based on the alternation of three and four small particles in the interstices between large particles. PMID:27574790

  20. Self-Assembly of Single-Sized and Binary Colloidal Particles at Air/Water Interface by Surface Confinement and Water Discharge.

    PubMed

    Lotito, Valeria; Zambelli, Tomaso

    2016-09-20

    We present an innovative apparatus allowing self-assembly at air/water interface in a smooth and reproducible way. The combination of water discharge and surface confinement of the area over which self-assembly takes place allows transfer of the assembled monolayer without any risk of damage to the colloidal crystal. As we demonstrate, the designed approach offers remarkable advantages in terms of cost and robustness compared to state-of-the art methods and is suitable for the fabrication of highly ordered monolayers even for more challenging assembly experiments such as transfer on rough substrates or assembly of binary colloids. Hence, our apparatus represents a significant headway toward high scale production of large area colloidal crystals. For the binary colloid assembly experiments, we also report the first experimental demonstration of a morphology based on the alternation of three and four small particles in the interstices between large particles.

  1. Self-assembly of diblock co-polymers at air-water interface: A microscopy and x-ray scattering study

    NASA Astrophysics Data System (ADS)

    Giri, R. P.; Mukhopadhyay, M. K.

    2016-05-01

    The spontaneous surface aggregation of diblock copolymer, containing polystyrene-polydimethylsiloxane or PS-PDMS, have been studied at air-water interface using Brewster's angle microscopy (BAM) and grazing incidence small angle x-ray scattering (GISAXS) technique. Pronounced differences in the molecular weight and solvent dependence of the size of aggregation on the water surface are observed. Structural characterization is done using atomic force microscopy (AFM) for a monolayer transferred to Si substrate. It shows that, individual polymer chains coalesce to form some disc like micelle aggregation on the Si surface which is also evident from the BAM image of the water floated monolayer. GISAXS study is also corroborating the same result.

  2. Molecular recognition of 7-(2-octadecyloxycarbonylethyl)guanine to cytidine at the air/water interface and LB film studied by Fourier transform infrared spectroscopy.

    PubMed

    Miao, Wangen; Luo, Xuzhong; Liang, Yingqiu

    2003-03-15

    Monolayer behavior of a nucleolipid amphiphile, 7-(2-octadecyloxycarbonylethyl)guanine (ODCG), on aqueous cytidine solution was investigated by means of surface-molecular area (pi-A) isotherms. It indicates that molecular recognition by hydrogen bonding is present between ODCG monolayer and the cytidine in subphase. The Fourier transform infrared (FTIR) transmission spectroscopic result indicates that the cytidine molecules in the subphase can be transferred onto solid substrates by Langmuir-Blodgett (LB) technique as a result of the formation of Watson-Crick base-pairing at the air/water interface. Investigation by rotating polarized FTIR transmission also suggests that the headgroup recognition of this amphiphile to the dissolved cytidine influence the orientation of the tailchains.

  3. Towards a unified picture of the water self-ions at the air-water interface: a density functional theory perspective

    SciTech Connect

    Baer, Marcel D.; Kuo, I-F W.; Tobias, Douglas J.; Mundy, Christopher J.

    2014-07-17

    The propensities of the water self ions, H3O+ and OH- , for the air-water interface has implications for interfacial acid-base chemistry. Despite numerous experimental and computational studies, no consensus has been reached on the question of whether or not H3O+ and/or OH- prefer to be at the water surface or in the bulk. Here we report a molecular dynamics simulation study of the bulk vs. interfacial behavior of H3O+ and OH- that employs forces derived from density functional theory with a generalized gradient approximation exchangecorrelation functional (specifically, BLYP) and empirical dispersion corrections. We computed the potential of mean force (PMF) for H3O+ as a function of the position of the ion in a 215-molecule water slab. The PMF is flat, suggesting that H3O+ has equal propensity for the air-water interface and the bulk. We compare the PMF for H3O+ to our previously computed PMF for OH- adsorption, which contains a shallow minimum at the interface, and we explore how differences in solvation of each ion at the interface vs. the bulk are connected with interfacial propensity. We find that the solvation shell of H3O+ is only slightly dependent on its position in the water slab, while OH- partially desolvates as it approaches the interface, and we examine how this difference in solvation behavior is manifested in the electronic structure and chemistry of the two ions. DJT was supported by National Science Foundation grant CHE-0909227. CJM was supported by the U.S. Department of Energy‘s (DOE) Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is operated for the Department of Energy by Battelle. The potential of mean force required resources of the Oak Ridge Leadership Computing Facility at the Oak Ridge National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DEAC05-00OR22725. The remaining simulations

  4. Reorientation of the ‘free OH’ group in the top-most layer of air/water interface of sodium fluoride aqueous solution probed with sum-frequency generation vibrational spectroscopy

    SciTech Connect

    Feng, Ran-Ran; Guo, Yuan; Wang, Hongfei

    2014-09-17

    Many experimental and theoretical studies have established the specific anion, as well as cation effects on the hydrogen-bond structures at the air/water interface of electrolyte solutions. However, the ion effects on the top-most layer of the air/water interface, which is signified by the non-hydrogen-bonded so-called ‘free O-H’ group, has not been discussed or studied. In this report, we present the measurement of changes of the orientational angle of the ‘free O-H’ group at the air/water interface of the sodium fluoride (NaF) solutions at different concentrations using the interface selective sum-frequency generation vibrational spectroscopy (SFG-VS) in the ssp and ppp polarizations. The polarization dependent SFG-VS results show that the average tilt angle of the ‘free O-H’ changes from about 35.3 degrees ± 0.5 degrees to 43.4 degrees ± 2.1degrees as the NaF concentration increase from 0 to 0.94M (nearly saturated). Such tilt angle change is around the axis of the other O-H group of the same water molecule at the top-most layer at the air/water interface that is hydrogen-bonded to the water molecules below the top-most layer. These results provide quantitative molecular details of the ion effects of the NaF salt on the structure of the water molecules at the top-most layer of the air/water interfacial, even though both the Na+ cation and the F- anion are believed to be among the most excluded ions from the air/water interface.

  5. Direct impact of nonequilibrium aggregates on the structure and morphology of Pdadmac/SDS layers at the air/water interface.

    PubMed

    Campbell, Richard A; Yanez Arteta, Marianna; Angus-Smyth, Anna; Nylander, Tommy; Noskov, Boris A; Varga, Imre

    2014-07-29

    We discuss different nonequilibrium mechanisms by which bulk aggregates directly modify, and can even control, the interfacial structure and morphology of an oppositely charged polyelectrolyte/surfactant (P/S) mixture. Samples are categorized at the air/water interface with respect to the dynamic changes in the bulk phase behavior, the bulk composition, and the sample history using complementary surface-sensitive techniques. First, we show that bulk aggregates can spontaneously interact with the adsorption layer and are retained in it and that this process occurs most readily for positively charged aggregates with an expanded structure. In this case, key nonequilibrium issues of aggregate dissociation and spreading of surface-active material at the interface have a marked influence on the macroscopic interfacial properties. In a second distinct mechanism, aggregates inherently become trapped at the interface during its creation and lateral flocculation occurs. This irreversible process is most pronounced for aggregates with the lowest charge. A third mechanism involves the deposition of aggregates at interfaces due to their transport under gravity. The specificity of this process at an interface depends on its location and is mediated by density effects in the bulk. The prevalence of each mechanism critically depends on a number of different factors, which are outlined systematically here for the first time. This study highlights the sheer complexity by which aggregates can directly impact the interfacial properties of a P/S mixture. Our findings offer scope for understanding seemingly mysterious irreproducible effects which can compromise the performance of formulations in wide-ranging applications from foams to emulsions and lubricants.

  6. Spectroscopic [correction of eSpectroscopic] and structural properties of valine gramicidin A in monolayers at the air-water interface.

    PubMed Central

    Lavoie, Hugo; Blaudez, Daniel; Vaknin, David; Desbat, Bernard; Ocko, Benjamin M; Salesse, Christian

    2002-01-01

    Monomolecular films of valine gramicidin A (VGA) were investigated in situ at the air-water interface by x-ray reflectivity and x-ray grazing incidence diffraction as well as polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS). These techniques were combined to obtain information on the secondary structure and the orientation of VGA and to characterize the shoulder observed in its pi-A isotherm. The thickness of the film was obtained by x-ray reflectivity, and the secondary structure of VGA was monitored using the frequency position of the amide I band. The PM-IRRAS spectra were compared with the simulated ones to identify the conformation adopted by VGA in monolayer. At large molecular area, VGA shows a disordered secondary structure, whereas at smaller molecular areas, VGA adopts an anti-parallel double-strand intertwined beta(5.6) helical conformation with 30 degrees orientation with respect to the normal with a thickness of 25 A. The interface between bulk water and the VGA monolayer was investigated by x-ray reflectivity as well as by comparing the experimental and the simulated PM-IRRAS spectra on D(2)O and H(2)O, which suggested the presence of oriented water molecules between the bulk and the monolayer. PMID:12496123

  7. Langmuir structure of poly (2-vinylpyridine-b-hexyl isocyanate) rod-coil diblock copolymers at the air/water Interface

    NASA Astrophysics Data System (ADS)

    Ahmad, Farhan

    2005-03-01

    We conducted a systematic interfacial study for the complete range (5%-90% of rod mole percentage) of an amphiphilic rod-coil system, poly (hexyl isocyanate)-b-(2-vinylpyridine) at the air/water and air/solid interface. We applied Langmuir balance technique, scanning probe microscopy (SPM), transmission electron microscopy (TEM) and X-ray reflectivity for the complete characterization of the monolayer at the interfaces. The phase isotherms showed the well amphiphilic balance for the diblock copolymers, and the formation of stable monolayers. With the increasing rod content, the consistent increase in the monolayer packing density was observed by the phase isotherms and supported by X-ray reflectivity. SPM and TEM characterization showed their interesting surface morphology according to the varying rod mole percentage in the rod-coil system. Rod mole percentage 5%-15% showed micellar morphology. Rod mole percentage 23%-32% showed distinct and dispersed rods, whereas rod mole percentage 70%-90% showed well packed structure similar to lamella phase. We found the tendency of the diblock system to adopt a packed monomolecular structure has increased by the increasing rod content. This lead us to conclude that it is the hexyl-isocyanate (rod part) that governs mostly the interfacial behavior of rod-coil block copolymers.

  8. Efficient Spectral Diffusion at the Air/Water Interface Revealed by Femtosecond Time-Resolved Heterodyne-Detected Vibrational Sum Frequency Generation Spectroscopy.

    PubMed

    Inoue, Ken-Ichi; Ishiyama, Tatsuya; Nihonyanagi, Satoshi; Yamaguchi, Shoichi; Morita, Akihiro; Tahara, Tahei

    2016-05-19

    Femtosecond vibrational dynamics at the air/water interface is investigated by time-resolved heterodyne-detected vibrational sum frequency generation (TR-HD-VSFG) spectroscopy and molecular dynamics (MD) simulation. The low- and high-frequency sides of the hydrogen-bonded (HB) OH stretch band at the interface are selectively excited with special attention to the bandwidth and energy of the pump pulses. Narrow bleach is observed immediately after excitation of the high-frequency side of the HB OH band at ∼3500 cm(-1), compared to the broad bleach observed with excitation of the low-frequency side at ∼3300 cm(-1). However, the time-resolved spectra observed with the two different excitations become very similar at 0.5 ps and almost indistinguishable by 1.0 ps. This reveals that efficient spectral diffusion occurs regardless of the difference of the pump frequency. The experimental observations are well-reproduced by complementary MD simulation. There is no experimental and theoretical evidence that supports extraordinary slow dynamics in the high-frequency side of the HB OH band, which was reported before. PMID:27120559

  9. Influence of dissolved humic substances on the mass transfer of organic compounds across the air-water interface.

    PubMed

    Ramus, Ksenia; Kopinke, Frank-Dieter; Georgi, Anett

    2012-01-01

    The effect of dissolved humic substances (DHS) on the rate of water-gas exchange of two volatile organic compounds was studied under various conditions of agitation intensity, solution pH and ionic strength. Mass-transfer coefficients were determined from the rate of depletion of model compounds from an apparatus containing a stirred aqueous solution with continuous purging of the headspace above the solution (dynamic system). Under these conditions, the overall transfer rate is controlled by the mass-transfer resistance on the water side of the water-gas interface. The experimental results show that the presence of DHS hinders the transport of the organic molecules from the water into the gas phase under all investigated conditions. Mass-transfer coefficients were significantly reduced even by low, environmentally relevant concentrations of DHS. The retardation effect increased with increasing DHS concentration. The magnitude of the retardation effect on water-gas exchange was compared for Suwannee River fulvic and humic acids, a commercially available leonardite humic acid and two synthetic surfactants. The observed results are in accordance with the concept of hydrodynamic effects. Surface pressure forces due to surface film formation change the hydrodynamic characteristics of water motion at the water-air interface and thus impede surface renewal.

  10. Surface activity and molecular organization of metallacarboranes at the air-water interface revealed by nonlinear optics.

    PubMed

    Gassin, Pierre-Marie; Girard, Luc; Martin-Gassin, Gaelle; Brusselle, Damien; Jonchère, Alban; Diat, Olivier; Viñas, Clara; Teixidor, Francesc; Bauduin, Pierre

    2015-03-01

    Because of their amphiphilic structure, surfactants adsorb at the water-air interface with their hydrophobic tails pointing out of the water and their polar heads plunging into the liquid phase. Unlike classical surfactants, metallabisdicarbollides (MCs) do not have a well-defined amphiphilic structure. They are nanometer-sized inorganic anions with an ellipsoidal shape composed of two carborane semicages sandwiching a metal ion. However, MCs have been shown to share many properties with surfactants, such as self-assembly in water (formation of micelles and vesicles), formation of lamellar lyotropic phases, and surface activity. By combining second harmonic generation and surface tension measurement, we show here that cobaltabis(dicarbollide) anion {[(C2B9H11)2Co](-) also named [COSAN](-)} with H(+) as a counterion, the most representative metallacarborane, adsorbs vertically at the water surface with its long axis normal to the surface. This vertical molecular orientation facilitates the formation of intermolecular and nonconventional dihydrogen bonds such as the B-H(δ-)···(δ+)H-C bond that has recently been proven to be at the origin of the self-assembly of MCs in water. Therefore, it appears here that lateral dihydrogen bonds are also involved in the surface activity of MCs.

  11. Surface rheology of PEO-PPO-PEO triblock copolymers at the air-water interface: comparison of spread and adsorbed layers.

    PubMed

    Blomqvist, B Rippner; Wärnheim, T; Claesson, P M

    2005-07-01

    The dilatational rheological properties of monolayers of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)-type block copolymers at the air-water interface have been investigated by employing an oscillating ring trough method. The properties of adsorbed monolayers were compared to spread layers over a range of surface concentrations. The studied polymers were PEO26-PPO39-PEO26 (P85), PEO103-PPO40-PEO103 (F88), and PEO99-PPO65-PEO99 (F127). Thus, two of the polymers have similar PPO block size and two of them have similar PEO block size, which allows us to draw conclusions about the relationship between molecular structure and surface dilatational rheology. The dilatational properties of adsorbed monolayers were investigated as a function of time and bulk solution concentration. The time dependence was found to be rather complex, reflecting structural changes in the layer. When the dilatational modulus measured at different concentrations was replotted as a function of surface pressure, one unique master curve was obtained for each polymer. It was found that the dilatational behavior of spread (Langmuir) and adsorbed (Gibbs) monolayers of the same polymer is close to identical up to surface concentrations of approximately 0.7 mg/m2. At higher coverage, the properties are qualitatively alike with respect to dilatational modulus, although some differences are noticeable. Relaxation processes take place mainly within the interfacial layers by a redistribution of polymer segments. Several conformational transitions were shown to occur as the area per molecule decreased. PEO desorbs significantly from the interface at segmental areas below 20 A(2), while at higher surface coverage, we propose that segments of PPO are forced to leave the interface to form a mixed sublayer in the aqueous region. PMID:15982044

  12. Surface adsorption of oppositely charged C14TAB-PAMPS mixtures at the air/water interface and the impact on foam film stability.

    PubMed

    Fauser, Heiko; von Klitzing, Regine; Campbell, Richard A

    2015-01-01

    We have studied the oppositely charged polyelectrolyte/surfactant mixture of poly(acrylamidomethylpropanesulfonate) sodium salt (PAMPS) and tetradecyl trimethylammonium bromide (C14TAB) using a combination of neutron reflectivity and ellipsometry measurements. The interfacial composition was determined using three different analysis methods involving the two techniques for the first time. The bulk surfactant concentration was fixed at a modest value while the bulk polyelectrolyte concentration was varied over a wide range. We reveal complex changes in the surface adsorption behavior. Mixtures with low bulk PAMPS concentrations result in the components interacting synergistically in charge neutral layers at the air/water interface. At the bulk composition where PAMPS and C14TAB are mixed in an equimolar charge ratio in the bulk, we observe a dramatic drop in the surfactant surface excess to leave a large excess of polyelectrolyte at the interface, which we infer to have loops in its interfacial structure. Further increase of the bulk PAMPS concentration leads to a more pronounced depletion of material from the surface. Mixtures containing a large excess of PAMPS in the bulk showed enhanced adsorption, which is attributed to the large increase in total ionic strength of the system and screening of the surfactant headgroup charges. The data are compared to our former results on PAMPS/C14TAB mixtures [Kristen et al. J. Phys. Chem. B, 2009, 23, 7986]. A peak in the surface tension is rationalized in terms of the changing surface adsorption and, unlike in more concentrated systems, is unrelated to bulk precipitation. Also, a comparison between the determined interfacial composition with zeta potential and foam film stability data shows that the highest film stability occurs when there is enhanced synergistic adsorption of both components at the interface due to charge screening when the total ionic strength of the system is highest. The additional contribution to the

  13. Organization of lipids in the artificial outer membrane of bull spermatozoa reconstructed at the air-water interface.

    PubMed

    Le Guillou, J; Ropers, M-H; Gaillard, C; David-Briand, E; Desherces, S; Schmitt, E; Bencharif, D; Amirat-Briand, L; Tainturier, D; Anton, M

    2013-08-01

    Cryopreservation is widely used to preserve the quality of bull spermatozoa over time. Sequestration of seminal plasma proteins by low density lipoproteins and formation of a protective film around the spermatozoa membrane by low density lipoproteins were the main mechanisms proposed. However, the organization of lipids in the outer leaflet of the spermatozoa membrane has been never considered as a possible parameter. This study evaluated whether a change in the organization of the outer leaflet of the spermotozoa membrane could occur during cooling down. The organization of the main components of the spermatozoa membrane's outer layer at the liquid-gas interface was analysed. Cryopreservative media (at 8° and 34°C) were used to study the miscibility of the spermatozoa membrane lipids using epifluorescence imaging and by tensiometry on Langmuir films. The results show that the four lipids: sphingomyelin, cholesterol, 1-palmitoyl-2-docosahexaenoyl-sn-glycero-3-phosphocholine (PC) and plasmalogen 1-(1Z-octadecenyl)-2-docosahexaenoyl-sn-glycero-3-phosphocholine (P-PC) were not fully miscible and their organization was controlled by temperature. Cholesterol and sphingomyelin form condensed domains surrounded by a mixture of PC and P-PC at 34°C while these condensed domains are surrounded by separated domains of pure PC and pure P-PC at 8°C. The organization of the outer membrane lipids, in particular the separation of PC and P-PC lipids during cooling down, must be considered to fully understand preservation of membrane integrity during cryopreservation. PMID:23563290

  14. Ligand Shell Composition-Dependent Effects on the Apparent Hydrophobicity and Film Behavior of Gold Nanoparticles at the Air-Water Interface.

    PubMed

    Bradford, Stephen M; Fisher, Elizabeth A; Meli, M-Vicki

    2016-09-27

    Nanoparticles with well-defined interfacial energy and wetting properties are needed for a broad range of applications involving nanoparticle self-assembly including the formation of superlattices, stability of Pickering emulsions, and for the control of nanoparticle interactions with biological membranes. Theoretical, simulated, and recent experimental studies have found nanometer-scale chemical heterogeneity to have important effects on hydrophobic interactions. Here we report the study of 4 nm gold nanoparticles with compositionally well-defined mixed ligand shells of hydroxyl-(OH) and methyl-(CH3) terminated alkylthiols as Langmuir films. Compositions ranging from 0-25% hydroxyl were examined and reveal nonmonotonic changes in particle hydrophobicity at the air-water interface. Unlike nanoparticles capped exclusively with a methyl-terminated alkylthiol, extensive particle aggregation is found for ligand shells containing <2% hydroxyl-terminated chains. This aggregation was lessened upon increasing the quantity of OH-terminated chains. Nanoparticles capped with 25% OH yield films of well-separated nanoparticles exhibiting a fluid-phase regime in the surface pressure vs area isotherm. Compression-expansion hysteresis, monolayer collapse, and mean nanoparticle area measurements support the TEM-observed changes in film morphology. Such clear changes in the hydrophobicity of nanoparticles based on very small changes in the ligand shell composition are shown to impact the process of interfacial nanoparticle self-assembly and are an important demonstration of nanoscale wetting with consequences in both materials and biological applications of nanoparticles that require tunable hydrophobicity. PMID:27594307

  15. Bio-inspired fabrication of hierarchical FeOOH nanostructure array films at the air-water interface, their hydrophobicity and application for water treatment.

    PubMed

    Liu, Lei; Yang, Liu-Qing; Liang, Hai-Wei; Cong, Huai-Ping; Jiang, Jun; Yu, Shu-Hong

    2013-02-26

    Hierarchical FeOOH nanostructure array films constructed by different nanosized building blocks can be synthesized at the air-water interface via a bio-inspired gas-liquid diffusion method. In this approach, poly(acrylic acid) (PAA) as a crystal growth modifier plays a crucial role in mediating the morphology and polymorph of FeOOH crystals. With the increase of PAA concentration, the shape of the building blocks assembling into FeOOH films can be tailored from nanosheets, to rice spikes, then to branched fibers, and finally to nanowires. What is more, a low concentration of PAA will induce the formation of α-FeOOH, while a high one could stabilize FeOOH in the form of the γ-FeOOH phase. After being modified with a thin layer of polydimethylsiloxane (PDMS), the as-prepared FeOOH films exhibited strong hydrophobicity with water contact angles (CA) from 134° to 148° or even superhydrophobicity with a CA of 164° in the sample constructed by nanosheets. When the FeOOH nanostructures were dispersed in water by ultrasound, they displayed quite promising adsorption performance of heavy metal ions for water treatment, where the highest adsorption capacity can reach 77.2 mg·g⁻¹ in the sample constructed by nanowires. This bio-inspired approach may open up the possibilities for the fabrication of other functional nanostructure thin films with unique properties.

  16. Surface interactions, thermodynamics and topography of binary monolayers of Insulin with dipalmitoylphosphatidylcholine and 1-palmitoyl-2-oleoylphosphatidylcholine at the air/water interface.

    PubMed

    Grasso, E J; Oliveira, R G; Maggio, B

    2016-02-15

    The molecular packing, thermodynamics and surface topography of binary Langmuir monolayers of Insulin and DPPC (dipalmitoylphosphatidylcholine) or POCP (1-palmitoyl-2-oleoylphosphatidylcholine) at the air/water interface on Zn(2+) containing solutions were studied. Miscibility and interactions were ascertained by the variation of surface pressure-mean molecular area isotherms, surface compressional modulus and surface (dipole) potential with the film composition. Brewster Angle Microscopy was used to visualize the surface topography of the monolayers. Below 20mN/m Insulin forms stable homogenous films with DPPC and POPC at all mole fractions studied (except for films with XINS=0.05 at 10mN/m where domain coexistence was observed). Above 20mN/m, a segregation process between mixed phases occurred in all monolayers without squeezing out of individual components. Under compression the films exhibit formation of a viscoelastic or kinetically trapped organization leading to considerable composition-dependent hysteresis under expansion that occurs with entropic-enthalpic compensation. The spontaneously unfavorable interactions of Insulin with DPPC are driven by favorable enthalpy that is overcome by unfavorable entropic ordering; in films with POPC both the enthalpic and entropic effects are unfavorable. The surface topography reveals domain coexistence at relatively high pressure showing a striped appearance. The interactions of Insulin with two major membrane phospholipids induces composition-dependent and long-range changes of the surface organization that ought to be considered in the context of the information-transducing capabilities of the hormone for cell functioning.

  17. Binding structure and kinetics of surfactin monolayer formed at the air/water interface to counterions: A molecular dynamics simulation study.

    PubMed

    Gang, Hongze; Liu, Jinfeng; Mu, Bozhong

    2015-10-01

    The binding structure and kinetics of ionized surfactin monolayer formed at the air/water interface to five counterions, Li+, Na+, K+, Ca2+, and Ba2+ (molar ratios of surfactin to monovalent and divalent counterions are 1:2 and 1:1 respectively), have been studied using molecular dynamics simulation. The results show that surfactin exhibits higher binding affinity to divalent counterions, Ca2+, and Ba2+, and smaller monovalent counterion, Li+, than Na+ and K+. Both carboxyl groups in surfactin are accessible for counterions, but the carboxyl group in Glu1 is easier to access by counterions than Asp5. Salt bridges are widely built between carboxyl groups by counterions, and the probability of the formation of intermolecular salt bridge is markedly larger than that of intramolecular salt bridge. Divalent counterions perform well in forming salt bridges between carboxyl groups. The salt bridges mediated by Ca2+ are so rigid that the lifetimes are about 0.13 ns, and the break rates of these salt bridges are 1-2 orders of magnitude smaller than those mediated by K+ which is about 5 ps in duration. The positions of the hydration layer of carboxyl groups are independent of counterions, but the bound counterions induce the dehydration of carboxyl groups and disturb the hydrogen bonds built between carboxyl group and hydration water.

  18. Combined effect of synthetic protein, Mini-B, and cholesterol on a model lung surfactant mixture at the air-water interface.

    PubMed

    Chakraborty, Aishik; Hui, Erica; Waring, Alan J; Dhar, Prajnaparamita

    2016-04-01

    The overall goal of this work is to study the combined effects of Mini-B, a 34 residue synthetic analog of the lung surfactant protein SP-B, and cholesterol, a neutral lipid, on a model binary lipid mixture containing dipalmitolphosphatidylcholine (DPPC) and palmitoyl-oleoyl-phosphatidylglycerol (POPG), that is often used to mimic the primary phospholipid composition of lung surfactants. Using surface pressure vs. mean molecular area isotherms, fluorescence imaging and analysis of lipid domain size distributions; we report on changes in the structure, function and stability of the model lipid-protein films in the presence and absence of varying composition of cholesterol. Our results indicate that at low cholesterol concentrations, Mini-B can prevent cholesterol's tendency to lower the line tension between lipid domain boundaries, while maintaining Mini-B's ability to cause reversible collapse resulting in the formation of surface associated reservoirs. Our results also show that lowering the line tension between domains can adversely impact monolayer folding mechanisms. We propose that small amounts of cholesterol and synthetic protein Mini-B can together achieve the seemingly opposing requirements of efficient LS: fluid enough to flow at the air-water interface, while being rigid enough to oppose irreversible collapse at ultra-low surface tensions. PMID:26775740

  19. Surface interactions, thermodynamics and topography of binary monolayers of Insulin with dipalmitoylphosphatidylcholine and 1-palmitoyl-2-oleoylphosphatidylcholine at the air/water interface.

    PubMed

    Grasso, E J; Oliveira, R G; Maggio, B

    2016-02-15

    The molecular packing, thermodynamics and surface topography of binary Langmuir monolayers of Insulin and DPPC (dipalmitoylphosphatidylcholine) or POCP (1-palmitoyl-2-oleoylphosphatidylcholine) at the air/water interface on Zn(2+) containing solutions were studied. Miscibility and interactions were ascertained by the variation of surface pressure-mean molecular area isotherms, surface compressional modulus and surface (dipole) potential with the film composition. Brewster Angle Microscopy was used to visualize the surface topography of the monolayers. Below 20mN/m Insulin forms stable homogenous films with DPPC and POPC at all mole fractions studied (except for films with XINS=0.05 at 10mN/m where domain coexistence was observed). Above 20mN/m, a segregation process between mixed phases occurred in all monolayers without squeezing out of individual components. Under compression the films exhibit formation of a viscoelastic or kinetically trapped organization leading to considerable composition-dependent hysteresis under expansion that occurs with entropic-enthalpic compensation. The spontaneously unfavorable interactions of Insulin with DPPC are driven by favorable enthalpy that is overcome by unfavorable entropic ordering; in films with POPC both the enthalpic and entropic effects are unfavorable. The surface topography reveals domain coexistence at relatively high pressure showing a striped appearance. The interactions of Insulin with two major membrane phospholipids induces composition-dependent and long-range changes of the surface organization that ought to be considered in the context of the information-transducing capabilities of the hormone for cell functioning. PMID:26624532

  20. Combined effect of synthetic protein, Mini-B, and cholesterol on a model lung surfactant mixture at the air-water interface.

    PubMed

    Chakraborty, Aishik; Hui, Erica; Waring, Alan J; Dhar, Prajnaparamita

    2016-04-01

    The overall goal of this work is to study the combined effects of Mini-B, a 34 residue synthetic analog of the lung surfactant protein SP-B, and cholesterol, a neutral lipid, on a model binary lipid mixture containing dipalmitolphosphatidylcholine (DPPC) and palmitoyl-oleoyl-phosphatidylglycerol (POPG), that is often used to mimic the primary phospholipid composition of lung surfactants. Using surface pressure vs. mean molecular area isotherms, fluorescence imaging and analysis of lipid domain size distributions; we report on changes in the structure, function and stability of the model lipid-protein films in the presence and absence of varying composition of cholesterol. Our results indicate that at low cholesterol concentrations, Mini-B can prevent cholesterol's tendency to lower the line tension between lipid domain boundaries, while maintaining Mini-B's ability to cause reversible collapse resulting in the formation of surface associated reservoirs. Our results also show that lowering the line tension between domains can adversely impact monolayer folding mechanisms. We propose that small amounts of cholesterol and synthetic protein Mini-B can together achieve the seemingly opposing requirements of efficient LS: fluid enough to flow at the air-water interface, while being rigid enough to oppose irreversible collapse at ultra-low surface tensions.

  1. Floatable, Self-Cleaning, and Carbon-Black-Based Superhydrophobic Gauze for the Solar Evaporation Enhancement at the Air-Water Interface.

    PubMed

    Liu, Yiming; Chen, Jingwei; Guo, Dawei; Cao, Moyuan; Jiang, Lei

    2015-06-24

    Efficient solar evaporation plays an indispensable role in nature as well as the industry process. However, the traditional evaporation process depends on the total temperature increase of bulk water. Recently, localized heating at the air-water interface has been demonstrated as a potential strategy for the improvement of solar evaporation. Here, we show that the carbon-black-based superhydrophobic gauze was able to float on the surface of water and selectively heat the surface water under irradiation, resulting in an enhanced evaporation rate. The fabrication process of the superhydrophobic black gauze was low-cost, scalable, and easy-to-prepare. Control experiments were conducted under different light intensities, and the results proved that the floating black gauze achieved an evaporation rate 2-3 times higher than that of the traditional process. A higher temperature of the surface water was observed in the floating gauze group, revealing a main reason for the evaporation enhancement. Furthermore, the self-cleaning ability of the superhydrophobic black gauze enabled a convenient recycling and reusing process toward practical application. The present material may open a new avenue for application of the superhydrophobic substrate and meet extensive requirements in the fields related to solar evaporation. PMID:26027770

  2. Floatable, Self-Cleaning, and Carbon-Black-Based Superhydrophobic Gauze for the Solar Evaporation Enhancement at the Air-Water Interface.

    PubMed

    Liu, Yiming; Chen, Jingwei; Guo, Dawei; Cao, Moyuan; Jiang, Lei

    2015-06-24

    Efficient solar evaporation plays an indispensable role in nature as well as the industry process. However, the traditional evaporation process depends on the total temperature increase of bulk water. Recently, localized heating at the air-water interface has been demonstrated as a potential strategy for the improvement of solar evaporation. Here, we show that the carbon-black-based superhydrophobic gauze was able to float on the surface of water and selectively heat the surface water under irradiation, resulting in an enhanced evaporation rate. The fabrication process of the superhydrophobic black gauze was low-cost, scalable, and easy-to-prepare. Control experiments were conducted under different light intensities, and the results proved that the floating black gauze achieved an evaporation rate 2-3 times higher than that of the traditional process. A higher temperature of the surface water was observed in the floating gauze group, revealing a main reason for the evaporation enhancement. Furthermore, the self-cleaning ability of the superhydrophobic black gauze enabled a convenient recycling and reusing process toward practical application. The present material may open a new avenue for application of the superhydrophobic substrate and meet extensive requirements in the fields related to solar evaporation.

  3. Two-dimensional crystallization of catalase on a monolayer film of poly(1-benzyl-L-histidine) spread at the air/water interface.

    PubMed

    Sato, A; Furuno, T; Toyoshima, C; Sasabe, H

    1993-03-01

    Two-dimensional (2D) crystals of beef liver catalase were prepared by adsorption to a film of synthetic polypeptide, poly(1-benzyl-L-histidine) (PBLH), spread at the air/water interface. The crystallization experiments were carried out in the pH range of 4.8-6.4 for catalase solutions at low concentration (10 micrograms/ml). The pH-dependence suggested an electrostatic interaction in the binding of catalase to the PBLH film. At lower pH, small crystals were formed at a low binding rate, and at higher pH the binding was rapid and densely-packed 2D arrays with poor crystallinity were formed. To stimulate crystal growth, a thermal treatment was applied. One-shot heating of the interfacial catalase-PBLH film to 35-40 degrees C was remarkably effective to form larger 2D crystals. The structure of catalase 2D crystals has been analyzed by Fourier filtering of the transmission electron micrographs. The crystal form is a new one, containing four catalase molecules in the unit cell with lattice parameters of alpha = 187 A, b = 225 A and gamma = 92.8 degrees.

  4. Spread mixed monolayers of deoxycholic and dehydrocholic acids at the air-water interface, effect of subphase pH. Characterization by axisymmetric drop shape analysis.

    PubMed

    Messina, Paula V; Fernández-Leyes, Marcos D; Prieto, Gerardo; Ruso, Juan M; Sarmiento, Félix; Schulz, Pablo C

    2008-01-01

    Bile acids (deoxycholic and dehydrocholic acids) spread mixed monolayers behavior at the air/water interface were studied as a function of subphase pH using a constant surface pressure penetration Langmuir balance based on the Axisymmetric Drop Shape Analysis (ADSA). We examined the influence of electrostatic, hydrophobic and hydration forces on the interaction between amphiphilic molecules at the interface by the collapse area values, the thermodynamic parameters and equation of state virial coefficients analysis. The obtained results showed that at neutral (pH=6.7) or basic (pH=10) subphase conditions the collapse areas values are similar to that of cholanoic acid and consistent with the cross-sectional area of the steroid nucleus (approximately 40 A(2)). The Gibbs energy of mixing values (DeltaG(mix)<0) and the first virial coefficients of the equation of state (b(0)<1) indicated that a miscible monolayer with laterally structured microdomains existed. The aggregation number (1/b(0)) was estimated within the order of 6 (pH=6.7) and 3 (pH=10). At pH=3.2, acidic subphase conditions, no phase separation occurs (DeltaG(mix)<0) but a high expanded effect of the monolayer could be noted. The mixed monolayer behavior was no ideal and no aggregates were formed (b(0)> or =1). Such behavior indicates that the polar groups of the molecules interacts each other more strongly by repulsive electrostatic forces than with the more hydrophobic part of the molecule.

  5. Measurement of the Surface Dilatational Viscosity of an Insoluble Surfactant Monolayer at the Air/Water Interface Using a Pendant Drop Apparatus

    NASA Technical Reports Server (NTRS)

    Lorenzo, Jose; Couzis, Alex; Maldarelli, Charles; Singh, Bhim S. (Technical Monitor)

    2000-01-01

    When a fluid interface with surfactants is at rest, the interfacial stress is isotropic (as given by the equilibrium interfacial tension), and is described by the equation of state which relates the surface tension to the surfactant surface concentration. When surfactants are subjected to shear and dilatational flows, flow induced interaction of the surfactants; can create interfacial stresses apart from the equilibrium surface tension. The simplest relationship between surface strain rate and surface stress is the Boussinesq-Scriven constitutive equation completely characterized by three coefficients: equilibrium interfacial tension, surface shear viscosity, and surface dilatational viscosity Equilibrium interfacial tension and surface shear viscosity measurements are very well established. On the other hand, surface dilatational viscosity measurements are difficult because a flow which change the surface area also changes the surfactant surface concentration creating changes in the equilibrium interfacial tension that must be also taken into account. Surface dilatational viscosity measurements of existing techniques differ by five orders of magnitude and use spatially damped surface waves and rapidly expanding bubbles. In this presentation we introduce a new technique for measuring the surface dilatational viscosity by contracting an aqueous pendant drop attached to a needle tip and having and insoluble surfactant monolayer at the air-water interface. The isotropic total tension on the surface consists of the equilibrium surface tension and the tension due to the dilation. Compression rates are undertaken slow enough so that bulk hydrodynamic stresses are small compared to the surface tension force. Under these conditions we show that the total tension is uniform along the surface and that the Young-Laplace equation governs the drop shape with the equilibrium surface tension replaced by the constant surface isotropic stress. We illustrate this technique using

  6. Self-assembly at Air/Water Interfaces and Carbohydrate Binding Properties of the Small Secreted Protein EPL1 from the fungus Trichoderma atroviride*

    PubMed Central

    Frischmann, Alexa; Neudl, Susanna; Gaderer, Romana; Bonazza, Klaus; Zach, Simone; Gruber, Sabine; Spadiut, Oliver; Friedbacher, Gernot; Grothe, Hinrich; Seidl-Seiboth, Verena

    2013-01-01

    The protein EPL1 from the fungus Trichoderma atroviride belongs to the cerato-platanin protein family. These proteins occur only in filamentous fungi and are associated with the induction of defense responses in plants and allergic reactions in humans. However, fungi with other lifestyles also express cerato-platanin proteins, and the primary function of this protein family has not yet been elucidated. In this study, we investigated the biochemical properties of the cerato-platanin protein EPL1 from T. atroviride. Our results showed that EPL1 readily self-assembles at air/water interfaces and forms protein layers that can be redissolved in water. These properties are reminiscent of hydrophobins, which are amphiphilic fungal proteins that accumulate at interfaces. Atomic force microscopy imaging showed that EPL1 assembles into irregular meshwork-like substructures. Furthermore, surface activity measurements with EPL1 revealed that, in contrast to hydrophobins, EPL1 increases the polarity of aqueous solutions and surfaces. In addition, EPL1 was found to bind to various forms of polymeric chitin. The T. atroviride genome contains three epl genes. epl1 was predominantly expressed during hyphal growth, whereas epl2 was mainly expressed during spore formation, suggesting that the respective proteins are involved in different biological processes. For epl3, no gene expression was detected under most growth conditions. Single and double gene knock-out strains of epl1 and epl2 did not reveal a detectable phenotype, showing that these proteins are not essential for fungal growth and development despite their abundant expression. PMID:23250741

  7. Structure of Ceramide-1-Phosphate at the Air-Water Solution Interface in the Absence and Presence of Ca[superscript 2+

    SciTech Connect

    Kooijman, Edgar E.; Vaknin, David; Bu, Wei; Joshi, Leela; Kang, Shin-Woong; Gericke, Arne; Mann, Elizabeth K.; Kumar, Satyendra

    2009-03-24

    Ceramide-1-phosphate, the phosphorylated form of ceramide, gained attention recently due to its diverse intracellular roles, in particular in inflammation mediated by cPLA{sub 2}{alpha}. However, surprisingly little is known about the physical chemical properties of this lipid and its potential impact on physiological function. For example, the presence of Ca{sup 2+} is indispensable for the interaction of Cer-1-P with the C2 domain of cPLA{sub 2}{alpha}. We report on the structure and morphology of Cer-1-P in monomolecular layers at the air/water solution interface in the absence and presence of Ca{sup 2+} using diverse biophysical techniques, including synchrotron x-ray reflectivity and grazing angle diffraction, to gain insight into the role and function of Cer-1-P in biomembranes. We show that relatively small changes in pH and the presence of monovalent cations dramatically affect the behavior of Cer-1-P. On pure water Cer-1-P forms a solid monolayer despite the negative charge of the phosphomonoester headgroup. In contrast, pH 7.2 buffer yields a considerably less solid-like monolayer, indicating that charge-charge repulsion becomes important at higher pH. Calcium was found to bind strongly to the headgroup of Cer-1-P even in the presence of a 100-fold larger Na{sup +} concentration. Analysis of the x-ray reflectivity data allowed us to estimate how much Ca{sup 2+} is bound to the headgroup, 0.5 Ca{sup 2+} and 1.0 Ca{sup 2+} ions per Cer-1-P molecule for the water and buffer subphase respectively. These results can be qualitatively understood based on the molecular structure of Cer-1-P and the electrostatic/hydrogen-bond interactions of its phosphomonoester headgroup. Biological implications of our results are also discussed.

  8. Surface characteristics of phosphatidylglycerol phosphate from the extreme halophile Halobacterium cutirubrum compared with those of its deoxy analogue, at the air/water interface.

    PubMed

    Quinn, P J; Kates, M; Tocanne, J F; Tomoaia-Cotişel, M

    1989-07-15

    The relationship between area per molecule and surface pressure of monolayers of phosphatidylglycerol phosphate from extreme halophile Halobacterium cutrirubrum and its deoxy analogue, deoxyphosphatidylglycerol phosphate, spread at an air/water interface was examined. The effect of ionization of the primary and secondary acidic functions of the phosphate groups of the two lipids on surface characteristics of compression isotherms was determined by spreading monolayers on subphases with pH values ranging from below the apparent pKa of the primary ionization (pH 0) to greater than that of secondary ionization (pH 10.9). The limiting molecular area increases with decreasing pH below 2. Ionization of the primary phosphate functions of both phospholipids (with bulk pK1 values close to 4) is associated with a marked expansion of the films, as judged by values of limiting molecular area. Ionization of the secondary phosphate functions causes further expansion of the films, with the apparent pK2 of deoxyphosphatidylglycerol phosphate slightly less than that indicated for phosphatidylglycerol phosphate. Values of surface-compressibility modulus calculated from the surface characteristics of the phosphatidylglcerol phosphate monolayers showed that films spread on subphases with a pH of about the apparent pK1 of the primary phosphate functions were the least compressible. Increasing or decreasing subphase pH caused an increase in compressibility; this effect on compressibility was much less with monolayers of deoxyphosphatidylglycerol phosphate at high pH. The effect of inorganic counter-ions on monolayer characteristics of phosphatidylglycerol phosphate was examined by using subphases of NaCl concentrations varying from 0.01 to 1 M. The limiting molecular area was found to increase exponentially with respect to the subphase NaCl concentration.

  9. Spider-web amphiphiles as artificial lipid clusters: design, synthesis, and accommodation of lipid components at the air-water interface.

    PubMed

    Ariga, Katsuhiko; Urakawa, Toshihiro; Michiue, Atsuo; Kikuchi, Jun-ichi

    2004-08-01

    As a novel category of two-dimensional lipid clusters, dendrimers having an amphiphilic structure in every unit were synthesized and labeled "spider-web amphiphiles". Amphiphilic units based on a Lys-Lys-Glu tripeptide with hydrophobic tails at the C-terminal and a polar head at the N-terminal are dendrically connected through stepwise peptide coupling. This structural design allowed us to separately introduce the polar head and hydrophobic tails. Accordingly, we demonstrated the synthesis of the spider-web amphiphile series in three combinations: acetyl head/C16 chain, acetyl head/C18 chain, and ammonium head/C16 chain. All the spider-web amphiphiles were synthesized in satisfactory yields, and characterized by 1H NMR, MALDI-TOFMS, GPC, and elemental analyses. Surface pressure (pi)-molecular area (A) isotherms showed the formation of expanded monolayers except for the C18-chain amphiphile at 10 degrees C, for which the molecular area in the condensed phase is consistent with the cross-sectional area assigned for all the alkyl chains. In all the spider-web amphiphiles, the molecular areas at a given pressure in the expanded phase increased in proportion to the number of units, indicating that alkyl chains freely fill the inner space of the dendritic core. The mixing of octadecanoic acid with the spider-web amphiphiles at the air-water interface induced condensation of the molecular area. From the molecular area analysis, the inclusion of the octadecanoic acid bears a stoichiometric characteristic; i.e., the number of captured octadecanoic acids in the spider-web amphiphile roughly agrees with the number of branching points in the spider-web amphiphile.

  10. Determination of chain orientation in the monolayers of amino-acid-derived schiff base at the air-water interface using in situ infrared reflection absorption spectroscopy.

    PubMed

    Liu, Huijin; Miao, Wangen; Du, Xuezhong

    2007-10-23

    The chain orientation in the monolayers of amino-acid-derived Schiff base, 4-(4-dodecyloxy)-2-hydroxybenzylideneamino)benzoic acid (DSA), at the air-water interface has been determined using infrared reflection absorption spectroscopy (IRRAS). On pure water, a condensed monolayer is formed with the long axes of Schiff base segments almost perpendicular to the water surface. In the presence of metal ions (Ca2+, Co2+, Zn2+, Ni2+, and Cu2+) in the subphase, the monolayer is expanded and the long axes of the Schiff base segments are inclined with respect to the monolayer normal depending on metal ion. The monolayer thickness, which is an important parameter for quantitative determination of orientation of hydrocarbon chains, is composed of alkyl chains and salicylideneaniline portions for the DSA monolayers. The effective thickness of the Schiff base portions is roughly estimated in the combination of the IRRAS results and surface pressure-area isotherms for computer simulation, since the only two observable p- and s-polarized reflectance-absorbance (RA) values can be obtained. The alkyl chains with almost all-trans conformations are oriented at an angle of about 10 degrees for H2O, 15 degrees for Ca2+, 30 degrees for Co2+, 35 degrees -40 degrees for Zn2+, and 35 degrees -40 degrees for Ni2+ with respect to the monolayer normal. The chain segments linked with gauche conformers in the case of Cu2+ are estimated to be 40 degrees -50 degrees away from the normal. PMID:17902721

  11. Surface pressure and elasticity of hydrophobin HFBII layers on the air-water interface: rheology versus structure detected by AFM imaging.

    PubMed

    Stanimirova, Rumyana D; Gurkov, Theodor D; Kralchevsky, Peter A; Balashev, Konstantin T; Stoyanov, Simeon D; Pelan, Eddie G

    2013-05-21

    Here, we combine experiments with Langmuir trough and atomic force microscopy (AFM) to investigate the reasons for the special properties of layers from the protein HFBII hydrophobin spread on the air-water interface. The hydrophobin interfacial layers possess the highest surface dilatational and shear elastic moduli among all investigated proteins. The AFM images show that the spread HFBII layers are rather inhomogeneous, (i.e., they contain voids, monolayer and multilayer domains). A continuous compression of the layer leads to filling the voids and transformation of a part of the monolayer into a trilayer. The trilayer appears in the form of large surface domains, which can be formed by folding and subduction of parts from the initial monolayer. The trilayer appears also in the form of numerous submicrometer spots, which can be obtained by forcing protein molecules out of the monolayer and their self-assembly into adjacent pimples. Such structures are formed because not only the hydrophobic parts, but also the hydrophilic parts of the HFBII molecules can adhere to each other in the water medium. If a hydrophobin layer is subjected to oscillations, its elasticity considerably increases, up to 500 mN/m, which can be explained with compaction. The relaxation of the layer's tension after expansion or compression follows the same relatively simple law, which refers to two-dimensional diffusion of protein aggregates within the layer. The characteristic diffusion time after compression is longer than after expansion, which can be explained with the impedence of diffusion in the more compact interfacial layer. The results shed light on the relation between the mesoscopic structure of hydrophobin interfacial layers and their unique mechanical properties that find applications for the production of foams and emulsions of extraordinary stability; for the immobilization of functional molecules at surfaces, and as coating agents for surface modification.

  12. Controlled deposition of functionalized silica coated zinc oxide nano-assemblies at the air/water interface for blood cancer detection.

    PubMed

    Pandey, Chandra Mouli; Dewan, Srishti; Chawla, Seema; Yadav, Birendra Kumar; Sumana, Gajjala; Malhotra, Bansi Dhar

    2016-09-21

    We report results of the studies relating to controlled deposition of the amino-functionalized silica-coated zinc oxide (Am-Si@ZnO) nano-assemblies onto an indium tin oxide (ITO) coated glass substrate using Langmuir-Blodgett (LB) technique. The monolayers have been deposited by transferring the spread solution of Am-Si@ZnO stearic acid prepared in chloroform at the air-water interface, at optimized pressure (16 mN/m), concentration (10 mg/ml) and temperature (23 °C). The high-resolution transmission electron microscopic studies of the Am-Si@ZnO nanocomposite reveal that the nanoparticles have a microscopic structure comprising of hexagonal assemblies of ZnO with typical dimensions of 30 nm. The surface morphology of the LB multilayer observed by scanning electron microscopy shows uniform surface of the Am-Si@ZnO film in the nanometer range (<80 nm). These electrodes have been utilized for chronic myelogenous leukemia (CML) detection by covalently immobilizing the amino-terminated oligonucleotide probe sequence via glutaraldehyde as a crosslinker. The response studies of these fabricated electrodes carried out using electrochemical impedance spectroscopy show that this Am-Si@ZnO LB film based nucleic acid sensor exhibits a linear response to complementary DNA (10(-6)-10(-16) M) with a detection limit of 1 × 10(-16) M. This fabricated platform is validated with clinical samples of CML positive patients and the results demonstrate its immense potential for clinical diagnosis. PMID:27590542

  13. Adsorption of egg phosphatidylcholine to an air/water and triolein/water bubble interface: use of the 2-dimensional phase rule to estimate the surface composition of a phospholipid/triolein/water surface as a function of surface pressure.

    PubMed

    Mitsche, Matthew A; Wang, Libo; Small, Donald M

    2010-03-11

    Phospholipid monolayers play a critical role in the structure and stabilization of biological interfaces, including all membranes, the alveoli of the lungs, fat droplets in adipose tissue, and lipoproteins. The behavior of phospholipids in bilayers and at an air-water interface is well understood. However, the study of phospholipids at oil-water interfaces is limited due to technical challenges. In this study, egg phosphatidylcholine (EPC) was deposited from small unilamellar vesicles onto a bubble of either air or triolein (TO) formed in a low-salt buffer. The surface tension (gamma) was measured using a drop tensiometer. We observed that EPC binds irreversibly to both interfaces and at equilibrium exerts approximately 12 and 15 mN/m of pressure (Pi) at an air and TO interface, respectively. After EPC was bound to the interface, the unbound EPC was washed out of the cuvette, and the surface was compressed to study the Pi/area relationship. To determine the surface concentration (Gamma), which cannot be measured directly, compression isotherms from a Langmuir trough and drop tensiometer were compared. The air-water interfaces had identical characteristics using both techniques; thus, Gamma on the bubble can be determined by overlaying the two isotherms. Both TO and EPC are surface-active, so in a mixed TO/EPC monolayer, both molecules will be exposed to water. Since TO is less surface-active than EPC, as Pi increases, the TO is progressively ejected. To understand the Pi/area isotherm of EPC on a TO bubble, a variety of TO-EPC mixtures were spread at the air-water interface. The isotherms show an abrupt break in the curve caused by the ejection of TO from the monolayer into a new bulk phase. By overlaying the compression isotherm above the ejection point with a TO bubble compression isotherm, Gamma can be estimated. This allows determination of Gamma of EPC on a TO bubble as a function of Pi.

  14. Investigating the pathway for the photochemical formation of VOCs in presence of an organic monolayer at the air/water interface.

    NASA Astrophysics Data System (ADS)

    Tinel, Liselotte; Rossignol, Stéphanie; Ciuraru, Raluca; George, Christian

    2015-04-01

    Investigating the pathway for the photochemical formation of VOCs in presence of an organic monolayer at the air/water interface. Liselotte Tinel, Stéphanie Rossignol, Raluca Ciuraru and Christian George Université de Lyon, Université Lyon 1, CNRS, UMR5256, IRCELYON, Institut de recherches sur la catalyse et l'environnement de Lyon, Villeurbanne, F-69626, France Recently the surface microlayer (SML) has received growing attention for its role in the deposition and emission of trace gases. This SML is presumably a highly efficient environment for photochemical reactions thanks to its physical and chemical properties, showing enrichment in chromophores [1]. Still, little is known about the possible photochemical processes that could influence the emission and deposition of volatile organic compounds (VOCs) in the SML. A recent study underlines the particularity of the presence of an organic microlayer, showing enhanced formation of peptide bonds at the air-water interface, although this reaction is thermodynamically disfavoured in bulk water [2]. Also, emissions of small gas phase carbonyl compounds formed photochemically by dissolved organic matter have been measured above natural water and glyoxal, for example, measured above the open ocean is thought to be photochemically produced [3, 4]. This study presents the results of a set of laboratory studies set up in order to better understand the role of the SML in the photochemical production of VOCs. Recently, our group has shown the formation of VOCs by light driven reactions in a small quartz reactor (14mL) containing aqueous solutions of humic acids (HA) in the presence of an organic (artificial or natural) microlayer [5]. The main VOCs produced were oxidized species, such as aldehydes, ketones and alcohols, as classically can be expected by the oxidation of the organics present at the interface initiated by triplet excited chromophores present in the HA. But also alkenes, dienes, including isoprene and

  15. Effect of the degree of dissociation of molecules in a monolayer at an air/water interface on the force between the monolayer and a like-charged particle in the subphase.

    PubMed

    McNamee, Cathy E; Kappl, Michael; Butt, Hans-Juergen; Nguyen, Hang; Sato, Shinichiro; Graf, Karlheinz; Healy, Thomas W

    2012-11-26

    We used the monolayer particle interaction apparatus to measure the force between a monolayer of stearic acid or octadecanol at the air/water interface and a colloidal silica sphere. The silica sphere approached the monolayer from the aqueous subphase. The aim was to analyze how the magnitude of the charge of a deformable interface affects the interaction between that interface and a like-charged hard particle. The charge density of the stearic acid monolayer was controlled by adjusting the pH (5.8-9) and the surface pressure. The octadecanol monolayer acted as a reference; the alcohol headgroup did not dissociate between pH 5.8-9.0. Stable monolayers of dissociated stearic acid molecules were formed at the air/water interface by dissolving stearic acid into the subphase to give a saturated concentration at each pH value studied. The approach force curve showed that the electrostatic repulsion increased with an increasing degree of dissociation and therefore the charge of the monolayer. The strength of the repulsion corresponded to that measured between two like-charged hard surfaces, but the apparent range of the repulsion was larger for a deformable interface. Retracting force curves displayed a significant adhesion, whose magnitude and range depended on the surface pressure and subphase pH.

  16. DIFFUSIVE EXCHANGE OF GASEOUS POLYCYCLIC AROMATIC HYDROCARBONS AND POLYCHLORINATED BIPHENYLS ACROSS THE AIR-WATER INTERFACE OF THE CHESAPEAKE BAY. (R825245)

    EPA Science Inventory

    Dissolved and gas-phase concentrations of nine polycyclic aromatic hydrocarbons and 46 polychlorinated biphenyl congeners were measured at eight sites on the Chesapeake Bay at four different times of the year to estimate net diffusive air-water gas exchange rates. Gaseous PAHs ar...

  17. Comparison of the influence of fluorocarbon and hydrocarbon surfactants on the adsorptions of SDS, DTAB and C12E8 at the air/water interface by MD simulation

    NASA Astrophysics Data System (ADS)

    Pang, Jinyu; Xu, Guiying

    2012-06-01

    Adsorptions of sodium dodecylsulfate (SDS), dodecyltrimethylammonium bromide (DTAB) and octaethylene glycol monododecyl ether (C12E8) at the air/water interface in the presence of hydrocarbon and fluorocarbon surfactants (HCEP and FCEP) were investigated by molecular dynamics (MD) simulation. With the addition of HCEP or FCEP, the monolayer is more organized than in individual surfactant systems. Extremely expanded C12E8 chain in a smaller tilt angle is discovered in C12E8/HCEP system. In SDS or DTAB systems, relatively small tilt angle of surfactants is observed in the presence of FCEP. Their analog, a silicone surfactant DSEP shows a favorable effect on interfacial properties with DTAB.

  18. Air/Water Purification

    NASA Technical Reports Server (NTRS)

    1992-01-01

    After 18 years of research into air/water pollution at Stennis Space Center, Dr. B. C. Wolverton formed his own company, Wolverton Environmental Services, Inc., to provide technology and consultation in air and water treatment. Common houseplants are used to absorb potentially harmful materials from bathrooms and kitchens. The plants are fertilized, air is purified, and wastewater is converted to clean water. More than 100 U.S. communities have adopted Wolverton's earlier water hyacinth and artificial marsh applications. Catfish farmers are currently evaluating the artificial marsh technology as a purification system.

  19. Diffusive exchange of polycyclic aromatic hydrocarbons across the air-water interface of the Patapsco River, an urbanized subestuary of the Chesapeake Bay

    SciTech Connect

    Bamford, H.A.; Offenberg, J.H.; Larsen, R.K.; Ko, F.C.; Baker, J.E.

    1999-07-01

    Air-water exchange fluxes of 13 polycyclic aromatic hydrocarbons (PAHs) were determined along a transect in the Patapsco River from the Inner Harbor of Baltimore, MD, to the mainstem of the northern Chesapeake Bay. Sampling took place at six sites during three sampling intensives (June 1996, February 1997, and July 1997) and at one site every ninth day between March 1997 and March 1998 to measure spatial, daily, and annual variability in the fluxes. The direction and magnitude of the daily fluxes of individual PAHs were strongly influenced by the wind speed and direction, by the air temperature, and by the highly variable PAH concentrations in the gas and dissolved phases. Individual fluxes ranged from 14,200 ng m{sup {minus}2} day{sup {minus}1} net volatilization of fluorene during high winds to 11,400 ng m{sup {minus}2} day{sup {minus}1} net absorption of phenanthrene when prevailing winds blowing from the northwest across the city of Baltimore elevated gaseous PAH concentrations over the water. The largest PAH volatilization fluxes occurred adjacent to the stormwater discharges, driven by elevated dissolved PAH concentrations in surface waters. Estimated annual volatilization fluxes ranged from 1.1 {micro}g m{sup {minus}2} yr{sup {minus}1} for chrysene to 800 {micro}g m{sup {minus}2} yr{sup {minus}1} for fluorene.

  20. Spatial Resolution Characterization for AWiFS Multispectral Images

    NASA Technical Reports Server (NTRS)

    Blonski, Slawomir; Ryan, Robert E.; Pagnutti, Mary; Stanley, Thomas

    2006-01-01

    Within the framework of the Joint Agency Commercial Imagery Evaluation program, the National Aeronautics and Space Administration, the National Geospatial-Intelligence Agency, and the U.S. Geological Survey cooperate in the characterization of high-to-moderate-resolution commercial imagery of mutual interest. One of the systems involved in this effort is the Advanced Wide Field Sensor (AWiFS) onboard the Indian Remote Sensing (IRS) Reourcesat-1 satellite, IRS-P6. Spatial resolution of the AWiFS multispectral images was characterized by estimating the value of the system Modulation Transfer Function (MTF) at the Nyquist spatial frequency. The Nyquist frequency is defined as half the sampling frequency, and the sampling frequency is equal to the inverse of the ground sample distance. The MTF was calculated as a ratio of the Fourier transform of a profile across an AWiFS image of the Lake Pontchartrain Causeway Bridge and the Fourier transform of a profile across an idealized model of the bridge for each spectral band evaluated. The mean MTF value for the AWiFS imagery evaluated was estimated to be 0.1.

  1. Simulated Solvation of Organic Ions II: Study of Linear Alkylated Carboxylate Ions in Water Nanodrops and in Liquid Water. Propensity for Air/Water Interface and Convergence to Bulk Solvation Properties.

    PubMed

    Houriez, Céline; Meot-Ner Mautner, Michael; Masella, Michel

    2015-09-10

    We investigated the solvation of carboxylate ions from formate to hexanoate, in droplets of 50 to 1000 water molecules and neat water, by computations using standard molecular dynamics and sophisticated polarizable models. The carboxylate ions from methanoate to hexanoate show strong propensity for the air/water interface in small droplets. Only the ions larger than propanoate retain propensity for the interface in larger droplets, where their enthalpic stabilization by ion/water dispersion is reduced there by 3 kcal mol(-1) per CH2 group. This is compensated by entropy effects over +3.3 cal mol(-1) K(-1) per CH2 group. On the surface, the anionic headgroups are strongly oriented toward the aqueous core, while the hydrophobic alkyl chains are repelled into air and lose their structure-making effects. These results reproduce the structure-making effects of alkyl groups in solution, and suggest that the hydrocarbon chains of ionic headgroups and alkyl substituents solvate independently. Extrapolation to bulk solution using standard extrapolation schemes yields absolute carboxylate solvation energies. The results for formate and acetate yield a proton solvation enthalpy of about 270 kcal mol(-1), close to the experiment-based value. The largest carboxylate ions yield a value smaller by about 10 kcal mol(-1), which requires studies in much larger droplets. PMID:26287943

  2. Intermolecular forces in lipid monolayers. Two-dimensional virial coefficients for pentadecanoic acid from micromanometry on spread monolayers at the air/water interface.

    PubMed

    Pallas, Norman R; Pethica, Brian A

    2009-07-01

    The lateral intermolecular forces between surfactant or lipid molecules in monolayers at interfaces are fundamental to understanding the phenomena of surface activity and the interactions of lipids in two-dimensional structures such as smectic phases and biomembranes. The classical approach to these forces is via the two-dimensional virial coefficients, which requires precise micromanometry on monolayer isotherms in the dilute gaseous region. Low pressure isotherms out to high surface areas in the two-dimensional gas range have been measured at 15, 25 and 30 degrees C for insoluble monolayers of n-pentadecanoic acid spread at the interface between water-vapour saturated air and a dilute aqueous solution of HCl. The data allow estimates of virial coefficients up to the third term. The second virial coefficients are compared with those predicted from a statistical mechanical model for monolayers of n-alkylcarboxylic acids treated as side-by-side parallel chains extended at the surface with the carboxyl head groups shielded in the water phase. The two sets coincide at approximately 26 degrees C, but the experimental estimates show a much larger dependence on temperature than the model predicts. Chain conformation effects, head group interactions and surface field polarization are discussed as possible temperature-dependent contributions to the lateral potentials of mean force.

  3. Amine Chemistry at Aqueous Interfaces: The Study of Organic Amines in Neutralizing Acidic Gases at an Air/Water Surface Using Vibrational Sum Frequency Spectroscopy

    NASA Astrophysics Data System (ADS)

    McWilliams, L.; Wren, S. N.; Valley, N. A.; Richmond, G.

    2014-12-01

    Small organic bases have been measured in atmospheric samples, with their sources ranging from industrial processing to animal husbandry. These small organic amines are often highly soluble, being found in atmospheric condensed phases such as fogwater and rainwater. Additionally, they display acid-neutralization ability often greater than ammonia, yet little is known regarding their kinetic and thermodynamic properties. This presentation will describe the molecular level details of a model amine system at the vapor/liquid interface in the presence of acidic gas. We find that this amine system shows very unique properties in terms of its bonding, structure, and orientation at aqueous surfaces. The results of our studies using a combination of computation, vibrational sum frequency spectroscopy, and surface tension will report the properties inherent to these atmospherically relevant species at aqueous surfaces.

  4. Study of the adsorption of sodium dodecyl sulfate (SDS) at the air/water interface: targeting the sulfate headgroup using vibrational sum frequency spectroscopy.

    PubMed

    Johnson, C Magnus; Tyrode, Eric

    2005-07-01

    The surface sensitive technique vibrational sum frequency spectroscopy (VSFS), has been used to study the adsorption behaviour of SDS to the liquid/vapour interface of aqueous solutions, specifically targeting the sulfate headgroup stretches. In the spectral region extending from 980 to 1850 cm(-1), only the vibrations due to the SO(3) group were detectable. The fitted amplitudes for the symmetric SO(3) stretch observed at 1070 cm(-1) for the polarization combinations ssp and ppp, were seen to follow the adsorption isotherm calculated from surface tension measurements. The orientation of the sulfate headgroup in the concentration range spanning from 1.0 mM to above the critical micellar concentration (c.m.c.) was observed to remain constant within experimental error, with the pseudo-C(3) axis close to the surface normal. Furthermore, the effect of increasing amounts of sodium chloride at SDS concentrations above c.m.c. was also studied, showing an increase of approximately 12% in the fitted amplitude for the symmetric SO(3) stretch when increasing the ionic strength from 0 to 300 mM NaCl. Interestingly, the orientation of the SDS headgroup was also observed to remain constant within this concentration range and identical to the case without NaCl.

  5. Formation of gas-phase carbonyls from heterogeneous oxidation of polyunsaturated fatty acids at the air-water interface and of the sea surface microlayer

    NASA Astrophysics Data System (ADS)

    Zhou, S.; Gonzalez, L.; Leithead, A.; Finewax, Z.; Thalman, R.; Vlasenko, A.; Vagle, S.; Miller, L. A.; Li, S.-M.; Bureekul, S.; Furutani, H.; Uematsu, M.; Volkamer, R.; Abbatt, J.

    2014-02-01

    Motivated by the potential for reactive heterogeneous chemistry occurring at the ocean surface, gas-phase products were observed when a reactive sea surface microlayer (SML) component, i.e. the polyunsaturated fatty acids (PUFA) linoleic acid (LA), was exposed to gas-phase ozone at the air-seawater interface. Similar oxidation experiments were conducted with SML samples collected from two different oceanic locations, in the eastern equatorial Pacific Ocean and from the west coast of Canada. Online proton-transfer-reaction mass spectrometry (PTR-MS) University of Colorado light-emitting diode cavity-enhanced differential optical absorption spectroscopy (LED-CE-DOAS) were used to detect oxygenated gas-phase products from the ozonolysis reactions. The LA studies indicate that oxidation of a PUFA monolayer on seawater gives rise to prompt and efficient formation of gas-phase aldehydes. The products are formed via the decomposition of primary ozonides which form upon the initial reaction of ozone with the carbon-carbon double bonds in the PUFA molecules. In addition, two highly reactive dicarbonyls, malondialdehyde (MDA) and glyoxal, were also generated, likely as secondary products. Specific yields relative to reactant loss were 78%, 29%, 4% and < 1% for n-hexanal, 3-nonenal, MDA and glyoxal, respectively, where the yields for MDA and glyoxal are likely lower limits. Heterogeneous oxidation of SML samples confirm for the first time that similar carbonyl products are formed via ozonolysis of environmental samples.

  6. Formation of gas-phase carbonyls from heterogeneous oxidation of polyunsaturated fatty acids at the air-water interface and of the sea surface microlayer

    NASA Astrophysics Data System (ADS)

    Zhou, S.; Gonzalez, L.; Leithead, A.; Finewax, Z.; Thalman, R.; Vlasenko, A.; Vagle, S.; Miller, L.; Li, S.-M.; Bureekul, S.; Furutani, H.; Uematsu, M.; Volkamer, R.; Abbatt, J.

    2013-07-01

    Motivated by the potential for reactive heterogeneous chemistry occurring at the ocean surface, gas-phase products were observed when a reactive sea surface microlayer (SML) component, i.e. the polyunsaturated fatty acid (PUFA) linoleic acid (LA), was exposed to gas-phase ozone at the air-seawater interface. Similar oxidation experiments were conducted with SML samples collected from two different oceanic locations, in the eastern equatorial Pacific Ocean and from the west coast of Canada. Online proton-transfer-reaction mass spectrometry (PTR-MS) and light-emitting diode cavity enhanced differential optical absorption spectroscopy (LED-CE-DOAS) were used to detect oxygenated gas-phase products from the ozonolysis reactions. The LA studies indicate that oxidation of a PUFA monolayer on seawater gives rise to prompt and efficient formation of gas phase aldehydes. The products are formed via the decomposition of primary ozonides which form upon the initial reaction of ozone with the carbon-carbon double bonds in the PUFA molecules. In addition, two highly reactive di-carbonyls, malondialdehyde (MDA) and glyoxal, were also generated, likely as secondary products. Specific yields relative to reactant loss were 78%, 29%, 4% and <1% for n-hexanal, 3-nonenal, MDA and glyoxal, respectively, where the yields for MDA and glyoxal are likely lower limits. Heterogeneous oxidation of SML samples confirm for the first time that similar carbonyl products are formed via ozonolysis of environmental samples. The potential impact of such chemistry on the atmosphere of the marine boundary layer is discussed.

  7. The formation of surface multilayers at the air-water interface from sodium diethylene glycol monoalkyl ether sulfate/AlCl3 solutions: the role of the alkyl chain length.

    PubMed

    Xu, Hui; Penfold, Jeffrey; Thomas, Robert K; Petkov, Jordan T; Tucker, Ian; Webster, John P R

    2013-10-15

    The influence of the alkyl chain length on surface multilayer formation at the air-water interface for the anionic surfactant sodium diethylene glycol monoalkyl ether sulfate, SAE2S, in the presence of Al(3+) multivalent counterions, in the form of AlCl3, is described. In the absence of electrolyte, the saturated monolayer adsorption is determined by the headgroup geometry and is independent of the alkyl chain length. In the presence of Al(3+) counterions, surface multilayer formation occurs, due to the strong SAE2S/Al(3+) binding and complexation. The neutron reflection data show that the alkyl chain length of the surfactant has a significant impact upon the evolution of the surface multilayer structure with surfactant and AlCl3 concentration. Increasing the alkyl chain length from decyl to tetradecyl results in the surface multilayer formation occurring at lower surfactant and AlCl3 concentrations. At the short alkyl chain lengths, decyl and dodecyl, the regions of multilayer formation with a small number of bilayers are increasingly extended with decreasing alkyl chain length. For the alkyl chain lengths of tetradecyl and hexadecyl, the surface behavior is further affected by decreases in the surfactant solubility in the presence of AlCl3, and this ultimately dominates the surface behavior at the longer alkyl chain lengths.

  8. Initial Radiometric Calibration of the AWiFS Using Vicarious Calibration Techniques

    NASA Technical Reports Server (NTRS)

    Pagnutti, Mary

    2007-01-01

    The NASA team of University of Arizona, South Dakota State University, and NASA SSC produce consistent results. The AWiFS calibration coefficients agree reasonably well with the NASA team estimate. The NASA team will continue to assess AWiFS radiometric accuracy.

  9. Pulmonary surfactant proteins SP-B and SP-C in spread monolayers at the air-water interface: I. Monolayers of pulmonary surfactant protein SP-B and phospholipids.

    PubMed Central

    Taneva, S; Keough, K M

    1994-01-01

    The effects of pulmonary surfactant protein SP-B on the properties of monolayers of dipalmitoylphosphatidylcholine (DPPC) and dipalmitoylphosphatidylglycerol (DPPG), and a mixture of DPPC:DPPG (7:3, mol:mol) were studied using spread films at the air-water interface. The addition of SP-B to the phospholipid monolayers gave positive deviations from additivity of the mean areas in the films. At low protein concentrations (less than 45% amino acid residues which corresponds to 0.5 mol% or 10 weight% SP-B) monolayers of SP-B/DPPC, SP-B/DPPG and SP-B/(DPPC:DPPG) collapsed at surface pressures of about 70 mN.m-1, comparable to those of the lipids alone. At higher concentrations of SP-B in the protein-lipid monolayers, kink points appeared in the isotherms at about 40-45 mN.m-1, implying possible exclusion of material from the films, hence, changes in the original monolayer compositions. Calculated analyses of the monolayer compositions as a function of surface pressure indicated that nearly pure SP-B, associated with small amounts of phospholipid (2-3 lipid molecules per SP-B dimer), was lost from SP-B/DPPC, SP-B/DPPG, and SP-B/(DPPC:DPPG) films at surface pressures higher than 40-45 mN.m-1. The results are consistent with a low effectiveness of SP-B in removing saturated phospholipids, DPPC or DPPG, from the spread SP-B/phospholipid films. PMID:8038385

  10. Self-Organization of Polystyrene-b-polyacrylic Acid (PS-b-PAA) Monolayer at the Air/Water Interface: A Process Driven by the Release of the Solvent Spreading.

    PubMed

    Guennouni, Zineb; Cousin, Fabrice; Fauré, Marie-Claude; Perrin, Patrick; Limagne, Denis; Konovalov, Oleg; Goldmann, Michel

    2016-03-01

    We present an in situ structural study of the surface behavior of PS-b-PAA monolayers at the air/water interface at pH 2, for which the PAA blocks are neutral and using N,N-dimethyformamide (DMF) as spreading solvent. The surface pressure versus molecular area isotherm shows a perfectly reversible pseudoplateau over several cycles of compression/decompression. The width of such plateau enlarges when increasing temperature, conversely to what is classically observed in the case of an in-plane first order transition. We combined specular neutron reflectivity (SNR) experiments with contrast variation to solve the profile of each block perpendicular to the surface with grazing-incidence small-angle scattering (GISAXS) measurements to determine the in-plane structure of the layer. SNR experiments showed that both PS and PAA blocks remain adsorbed on the surface for all surface pressure probed. A correlation peak at Q(xy)* = 0.021 Å(-1) is evidenced by GISAXS at very low surface pressure which intensity first increases on the plateau. When compressing further, its intensity decays while Q(xy)* is shifted toward low Q(xy). The peak fully disappears at the end of the plateau. These results are interpreted by the formation of surface aggregates induced by DMF molecules at the surface. These DMF molecules remain adsorbed within the PS core of the aggregates. Upon compression, they are progressively expelled from the monolayer, which gives rise to the pseudoplateau on the isotherm. The intensity of the GISAXS correlation peak is set by the amount of DMF within the monolayer as it vanishes when all DMF molecules are expelled. This result emphizes the role of the solvent in Langmuir monolayer formed by amphiphilic copolymers which hydrophobic and hydrophilic parts are composed by long polymer chains.

  11. SSC Geopositional Assessment of an AWiFS Image Orthorectified Product

    NASA Technical Reports Server (NTRS)

    Kenton, Ross; Stubbs, Ruby

    2007-01-01

    The geopositional accuracy of an AWiFS (Advanced Wide Field Sensor) orthorectified product was evaluated. Specifically, the image products were acquired by the Indian Remote Sensing Resourcesat-1 satellite, then orthorectified by GeoEye . Analysis was performed using DOQs (digital orthophoto quadrangles) and other reference sources of similar accuracy. A total of six AWiFS images were characterized. These images were acquired over the continental United States from June through September 2005. The images were equally divided between the two AWiFS cameras. Forty to fifty check points were collected manually per scene and analyzed to determine overall circular error, estimates of horizontal bias, and other systematic errors.

  12. Stereoselective synthesis of (2S,3S,4Z)-4-fluoro-1,3-dihydroxy-2-(octadecanoylamino)octadec-4-ene, [(Z)-4-fluoroceramide], and its phase behavior at the air/water interface

    PubMed Central

    Nikolova, Gergana S

    2008-01-01

    natural ceramide. Conclusions Asymmetric aldol reaction proved to be successful for the preparation of enantiopure 4-fluoroceramide. Surface/pressure isotherms and hysteresis curves of ceramide and its 4-fluoro derivative showed that the presence of fluorine leads to stronger intermolecular interactions between the hydrophobic chains of neighboring molecules, and therefore to increasing stability of the monolayer of 4-fluoroceramide at the air water interface. PMID:18941484

  13. Crop Acreage Estimation: Landsat TM and Resourcesat-1 AWiFS Sensor Assessment of the Mississippi River Delta, 2005

    NASA Technical Reports Server (NTRS)

    Boryan, Claire; Johnson, Dave; Craig, Mike; Seffrin, Bob; Mueller, RIck

    2007-01-01

    AWiFs data are appropriate for crop acreage estimation over large, spectrally homogenous, crop areas such as the Mid-West, the Delta and the Northern Great Plains. Regression and Kappa statistics for soybean, corn, cotton, rice and sorghum produced using both the Landsat TM and AWiFS data are very similar. AWiFS data appear to be a suitable alternative or supplement to Landsat TM data for production of NASS'Cropland Data Layer product.

  14. Effects of Temperature, Oxygen Level, Ionic Strength, and pH on the Reaction of Benzene with Hydroxyl Radicals at the Air-Water Interface in Comparison to the Bulk Aqueous Phase.

    PubMed

    Heath, Aubrey A; Valsaraj, Kalliat T

    2015-08-01

    Atmospheric aerosols (e.g., fog droplets) are complex, multiphase mediums. Depending on location, time of day, and/or air mass source, there can be considerable variability within these droplets, relating to temperature, pH, and ionic strength. Due to the droplets' inherently small size, the reactions that occur within these droplets are determined by bulk aqueous phase and air-water interfacial conditions. In this study, the reaction of benzene and hydroxyl radicals is examined kinetically in a thin-film flow-tube reactor. By varying the aqueous volume (e.g., film thickness) along the length of the reactor, both bulk and interfacial reaction rates are measured from a single system. Temperature, pH, and ionic strength are varied to model conditions typical of fog events. Oxygen-poor conditions are measured to study oxygen's overall effect on the reaction pathway. Initial rate activation energies and the bulk aqueous phase and interfacial contributions to the overall rate constant are also obtained. PMID:26158391

  15. Effects of Temperature, Oxygen Level, Ionic Strength, and pH on the Reaction of Benzene with Hydroxyl Radicals at the Air-Water Interface in Comparison to the Bulk Aqueous Phase.

    PubMed

    Heath, Aubrey A; Valsaraj, Kalliat T

    2015-08-01

    Atmospheric aerosols (e.g., fog droplets) are complex, multiphase mediums. Depending on location, time of day, and/or air mass source, there can be considerable variability within these droplets, relating to temperature, pH, and ionic strength. Due to the droplets' inherently small size, the reactions that occur within these droplets are determined by bulk aqueous phase and air-water interfacial conditions. In this study, the reaction of benzene and hydroxyl radicals is examined kinetically in a thin-film flow-tube reactor. By varying the aqueous volume (e.g., film thickness) along the length of the reactor, both bulk and interfacial reaction rates are measured from a single system. Temperature, pH, and ionic strength are varied to model conditions typical of fog events. Oxygen-poor conditions are measured to study oxygen's overall effect on the reaction pathway. Initial rate activation energies and the bulk aqueous phase and interfacial contributions to the overall rate constant are also obtained.

  16. Cleaning verification by air/water impingement

    NASA Technical Reports Server (NTRS)

    Jones, Lisa L.; Littlefield, Maria D.; Melton, Gregory S.; Caimi, Raoul E. B.; Thaxton, Eric A.

    1995-01-01

    This paper will discuss how the Kennedy Space Center intends to perform precision cleaning verification by Air/Water Impingement in lieu of chlorofluorocarbon-113 gravimetric nonvolatile residue analysis (NVR). Test results will be given that demonstrate the effectiveness of the Air/Water system. A brief discussion of the Total Carbon method via the use of a high temperature combustion analyzer will also be given. The necessary equipment for impingement will be shown along with other possible applications of this technology.

  17. Air/water interfacial formation of freestanding, stimuli-responsive, self-healing catecholamine Janus-faced microfilms.

    PubMed

    Hong, Seonki; Schaber, Clemens F; Dening, Kirstin; Appel, Esther; Gorb, Stanislav N; Lee, Haeshin

    2014-12-01

    A catecholamine freestanding film is discovered to be spontaneously formed at the air-water interface, and the film has unique properties of robust surface adhesiveness, self-healing, and stimuli-responsive properties. The interfacial film-producing procedure is a simple single step containing polyamines and catechol(amine)s. It is found that oxygen-rich regions existing at an air-water interface greatly accelerate the catecholamine crosslinking reaction. PMID:25220108

  18. Air/water interfacial formation of freestanding, stimuli-responsive, self-healing catecholamine Janus-faced microfilms.

    PubMed

    Hong, Seonki; Schaber, Clemens F; Dening, Kirstin; Appel, Esther; Gorb, Stanislav N; Lee, Haeshin

    2014-12-01

    A catecholamine freestanding film is discovered to be spontaneously formed at the air-water interface, and the film has unique properties of robust surface adhesiveness, self-healing, and stimuli-responsive properties. The interfacial film-producing procedure is a simple single step containing polyamines and catechol(amine)s. It is found that oxygen-rich regions existing at an air-water interface greatly accelerate the catecholamine crosslinking reaction.

  19. Impact of AWiFS derived land use land cover on simulation of heavy rainfall

    NASA Astrophysics Data System (ADS)

    Karri, Srinivasarao; Gharai, Biswadip; Sai Krishna, S. V. S.; Rao, P. V. N.

    2016-05-01

    Land use/land cover (LU/LC) changes are considered to be one of the most important factors affecting regional climate and are thus an area of public concern. The land surface plays a crucial role in boundary layer evolution and precipitation patterns thereby establishing the need for LU/LC inputs as a critical part of modeling systems. Inaccurate LU/LC information often leads to very large errors in surface energy fluxes thus leading to errors in boundary layer state. We have investigated an incident of heavy rainfall during August 2015 over West Bengal, India using Weather Research and Forecast (WRF) model by incorporating different LU/LC datasets, IRS P6 Advanced Wide Field Sensor (AWiFS) LU/LC data for 2012-13 and the default Moderate Resolution Imaging Spectro-radiometer (MODIS) derived USGS LU/LC data for 2001. In the present study, we have made a comparative assessment between AWiFS derived LU/LC and USGS LU/LC by incorporating these datasets as one of the lower boundary conditions over Indian region in WRF model version 3.5.1 to simulate, at 10km resolution, a heavy rainfall event associated with landfall of a cyclonic system over West Bengal. The results of the study suggested influence of LU/LC in occurrence of heavy rainfall with WRF model using AWiFS LU/LC showing more realistic simulation as AWiFS LU/LC is more up-to-date and features recent changes in LU/LC over India.

  20. Complementarity of ResourceSat-1 AWiFS and Landsat TM/ETM+ sensors

    USGS Publications Warehouse

    Goward, S.N.; Chander, G.; Pagnutti, M.; Marx, A.; Ryan, R.; Thomas, N.; Tetrault, R.

    2012-01-01

    Considerable interest has been given to forming an international collaboration to develop a virtual moderate spatial resolution land observation constellation through aggregation of data sets from comparable national observatories such as the US Landsat, the Indian ResourceSat and related systems. This study explores the complementarity of India's ResourceSat-1 Advanced Wide Field Sensor (AWiFS) with the Landsat 5 Thematic Mapper (TM) and Landsat 7 Enhanced Thematic Mapper Plus (ETM+). The analysis focuses on the comparative radiometry, geometry, and spectral properties of the two sensors. Two applied assessments of these data are also explored to examine the strengths and limitations of these alternate sources of moderate resolution land imagery with specific application domains. There are significant technical differences in these imaging systems including spectral band response, pixel dimensions, swath width, and radiometric resolution which produce differences in observation data sets. None of these differences was found to strongly limit comparable analyses in agricultural and forestry applications. Overall, we found that the AWiFS and Landsat TM/ETM+ imagery are comparable and in some ways complementary, particularly with respect to temporal repeat frequency. We have found that there are limits to our understanding of the AWiFS performance, for example, multi-camera design and stability of radiometric calibration over time, that leave some uncertainty that has been better addressed for Landsat through the Image Assessment System and related cross-sensor calibration studies. Such work still needs to be undertaken for AWiFS and similar observatories that may play roles in the Global Earth Observation System of Systems Land Surface Imaging Constellation.

  1. Applications of TsunAWI: Operational scenario database in Indonesia, case studies in Chile

    NASA Astrophysics Data System (ADS)

    Rakowsky, Natalja; Harig, Sven; Immerz, Antonia; Androsov, Alexey; Hiller, Wolfgang; Schröter, Jens

    2016-04-01

    The numerical simulation code TsunAWI was developed in the framework of the German-Indonesian Tsunami Early Warning System (GITEWS). The Numerical simulation of prototypic tsunami scenarios plays a decisive role in the a priori risk assessment for coastal regions and in the early warning process itself. TsunAWI is suited for both tasks. It is based on a finite element discretisation, employs unstructured grids with high resolution along the coast, and includes inundation. This contribution presents two fields of applications. In the Indonesian tsunami early warning system, the existing TsunAWI scenario database covers the Sunda subduction zone from Sumatra to the Lesser Sunda Islands with 715 epicenters and 4500 scenarios. In a collaboration with Geoscience Australia, we support the scientific staff at the Indonesian warning center to extend the data base to the remaining tectonic zones in the Indonesian Archipelago. The extentension started for North Sulawesi, West and East Maluku Islands. For the Hydrographic and Oceanographic Service of the Chilean Navy (SHOA), we calculated a small scenario database of 100 scenarios (sources by Universidad de Chile) for a lightweight decision support system prototype (built by DLR). The earthquake and tsunami events on 1 April 2014 and 16 November 2016 showed the practical use of this approach in comparison to hind casts of these events.

  2. Radiometric Calibration of the AWiFS Using Vicarious Calibration Techniques

    NASA Technical Reports Server (NTRS)

    Pagnutti, Mary; Holekamp, Kara

    2007-01-01

    A radiometric calibration assessment of the AWiFS (Advanced Wide Field Sensor) on the Indian Remote Sensing Resourcesat-1 satellite was performed by the NASA Applied Research & Technology Project Office (formerly the Applied Sciences Directorate) at the John C. Stennis Space Center. A reflectance-based vicarious calibration approach, requiring ground-based measurements coincident with satellite acquisitions and radiative transfer calculations, was used to estimate at-sensor radiance. The AWiFS is a 4-band, multispectral, moderate-resolution (60 m) imaging sensor that operates in the visible through short-wave infrared spectrum and is currently being considered as a Landsat-like alternative. Several study sites near the Stennis Space Center that attempted to span the dynamic range of the sensor were employed. Satellite at-sensor radiance values were compared to those estimated to determine the sensor's radiometric accuracy. The results of this evaluation provide the user community with an independent assessment of the radiometric accuracy of AWiFS image products, which are commercially available through GeoEye. These results are an extension of an independent assessment made by the University of Arizona Remote Sensing Group, the South Dakota State University Satellite Calibration Group & Image Processing Lab, and the NASA Applied Sciences Directorate at the John C. Stennis Space Center the previous year.

  3. Two-dimensional pigment monolayer assemblies for light-harvesting applications: Structural characterization at the air/water interface with X-ray specular reflectivity and on solid substrates by optical absorption spectroscopy

    SciTech Connect

    Gregory, B.W.; Vaknin, D.; Gray, J.D. |; Ocko, B.M.; Stroeve, P.; Cotton, T.M.; Struve, W.S.

    1997-03-13

    X-ray specular reflectivity at the liquid/gas interface of dihexadecyl phosphate (DHDP) on pure H{sub 2}O and on a series of pigment-containing aqueous solutions are reported along with visible absorption spectra of corresponding monomolecular Langmuir-Blodgett films on quartz substrates. Reflectivity from DHDP reveals that at large surface pressure, the film is closely packed with untilted hydrocarbon chains and hydrated phosphate headgroups. Visible absorption spectra of all transferred films indicate a closely packed single pigment layer, consistent with reflectivity results. The existence of a complete pigment monolayer over the measured surface-pressure-molecular area isotherms has been evidenced by both X-ray reflectivity and visible optical studies. 64 refs., 8 figs., 3 tabs.

  4. OH-radical specific addition to the antioxidant glutathione S-atom at the air-water interface - Relevance to the redox balance of the lung epithelial lining fluid and the causality of adverse health effects induced by air pollution

    NASA Astrophysics Data System (ADS)

    Colussi, A. J.; Enami, S.; Hoffmann, M. R.

    2015-12-01

    Inhalation of oxidant pollutants upsets the redox balance (RB) of the lung epithelial lining fluid (ELF) by triggering the formation of reactive OH-radicals therein. RB is deemed to be controlled by the equilibrium between the most abundant ELF protective antioxidant glutathione (GSH) and its putative disulfide GSSG oxidation product. The actual species produced from the oxidation of GSH initiated by ·OH in ELF interfacial layers exposed to air, i.e., under realistic ELF conditions, however, were never identified. Here we report the online electrospray mass spectrometric detection of sulfenate (GSO-), sulfinate (GSO2-) and sulfonate (GSO3-) on the surface of aqueous GSH solutions collided with ·OH(g). We show that these products arise from ·OH specific additions to S-atoms, rather than via H-abstraction from GS-H. The remarkable specificity of ·OH in interfacial water vis-a-vis its lack of selectivity in bulk water implicates an unprecedented steering process during ·OH-GSH encounters at water interfaces. A non-specific systemic immune response to inhaled oxidants should be expected if they were initially converted into a common ·OH intermediate on the ELF (e.g., via fast Fenton chemistry) and oxidative stress signaled by the [GSH]/[GSOH] ratio.

  5. Radiometric Calibration of the AWiFS Sensor and a Cross-calibration Enhanced Vicarious Calibration Technique

    NASA Technical Reports Server (NTRS)

    Aaron, David

    2007-01-01

    Using vicarious calibration validation of moderate resolution sensors such as AWiFS is complicated by requiring more land area to ensure proper registration and sufficient pixel numbers. A trial AWiFS calibration was performed on a grass site that consisted of two dramatically different grass heights. Ground truth data was collected over relatively small areas representing only a few pixels. The radiometric gain results for each of these areas will be reported. To enhance this analysis, since a near coincidence high resolution image was collected, the high resolution data was effectively resized to produce pixels comparable to AWiFS and the atmospheric model was used to produce a top of canopy radiance map. Multiple uniform vegetated areas of several radiances were then identified and subsequently propagated to the top of atmosphere viewpoint of the moderate resolution (AWiFS) satellite. The radiometric gain was then calculated based on the vendor high resolution satellite gains (for the 3 bands with comparable wavelengths). Band-to-band conversion was performed assuming a hyperspectral reflectance based on the standard vegetated site. The initial comparison produces AWiFS radiometric gain values that agree to better than 10% of the values measured using the standard vicarious gain technique.

  6. Cross-sensor comparisons between Landsat 5 TM and IRS-P6 AWiFS and disturbance detection using integrated Landsat and AWiFS time-series images

    USGS Publications Warehouse

    Chen, Xuexia; Vogelmann, James E.; Chander, Gyanesh; Ji, Lei; Tolk, Brian; Huang, Chengquan; Rollins, Matthew

    2013-01-01

    Routine acquisition of Landsat 5 Thematic Mapper (TM) data was discontinued recently and Landsat 7 Enhanced Thematic Mapper Plus (ETM+) has an ongoing problem with the scan line corrector (SLC), thereby creating spatial gaps when covering images obtained during the process. Since temporal and spatial discontinuities of Landsat data are now imminent, it is therefore important to investigate other potential satellite data that can be used to replace Landsat data. We thus cross-compared two near-simultaneous images obtained from Landsat 5 TM and the Indian Remote Sensing (IRS)-P6 Advanced Wide Field Sensor (AWiFS), both captured on 29 May 2007 over Los Angeles, CA. TM and AWiFS reflectances were compared for the green, red, near-infrared (NIR), and shortwave infrared (SWIR) bands, as well as the normalized difference vegetation index (NDVI) based on manually selected polygons in homogeneous areas. All R2 values of linear regressions were found to be higher than 0.99. The temporally invariant cluster (TIC) method was used to calculate the NDVI correlation between the TM and AWiFS images. The NDVI regression line derived from selected polygons passed through several invariant cluster centres of the TIC density maps and demonstrated that both the scene-dependent polygon regression method and TIC method can generate accurate radiometric normalization. A scene-independent normalization method was also used to normalize the AWiFS data. Image agreement assessment demonstrated that the scene-dependent normalization using homogeneous polygons provided slightly higher accuracy values than those obtained by the scene-independent method. Finally, the non-normalized and relatively normalized ‘Landsat-like’ AWiFS 2007 images were integrated into 1984 to 2010 Landsat time-series stacks (LTSS) for disturbance detection using the Vegetation Change Tracker (VCT) model. Both scene-dependent and scene-independent normalized AWiFS data sets could generate disturbance maps similar to

  7. Historicizing Teaching in Awgni as a Mother Tongue Language at Primary Schools of Awi Nationality Administrative Zone: Challenges and Implementation

    ERIC Educational Resources Information Center

    Engida, Alemayehu Erkihun

    2015-01-01

    This study examined the challenges facing the teaching as well as the implementation of Awgni as a mother tongue language in primary schools of Awi administrative zone. The need to teach through mother tongue in Ethiopia was widely discussed following the change of the politics in 1991. To this end, the government issued new education and training…

  8. Air-water flow in subsurface systems

    NASA Astrophysics Data System (ADS)

    Hansen, A.; Mishra, P.

    2013-12-01

    Groundwater traces its roots to tackle challenges of safe and reliable drinking water and food production. When the groundwater level rises, air pressure in the unsaturated Vadose zone increases, forcing air to escape from the ground surface. Abnormally high and low subsurface air pressure can be generated when the groundwater system, rainfall, and sea level fluctuation are favorably combined [Jiao and Li, 2004]. Through this process, contamination in the form of volatile gases may diffuse from the ground surface into residential areas, or possibly move into groundwater from industrial waste sites. It is therefore crucial to understand the combined effects of air-water flow in groundwater system. Here we investigate theoretically and experimentally the effects of air and water flow in groundwater system.

  9. Diversity and habitat association of small mammals in Aridtsy forest, Awi Zone, Ethiopia

    PubMed Central

    BANTIHUN, Getachew; BEKELE, Afework

    2015-01-01

    Here, we conducted a survey to examine the diversity, distribution and habitat association of small mammals from August 2011 to February 2012 incorporating both wet and dry seasons in Aridtsy forest, Awi Zone, Ethiopia. Using Sherman live traps and snap traps in four randomly selected trapping grids, namely, natural forest, bushland, grassland and farmland, a total of 468 individuals comprising eight species of small mammals (live traps) and 89 rodents of six species (snap traps) were trapped in 2352 and 1200 trap nights, respectively. The trapped small mammals included seven rodents and one insectivore: Lophuromys flavopuntatus (30.6%), Arvicanthis dembeensis (25.8%), Stenocephalemys albipes (20%), Mastomys natalensis (11.6%), Pelomys harringtoni (6.4%), Acomys cahirinus (4.3%), Lemniscomys zebra (0.2%) and the greater red musk shrew (Crocidura flavescens, 1.1%). Analysis showed statistically significant variations in the abundance and habitat preferences of small mammals between habitats during wet and dry seasons. PMID:25855227

  10. Diversity and habitat association of small mammals in Aridtsy forest, Awi Zone, Ethiopia.

    PubMed

    Bantihun, Getachew; Bekele, Afework

    2015-03-18

    Here, we conducted a survey to examine the diversity, distribution and habitat association of small mammals from August 2011 to February 2012 incorporating both wet and dry seasons in Aridtsy forest, Awi Zone, Ethiopia. Using Sherman live traps and snap traps in four randomly selected trapping grids, namely, natural forest, bushland, grassland and farmland, a total of 468 individuals comprising eight species of small mammals (live traps) and 89 rodents of six species (snap traps) were trapped in 2352 and 1200 trap nights, respectively. The trapped small mammals included seven rodents and one insectivore: Lophuromys flavopuntatus (30.6%), Arvicanthis dembeensis (25.8%), Stenocephalemys albipes (20%), Mastomys natalensis (11.6%), Pelomys harringtoni (6.4%), Acomys cahirinus (4.3%), Lemniscomys zebra (0.2%) and the greater red musk shrew (Crocidura flavescens, 1.1%). Analysis showed statistically significant variations in the abundance and habitat preferences of small mammals between habitats during wet and dry seasons.

  11. Surface Wave Driven Air-Water Plasmas

    NASA Astrophysics Data System (ADS)

    Tatarova, Elena; Henriques, Julio; Ferreira, Carlos

    2013-09-01

    The performance of a surface wave driven air-water plasma source operating at atmospheric pressure and 2.45 GHz has been analyzed. A 1D model has been developed in order to describe in detail the creation and loss processes of active species of interest and to provide a complete characterization of the axial structure of the source, including the discharge and the afterglow zones. The main electron creation channel was found to be the associative ionization process N +O -->NO+ + e. The NO(X) relative density in the afterglow plasma jet ranges from 1.2% to 1.6% depending on power and water percentage according to the model predictions and the measurements. Other types of species such as NO2 and nitrous acid HNO2 have also been detected by mass and FT-IR spectroscopy. Furthermore, high densities of O2(a1Δg) singlet delta oxygen molecules and OH radicals (1% and 5%, respectively) can be achieved in the discharge zone. In the late afterglow the O2(a1Δg) density is about 0.1% of the total density. The plasma source has a flexible operation and potential for channeling the energy in ways that maximize the density of active species of interest. This study was funded by the Foundation for Science and Technology, Portuguese Ministry of Education and Science, under the research contract PTDC/FIS/108411/2008.

  12. A Narrow Amide I Vibrational Band Observed by Sum Frequency Generation Spectroscopy Reveals Highly Ordered Structures of a Biofilm Protein at the Air/Water Interface†

    PubMed Central

    Wang, Zhuguang; Morales-Acosta, M. Daniela; Li, Shanghao; Liu, Wei; Kanai, Tapan; Liu, Yuting; Chen, Ya-Na; Walker, Frederick J.; Ahn, Charles H.; Leblanc, Roger M.

    2016-01-01

    We characterized BslA, a bacterial biofilm protein, at the air/water interface using vibrational sum frequency generation spectroscopy and observed one of the sharpest amide I band ever reported. Combining methods of surface pressure measurements, thin film X-ray reflectivity, and atomic force microscopy, we showed extremely ordered BslA at the interface. PMID:26779572

  13. Ground based measurements on reflectance towards validating atmospheric correction algorithms on IRS-P6 AWiFS data

    NASA Astrophysics Data System (ADS)

    Rani Sharma, Anu; Kharol, Shailesh Kumar; Kvs, Badarinath; Roy, P. S.

    In Earth observation, the atmosphere has a non-negligible influence on the visible and infrared radiation which is strong enough to modify the reflected electromagnetic signal and at-target reflectance. Scattering of solar irradiance by atmospheric molecules and aerosol generates path radiance, which increases the apparent surface reflectance over dark surfaces while absorption by aerosols and other molecules in the atmosphere causes loss of brightness to the scene, as recorded by the satellite sensor. In order to derive precise surface reflectance from satellite image data, it is indispensable to apply the atmospheric correction which serves to remove the effects of molecular and aerosol scattering. In the present study, we have implemented a fast atmospheric correction algorithm to IRS-P6 AWiFS satellite data which can effectively retrieve surface reflectance under different atmospheric and surface conditions. The algorithm is based on MODIS climatology products and simplified use of Second Simulation of Satellite Signal in Solar Spectrum (6S) radiative transfer code, which is used to generate look-up-tables (LUTs). The algorithm requires information on aerosol optical depth for correcting the satellite dataset. The proposed method is simple and easy to implement for estimating surface reflectance from the at sensor recorded signal, on a per pixel basis. The atmospheric correction algorithm has been tested for different IRS-P6 AWiFS False color composites (FCC) covering the ICRISAT Farm, Patancheru, Hyderabad, India under varying atmospheric conditions. Ground measurements of surface reflectance representing different land use/land cover, i.e., Red soil, Chick Pea crop, Groundnut crop and Pigeon Pea crop were conducted to validate the algorithm and found a very good match between surface reflectance and atmospherically corrected reflectance for all spectral bands. Further, we aggregated all datasets together and compared the retrieved AWiFS reflectance with

  14. Surface Mechanical and Rheological Behaviors of Biocompatible Poly((D,L-lactic acid-ran-glycolic acid)-block-ethylene glycol) (PLGA-PEG) and Poly((D,L-lactic acid-ran-glycolic acid-ran-ε-caprolactone)-block-ethylene glycol) (PLGACL-PEG) Block Copolymers at the Air-Water Interface.

    PubMed

    Kim, Hyun Chang; Lee, Hoyoung; Khetan, Jawahar; Won, You-Yeon

    2015-12-29

    Air-water interfacial monolayers of poly((D,L-lactic acid-ran-glycolic acid)-block-ethylene glycol) (PLGA-PEG) exhibit an exponential increase in surface pressure under high monolayer compression. In order to understand the molecular origin of this behavior, a combined experimental and theoretical investigation (including surface pressure-area isotherm, X-ray reflectivity (XR) and interfacial rheological measurements, and a self-consistent field (SCF) theoretical analysis) was performed on air-water monolayers formed by a PLGA-PEG diblock copolymer and also by a nonglassy analogue of this diblock copolymer, poly((D,L-lactic acid-ran-glycolic acid-ran-caprolactone)-block-ethylene glycol) (PLGACL-PEG). The combined results of this study show that the two mechanisms, i.e., the glass transition of the collapsed PLGA film and the lateral repulsion of the PEG brush chains that occur simultaneously under lateral compression of the monolayer, are both responsible for the observed PLGA-PEG isotherm behavior. Upon cessation of compression, the high surface pressure of the PLGA-PEG monolayer typically relaxes over time with a stretched exponential decay, suggesting that in this diblock copolymer situation, the hydrophobic domain formed by the PLGA blocks undergoes glass transition in the high lateral compression state, analogously to the PLGA homopolymer monolayer. In the high PEG grafting density regime, the contribution of the PEG brush chains to the high monolayer surface pressure is significantly lower than what is predicted by the SCF model because of the many-body attraction among PEG segments (referred to in the literature as the "n-cluster" effects). The end-grafted PEG chains were found to be protein resistant even under the influence of the "n-cluster" effects.

  15. Propagation of density disturbances in air-water flow

    NASA Technical Reports Server (NTRS)

    Nassos, G. P.

    1969-01-01

    Study investigated the behavior of density waves propagating vertically in an atmospheric pressure air-water system using a technique based on the correlation between density change and electric resistivity. This information is of interest to industries working with heat transfer systems and fluid power and control systems.

  16. External exposure to radionuclides in air, water, and soil

    SciTech Connect

    Eckerman, K.F.; Ryman, J.C.

    1996-05-01

    Federal Guidance Report No. 12 tabulates dose coefficients for external exposure to photons and electrons emitted by radionuclides distributed in air, water, and soil. The dose coefficients are intended for use by Federal Agencies in calculating the dose equivalent to organs and tissues of the body.

  17. Numerical Modeling of Surfactant-Induced Flow During Laboratory Measurement of Air-Water Interfacial Area

    NASA Astrophysics Data System (ADS)

    Henry, E. J.; Costanza-Robinson, M. S.

    2010-12-01

    An understanding of the relationship between air-water interfacial area (AI) and moisture saturation (SW) is necessary for the accurate prediction of the subsurface transport of solutes that partition to the interface or are readily transferred across the interface. Interfacial areas are commonly measured in a laboratory soil column using the aqueous interfacial-partitioning tracer methodology (IPT), in which AI is calculated based on the ratio of travel times of interfacial and non-reactive tracers. IPTs are conducted in uniformly-wetted soil columns and therefore, allow the determination of AI at a particular value of SW. The interfacial tracers used are typically surfactants, such as sodium dodecyl benzene sulfonate (SDBS), which are reversibly retained the air-water interface. At the SDBS concentrations often used, the aqueous surface tension of the interfacial tracer solution is approximately 30% lower than that of the non-reactive tracer solution. Because capillary pressure gradients caused by surfactant-induced surface tension gradients can induce unsaturated flow, we used numerical modeling to examine the potential for perturbations in unsaturated flow, and thus non-uniform distributions in SW, to occur during IPT tests. We used HYDRUS 1D, modified to include concentration-dependent surfactant effects on capillary pressure, in order to simulate a typical IPT experimental configuration in which SDBS was the interfacial tracer. Linear partitioning of the tracer to the air-water interface and sorption to the solid were included as SDBS retention mechanisms. The simulation results indicated that the surface tension changes caused by SDBS were sufficient to induce significant transient unsaturated flow, which was manifested as localized drainage and wetting as the SDBS passed through the column. Average SW in the column subsequently rebounded and reached a new steady-state flow condition once SDBS had displaced resident tracer-free water. The average SW at the

  18. Forced convection heat transfer to air/water vapor mixtures

    NASA Technical Reports Server (NTRS)

    Richards, D. R.; Florschuetz, L. W.

    1986-01-01

    Heat transfer coefficients were measured using both dry air and air/water vapor mixtures in the same forced convection cooling test rig (jet array impingement configurations) with mass ratios of water vapor to air up to 0.23. The primary objective was to verify by direct experiment that selected existing methods for evaluation of viscosity and thermal conductivity of air/water vapor mixtures could be used with confidence to predict heat transfer coefficients for such mixtures using as a basis heat transfer data for dry air only. The property evaluation methods deemed most appropriate require as a basis a measured property value at one mixture composition in addition to the property values for the pure components.

  19. Thermodynamic and transport properties of air/water mixtures

    NASA Technical Reports Server (NTRS)

    Fessler, T. E.

    1981-01-01

    Subroutine WETAIR calculates properties at nearly 1,500 K and 4,500 atmospheres. Necessary inputs are assigned values of combinations of density, pressure, temperature, and entropy. Interpolation of property tables obtains dry air and water (steam) properties, and simple mixing laws calculate properties of air/water mixture. WETAIR is used to test gas turbine engines and components operating in relatively humid air. Program is written in SFTRAN and FORTRAN.

  20. 14 CFR 1274.926 - Clean Air-Water Pollution Control Acts.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 14 Aeronautics and Space 5 2011-01-01 2010-01-01 true Clean Air-Water Pollution Control Acts. 1274... AGREEMENTS WITH COMMERCIAL FIRMS Other Provisions and Special Conditions § 1274.926 Clean Air-Water Pollution Control Acts. Clean Air-Water Pollution Control Acts July 2002 If this cooperative agreement or...

  1. A criterion for the onset of slugging in horizontal stratified air-water countercurrent flow

    SciTech Connect

    Chun, Moon-Hyun; Lee, Byung-Ryung; Kim, Yang-Seok

    1995-09-01

    This paper presents an experimental and theoretical investigation of wave height and transition criterion from wavy to slug flow in horizontal air-water countercurrent stratified flow conditions. A theoretical formula for the wave height in a stratified wavy flow regime has been developed using the concept of total energy balance over a wave crest to consider the shear stress acting on the interface of two fluids. From the limiting condition of the formula for the wave height, a necessary criterion for transition from a stratified wavy flow to a slug flow has been derived. A series of experiments have been conducted changing the non-dimensional water depth and the flow rates of air in a horizontal pipe and a duct. Comparisons between the measured data and the predictions of the present theory show that the agreement is within {plus_minus}8%.

  2. Air/water oxydesulfurization of coal: laboratory investigation

    SciTech Connect

    Warzinski, R. P.; Friedman, S.; Ruether, J. A.; LaCount, R. B.

    1980-08-01

    Air/water oxidative desulfurization has been demonstrated in autoclave experiments at the Pittsburgh Energy Technology Center for various coals representative of the major US coal basins. This experimentation has shown that the reaction proceeds effectively for pulverized coals at temperatures of 150 to 200/sup 0/C with air at a total system pressure of 500 to 1500 psig. Above 200/sup 0/C, the loss of coal and product heating value increases due to oxidative consumption of carbon and hydrogen. The pyritic sulfur solubilization reactions are typically complete (95 percent removal) within 15 to 40 minutes at temperature; however, significant apparent organic sulfur removal requires residence times of up to 60 minutes at the higher temperatures. The principal products of the reaction are sulfuric acid, which can be neutralized with limestone, and iron oxide. Under certain conditions, especially for high pyritic sulfur coals, the precipitation of sulfur-containing compounds from the products of the pyrite reaction may cause anomalous variations in the sulfur form data. The influence of various parameters on the efficiency of sulfur removal from coal by air/water oxydesulfurization has been studied.

  3. Absolute vicarious calibration of Landsat-8 OLI and Resourcesat-2 AWiFS sensors over Rann of Kutch site in Gujarat

    NASA Astrophysics Data System (ADS)

    Sharma, Shweta; Sridhar, V. N.; Prajapati, R. P.; Rao, K. M.; Mathur, A. K.

    2016-05-01

    In this work, vicarious calibration coefficients for all the four bands (green, red, NIR and SWIR) of Resourcesat-2 AWiFS sensor for four dates during Dec 2013-Nov 2014 and for seven bands (blue, green, red, NIR, SWIR1, SWIR2 and PAN) of OLI sensor onboard Landsat-8 for six dates during Dec 2013-Feb 2015 were estimated using field measured reflectance and measured atmospheric parameters during sensor image acquisition over Rann of Kutch site in Gujarat. The top of atmosphere (TOA) at-satellite radiances for all the bands were simulated using 6S radiative transfer code with field measured reflectance, synchronous atmospheric measurements and respective sensor's spectral response functions as an input. These predicted spectral radiances were compared with the radiances from the respective sensor's image in the respective band over the calibration site. Cross-calibration between the sensors AWiFS and OLI was also attempted using near-simultaneous same day image acquisition. Effect of spectral band adjustment factor was also studied with OLI sensor taken as reference sensor. Results show that the variation in average estimated radiance ratio for the AWiFS sensor was found to be within 10% for all the bands, whereas, for OLI sensor, the variation was found to be within 6% for all the bands except green and SWIR2 for which the variation was 8% and 11% respectively higher than the 5% uncertainty of the OLI sensor specification for TOA spectral radiance. At the 1σ level, red, NIR, SWIR1 and Panchromatic bands of OLI sensor showed close agreement between sensor-measured and vicarious TOA radiance resulting no change in calibration coefficient and hence indicating no sensor degradation. Two sets of near-simultaneous SBAFs were derived from respective ground measured target reflectance profiles and applied to the AWiFS and it was observed that overall, SBAF compensation provides a significant improvement in sensor agreement. The reduction in the difference between AWiFS and

  4. ISSUES IN SIMULATING ELEMENTAL MERCURY AIR/WATER EXCHANGE AND AQUEOUS MONOMETHYLMERCURY SPECIATION

    EPA Science Inventory

    This presentation focuses on two areas relevant to assessing the global fate and bioavailability of mercury: elemental mercury air/water exchange and aqueous environmental monomethylmercury speciation.

  5. Wind driven vertical transport in a vegetated, wetland water column with air-water gas exchange

    NASA Astrophysics Data System (ADS)

    Poindexter, C.; Variano, E. A.

    2010-12-01

    Flow around arrays of cylinders at low and intermediate Reynolds numbers has been studied numerically, analytically and experimentally. Early results demonstrated that at flow around randomly oriented cylinders exhibits reduced turbulent length scales and reduced diffusivity when compared to similarly forced, unimpeded flows (Nepf 1999). While horizontal dispersion in flows through cylinder arrays has received considerable research attention, the case of vertical dispersion of reactive constituents has not. This case is relevant to the vertical transfer of dissolved gases in wetlands with emergent vegetation. We present results showing that the presence of vegetation can significantly enhance vertical transport, including gas transfer across the air-water interface. Specifically, we study a wind-sheared air-water interface in which randomly arrayed cylinders represent emergent vegetation. Wind is one of several processes that may govern physical dispersion of dissolved gases in wetlands. Wind represents the dominant force for gas transfer across the air-water interface in the ocean. Empirical relationships between wind and the gas transfer coefficient, k, have been used to estimate spatial variability of CO2 exchange across the worlds’ oceans. Because wetlands with emergent vegetation are different from oceans, different model of wind effects is needed. We investigated the vertical transport of dissolved oxygen in a scaled wetland model built inside a laboratory tank equipped with an open-ended wind tunnel. Plastic tubing immersed in water to a depth of approximately 40 cm represented emergent vegetation of cylindrical form such as hard-stem bulrush (Schoenoplectus acutus). After partially removing the oxygen from the tank water via reaction with sodium sulfite, we used an optical probe to measure dissolved oxygen at mid-depth as the tank water re-equilibrated with the air above. We used dissolved oxygen time-series for a range of mean wind speeds to estimate the

  6. Harmonization of environmental quality objectives for air, water and soil

    SciTech Connect

    Plassche, E.J. van de

    1994-12-31

    Environmental quality objectives (EQO) are often derived for single compartments only. However, concentrations at or below EQO level for one compartment may lead to exceeding of the EQO in another compartment due to intermedia transport of the chemical. Hence, achieving concentrations lower than the EQO in e.g. air does not necessarily mean that a ``safe`` concentration in soil can be maintained because of deposition from air to soil. This means that EQOs for air, water and soil must be harmonized in such a way that they meet a coherence criterion. This criterion implies that a EQO for one compartment has to be set at a level that full protection to organisms living in other compartments is ensured. In The Netherlands a project has been started to derive harmonized EQOs for a large number of chemicals. First, EQ0s are derived for all compartments based on ecotoxicological data for single species applying extrapolation methods. Secondly, these independently derived EQOs are harmonized. For harmonization of EQOs for water, sediment and soil the equilibrium partitioning method is used. For harmonization of EQOs for water and soil with the E00s for air a procedure is used applying computed steady state concentration ratios rather than equilibrium partitioning. The model SimpleBox is used for these computations. Some results of the project mentioned above will be presented. Attention will be paid to the derivation of independent EQ0s as well as the harmonization procedures applied.

  7. Air-water gas exchange by waving vegetation stems

    NASA Astrophysics Data System (ADS)

    Foster-Martinez, M. R.; Variano, E. A.

    2016-07-01

    Exchange between wetland surface water and the atmosphere is driven by a variety of motions, ranging from rainfall impact to thermal convection and animal locomotion. Here we examine the effect of wind-driven vegetation movement. Wind causes the stems of emergent vegetation to wave back and forth, stirring the water column and facilitating air-water exchange. To understand the magnitude of this effect, a gas transfer velocity (k600 value) was measured via laboratory experiments. Vegetation waving was studied in isolation by mechanically forcing a model canopy to oscillate at a range of frequencies and amplitudes matching those found in the field. The results show that stirring due to vegetation waving produces k600 values from 0.55 cm/h to 1.60 cm/h. The dependence of k600 on waving amplitude and frequency are evident from the laboratory data. These results indicate that vegetation waving has a nonnegligible effect on gas transport; thus, it can contribute to a mechanistic understanding of the fluxes underpinning biogeochemical processes.

  8. The Effect of Rain on Air-Water Gas Exchange

    NASA Technical Reports Server (NTRS)

    Ho, David T.; Bliven, Larry F.; Wanninkhof, Rik; Schlosser, Peter

    1997-01-01

    The relationship between gas transfer velocity and rain rate was investigated at NASA's Rain-Sea Interaction Facility (RSIF) using several SF, evasion experiments. During each experiment, a water tank below the rain simulator was supersaturated with SF6, a synthetic gas, and the gas transfer velocities were calculated from the measured decrease in SF6 concentration with time. The results from experiments with IS different rain rates (7 to 10 mm/h) and 1 of 2 drop sizes (2.8 or 4.2 mm diameter) confirm a significant and systematic enhancement of air-water gas exchange by rainfall. The gas transfer velocities derived from our experiment were related to the kinetic energy flux calculated from the rain rate and drop size. The relationship obtained for mono-dropsize rain at the RSIF was extrapolated to natural rain using the kinetic energy flux of natural rain calculated from the Marshall-Palmer raindrop size distribution. Results of laboratory experiments at RSIF were compared to field observations made during a tropical rainstorm in Miami, Florida and show good agreement between laboratory and field data.

  9. Gas and liquid measurements in air-water bubbly flows

    SciTech Connect

    Zhou, X.; Doup, B.; Sun, X.

    2012-07-01

    Local measurements of gas- and liquid-phase flow parameters are conducted in an air-water two-phase flow loop. The test section is a vertical pipe with an inner diameter of 50 mm and a height of 3.2 m. The measurements are performed at z/D = 10. The gas-phase measurements are performed using a four-sensor conductivity probe. The data taken from this probe are processed using a signal processing program to yield radial profiles of the void fraction, bubble velocity, and interfacial area concentration. The velocity measurements of the liquid-phase are performed using a state-of-the-art Particle Image Velocimetry (PIV) system. The raw PIV images are acquired using fluorescent particles and an optical filtration device. Image processing is used to remove noise in the raw PIV images. The statistical cross correlation is introduced to determine the axial velocity field and turbulence intensity of the liquid-phase. Measurements are currently being performed at z/D = 32 to provide a more complete data set. These data can be used for computational fluid dynamic model development and validation. (authors)

  10. 14 CFR 1274.926 - Clean Air-Water Pollution Control Acts.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 5 2013-01-01 2013-01-01 false Clean Air-Water Pollution Control Acts...-Water Pollution Control Acts. Clean Air-Water Pollution Control Acts July 2002 If this cooperative... 91-604) and section 308 of the Federal Water Pollution Control Act, as amended (33 U.S.C. 1251 et...

  11. 14 CFR 1274.926 - Clean Air-Water Pollution Control Acts.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 5 2010-01-01 2010-01-01 false Clean Air-Water Pollution Control Acts...-Water Pollution Control Acts. Clean Air-Water Pollution Control Acts July 2002 If this cooperative... 91-604) and section 308 of the Federal Water Pollution Control Act, as amended (33 U.S.C. 1251 et...

  12. 14 CFR 1274.926 - Clean Air-Water Pollution Control Acts.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 5 2012-01-01 2012-01-01 false Clean Air-Water Pollution Control Acts...-Water Pollution Control Acts. Clean Air-Water Pollution Control Acts July 2002 If this cooperative... 91-604) and section 308 of the Federal Water Pollution Control Act, as amended (33 U.S.C. 1251 et...

  13. 14 CFR § 1274.926 - Clean Air-Water Pollution Control Acts.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 5 2014-01-01 2014-01-01 false Clean Air-Water Pollution Control Acts. Â...-Water Pollution Control Acts. Clean Air-Water Pollution Control Acts July 2002 If this cooperative... 91-604) and section 308 of the Federal Water Pollution Control Act, as amended (33 U.S.C. 1251 et...

  14. Conversion of Iodide to Hypoiodous Acid and Molecular Iodine at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Pillar, E. A.; Guzman, M. I.

    2013-12-01

    Sea spray aerosols continuously transfer a significant amount of halides to the marine boundary layer, where they play a major role in the depletion of tropospheric ozone. The reactivity of iodide is of special interest in sea spray aerosols, where this species is enriched relative to chloride and bromide in surface seawater. This work presents laboratory experiments that provide mechanistic information to understand the reactivity of halides in atmospheric aerosols. Pneumatically assisted electrospray is used to aerosolize solutions of sodium iodide (0.01-100 μM), which are rapidly (~3 μs) oxidized by ozone at 25 °C. Reaction products include HIO, IO2-, IO3-, I2, HI2O-, and I3-, all identified by mass spectrometry. The distribution of products varies along two different reaction pathways, one favoring the production of I2 and HIO for typical tropospheric ozone levels (~50 ppbv), and another one directed to the production of IO3- at higher oxidizer concentrations. The formation of products increases exponentially with rising concentrations of initial sodium iodide, [NaI]0. The process is determined to be pH independent for the pH range 6-8 representative of surface waters. The substitution of aqueous solutions by organic solvents, such as methanol or acetonitrile, causes a decrease in the surface tension and lifetime of the droplets, leading to larger I2 production. The presence of surface active organic compounds, which alter the structure of the interfacial region, promote the pathway of I2 formation over IO3-. In conclusion, this presentation will show how the oxidation of iodide in aqueous microdroplets can release reactive gas-phase species, such as I2 and HIO, capable to affect tropospheric ozone globally. Normalized intensity of products observed during the ozonolysis of iodide solutions at 130 ppbv ozone. Cone voltage = 70 V, needle voltage = 2.5 kV.

  15. Supramolecular Systems Behavior at the Air-Water Interface. Molecular Dynamic Simulation Study.

    NASA Astrophysics Data System (ADS)

    Sandoval, C.; Saavedra, M.; Gargallo, L.; Radić, D.

    2008-08-01

    Atomistic molecular dynamics simulation (MDS) was development to investigate the structural and dynamic properties of a monolayer of supramolecular systems. The simulations were performed at room temperature, on inclusion complexes (ICs) of α-cyclodextrin (CD) with poly(ethylene-oxide)(PEO), poly(ɛ-caprolactone)(PEC) and poly(tetrahydrofuran)(PTHF). The simulations were carried out for a surface area of 30Å. The trajectories of the MDS show that the system more stable was IC-PEC, being the less stable IC-PEO. The disordered monolayer for the systems was proved by the orientation correlation function and the radial distribution function between the polar groups of ICs and the water molecules. We found that the system IC-PEC was more stable that the systems IC-PTHF and IC-PEO.

  16. Long-timescale dynamics of thiol capped Au nanoparticle clusters at the air-water interface

    NASA Astrophysics Data System (ADS)

    Choudhuri, Madhumita; Datta, Alokmay

    2014-04-01

    A two-dimensional network of thiol-capped Au nanoparticle (AuNP) clusters is self-organized on a Stearic Acid (amphiphilic fatty acid) Langmuir monolayer on water surface. The AuNP clusters are found to form a pattern of connected and enclosed microspaces in the stearic acid template. The network features can be controlled by changing the surface pressure of the monolayer during compression. The two-dimensional dynamics of this network has been studied over a long timescale using Brewster Angle Microscopy (BAM). The dynamics is very slow, indicating the stability of the network system, and is essentially driven by the tendency to lower the number of nodes or joints in the network.

  17. Extracellular enzyme activity at the air-water interface of an estuarine lake

    NASA Astrophysics Data System (ADS)

    Mudryk, Z. J.; Skórczewski, P.

    2004-01-01

    Variations in hydrolytic activity of eight extracellular enzymes in surface and subsurface waters in estuarine Lake Gardno were measured. The ranking of potential activity rates of the assayed enzymes was the same in both surface and subsurface water, i.e. esterase > lipase > aminopeptidase > phosphatase > β-glucosidase > α-glucosidase > chitinase > β-lactosidase. The vertical activity profiles show that esterase, aminopeptidase, α-glucosidase, β-glucosidase and β-lactosidase reached the highest values in surface layer, whereas lipase, phosphatase and chitinase showed maximum activity in subsurface water. Significant differences in enzyme activity between different parts of the studied lake were demonstrated, with higher values in the seawater zone, and lower values in the freshwater zone.

  18. Nanostructure and salt effect of zwitterionic carboxybetaine brush at the air/water interface.

    PubMed

    Matsuoka, Hideki; Yamakawa, Yuta; Ghosh, Arjun; Saruwatari, Yoshiyuki

    2015-05-01

    Zwitterionic amphiphilic diblock copolymer, poly(ethylhexyl acrylate)-b-poly(carboxybetaine) (PEHA-b-PGLBT), was synthesized by the reversible addition-fragmentation chain transfer (RAFT) method with precise control of block length and polydispersity. The polymers thus obtained were spread onto the water surface to form a polymer monolayer. The fundamental property and nanostructure of the block copolymer monolayer were systematically studied by the surface pressure-molecular area (π-A) isotherm, Brewster angle microscopy (BAM), and X-ray reflectivity (XR) techniques. The π values of the monolayer increased by compression in relatively larger A regions. After showing a large plateau region by compression, the π value sharply increased at very small A regions, suggesting the formation of poly(GLBT) brush formation just beneath the water surface. The domain structure of μm size was observed by BAM in the plateau region. XR profiles for the monolayer at higher surface pressure regions clearly showed the PGLBT brush formation in addition to PGLBT carpet layer formation under the hydrophobic PEHA layer on the water surface, as was observed for both anionic and cationic brush layer in the water surface monolayer studied previously. The critical brush density, where the PGLBT brush is formed, was estimated to be about 0.30 chains/nm(2) for the (EHA)45-b-(GLBT)60 monolayer, which is relatively large compared to other ionic brushes. This observation is consistent with the fact that the origin of brush formation is mainly steric hindrance between brush chains. The brush thickness increased by compression and also by salt addition, unlike the normal ionic brush (anionic and cationic), whose thickness tended to decrease, i.e., shrink, by salt addition. This might be a character unique to the zwitterionic brush, and its origin is thought to be transition to an ionic nature from the almost nonionic inner salt caused by salt addition since both the cation and anion of the GLBT chain obtained counterions by the addition of salt. This stretching nature of the PGLBT brush depends on the ion species of the salt added, and it followed the Hofmeister series, i.e., more stretching in the order of Li(+) > Na(+) > K(+). However, it was rather insensitive to the anion species (Cl(-), Br(-), SCN(-)), which suggests that the carboxylic anion has a more dominant effect than the quaternized cation in GLBT although the former is a weak acid and the latter is believed to be a strong base.

  19. Effect of cation enrichment on dipalmitoylphosphatidylcholine (DPPC) monolayers at the air-water interface.

    PubMed

    Adams, Ellen M; Casper, Clayton B; Allen, Heather C

    2016-09-15

    The effect of highly concentrated salt solutions of marine-relevant cations (Na(+), K(+), Mg(2+), and Ca(2+)) on Langmuir monolayers of dipalmitoylphosphatidylcholine (DPPC) was investigated by means of surface pressure-area isotherms, Brewster angle microscopy (BAM), and infrared reflection-absorption spectroscopy (IRRAS). It was found that monovalent cations and Mg(2+) have similar phase behavior, causing DPPC monolayers to expand, while Ca(2+) induces condensation. All cations disrupted the surface morphology at high cation concentration, resulting in decreased reflectivity from the monolayer. Monolayer refractive index was calculated from BAM image intensity in the liquid condensed phase and decreased with increasing cation concentration, which suggests that orientation of the alkyl chains change. Monovalent ions increase ordering of the alkyl chains, more than divalents, yet have little interaction with the DPPC headgroup. Mg(2+) induces gauche defects in the alkyl chain and increases headgroup hydration at low lipid coverage but increases chain ordering and dehydrates the headgroup at high lipid coverage. Ca(2+) orders alkyl chains and dehydrates the phosphate moiety, independent of lipid phase. At the highest salt concentration investigated, significant narrowing of the asymmetric PO2(-) vibrational mode occurs and is attributed to considerable dehydration of the DPPC headgroup. PMID:27322949

  20. Forces Acting on Submillimeter Spheres at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Wang, Le-Feng; Liu, Lu; Xu, Hui-Chao; Rong, Wei-Bin; Sun, Li-Ning

    2015-11-01

    Not Available Supported by the National Natural Science Foundation of China under Grant No 61005072, and the Self-Planned Task of State Key Laboratory of Robotics and System under Grant Nos SKLRS201501A04 and SKLRS201301A01.

  1. Ammonia Flux at the Air-Water Interface of Tampa Bay

    NASA Astrophysics Data System (ADS)

    Mizak, C. A.; Poor, N. D.

    2003-12-01

    Recent nitrogen deposition research in the Tampa Bay Estuary indicates that ammonia deposition dominates the total dry nitrogen flux to the bay. Gaseous plus aerosol ammonia contribute approximately 450 tons per year or 60% of the total nitrogen deposition of 760 tons per year to the estuary. Research data also indicate that during the summer months, Tampa Bay may act as a source for atmospheric ammonia as water temperature and ammonium concentrations increase. Ammonia flux estimates will be derived from thirty days of daily summer air and water sampling at the Gandy Bridge air monitoring site located adjacent to Tampa Bay. Ammonia concentrations were measured at two heights with a URG, Inc. dual-pump annular denuder system (ADS), and water grab samples from two depths were analyzed in the laboratory for ammonium concentration. Hourly relative humidity, air and water temperature, pH and salinity were recorded at this site, and hourly wind speed and direction were obtained from the Environmental Protection Commission of Hillsborough County. Rainwater samples were obtained with a University of Michigan sequential rainwater collector and analyzed in the laboratory for ammonium concentration. The direction and magnitude for the ammonia flux will be calculated with a modified NOAA buoy model from measurements of wind speed, air and water temperature, air and water ammonia and ammonium concentrations, relative humidity, water pH and salinity. The results of this research will be used to improve the NOAA Buoy model, and to compare observed with modeled ammonia gradients.

  2. OXYGEN TRANSFER ACROSS THE AIR-WATER INTERFACE DUE TO NATURAL CONVECTION IN LAKES. (R825428)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  3. SUPRAMOLECULAR SYSTEMS BEHAVIOR AT THE AIR-WATER INTERFACE. MOLECULAR DYNAMIC SIMULATION STUDY

    SciTech Connect

    Sandoval, C.; Saavedra, M.; Gargallo, L.; Radic, D.

    2008-08-28

    Atomistic molecular dynamics simulation (MDS) was development to investigate the structural and dynamic properties of a monolayer of supramolecular systems. The simulations were performed at room temperature, on inclusion complexes (ICs) of {alpha}-cyclodextrin (CD) with poly(ethylene-oxide)(PEO), poly({epsilon}-caprolactone)(PEC) and poly(tetrahydrofuran)(PTHF). The simulations were carried out for a surface area of 30A ring . The trajectories of the MDS show that the system more stable was IC-PEC, being the less stable IC-PEO. The disordered monolayer for the systems was proved by the orientation correlation function and the radial distribution function between the polar groups of ICs and the water molecules. We found that the system IC-PEC was more stable that the systems IC-PTHF and IC-PEO.

  4. Behavior of lysozyme adsorbed onto biological liquid crystal lipid monolayer at the air/water interface

    NASA Astrophysics Data System (ADS)

    Lu, Xiaolong; Shi, Ruixin; Hao, Changchun; Chen, Huan; Zhang, Lei; Li, Junhua; Xu, Guoqing; Sun, Runguang

    2016-09-01

    The interaction between proteins and lipids is one of the basic problems of modern biochemistry and biophysics. The purpose of this study is to compare the penetration degree of lysozyme into 1,2-diapalmitoyl-sn-glycero-3-phosphocholine (DPPC) and 1,2-dipalmitoyl-sn-glycero-3-phosphoethano-lamine (DPPE) by analyzing the data of surface pressure-area (π-A) isotherms and surface pressure-time (π-T) curves. Lysozyme can penetrate into both DPPC and DPPE monolayers because of the increase of surface pressure at an initial pressure of 15 mN/m. However, the changes of DPPE are larger than DPPC, indicating stronger interaction of lysozyme with DPPE than DPPC. The reason may be due to the different head groups and phase state of DPPC and DPPE monolayers at the surface pressure of 15 mN/m. Atomic force microscopy reveals that lysozyme was absorbed by DPPC and DPPE monolayers, which leads to self-aggregation and self-assembly, forming irregular multimers and conical multimeric. Through analysis, we think that the process of polymer formation is similar to the aggregation mechanism of amyloid fibers. Project supported by the National Natural Science Foundation of China (Grant Nos. 21402114 and 11544009), the Natural Science Basic Research Plan in Shaanxi Province of China (Grant No. 2016JM2010), the Fundamental Research Funds for the Central Universities of China (Grant No. GK201603026), and the National University Science and Technology Innovation Project of China (Grant No. 201610718013).

  5. Phase Characteristics of 1-Monopalmitoyl-rac-glycerol Monolayers at the Air/Water Interface.

    PubMed

    Vollhardt, D; Brezesinski, G

    2016-07-26

    1-Monopalmitoyl-rac-glycerol is omnipresent in numerous biological and applied systems. Systematic GIXD measurements of 1-monopalmitoyl-rac-glycerol monolayers are carried out over a large pressure interval at 5, 10, and 15 °C to construct the phase diagram on the basis of reliable 2D lattice structures. These studies are complemented by other monolayer characteristics, such as π-A isotherms and mesoscopic domain topographies. A phase transition is found between the two orthorhombic structures with NN and NNN tilted alkyl chains at low temperatures (5 and 10 °C). It increases linearly with increasing temperature. With a further increase in temperature to 15 °C, only NN-tilted orthorhombic lattices are observed in the whole pressure region. The cross-sectional area, A0, is less affected by surface pressure and temperature and amounts to values of between 19.7 and 19.8 Å(2), as expected for a rotator phase at the lower limit. The tilt angle t with respect to the surface normal decreases with increasing pressure and is only slightly influenced by the temperature. The transition pressure to untilted alkyl chains, as determined by the extrapolation of 1/cos(t) to zero tilt angle, is >50 mN/m for all temperatures. The results of lattice distortion d versus sin 2(t) suggest for 10 and 15 °C the tilt of the aliphatic chains as the reason for the monolayer lattice distortion whereas at 5 °C the nonzero-tilt-angle intercept d0 could be an indication of the prevention of hexagonal packing. The generic π-T phase diagram of racemic monoacylglycerol monolayers is constructed on the basis of the phase diagrams of 1-monopalmitoyl-rac-glycerol and 1-monostearoyl-rac-glycerol, which shows that for 1-monopalmitoyl-rac-glycerol monolayers the oblique phase can occur only close to and below 0 °C. The possible phase behavior of other racemic monoacylglycerol monolayers with alkyl chain lengths of C14 and C20 is discussed on the basis of the generic phase diagram. PMID:27351635

  6. Phases, line tension and pattern formation in molecularly thin films at the air-water interface

    NASA Astrophysics Data System (ADS)

    Mandal, Pritam

    A Langmuir film, which is a molecularly thin insoluble film on a liquid substrate, is one practical realization of a quasi-two dimensional matter. The major advantages of this system for the study of phase separation and phase co-existence are (a) it allows accurate control of the components and molecular area of the film and (b) it can be studied by various methods that require very flat films. Phase separation in molecularly thin films plays an important role in a range of systems from biomembranes to biosensors. For example, phase-separated lipid nano-domains in biomembranes are thought to play crucial roles in membrane function. I use Brewster Angel Microscopy (BAM) coupled with Fluorescence Microscopy (FM) and static Light Scattering Microscopy (LSM) to image phases and patterns within Langmuir films. The three microscopic techniques --- BAM, FM and LSM --- are complimentary to each other, providing distinct sets of information. They allow direct comparison with literature results in lipid systems. I have quantitatively validated the use of detailed hydrodynamic simulations to determine line tension in monolayers. Line tension decreases as temperature rises. This decrease gives us information on the entropy associated with the line, and thus about line structure. I carefully consider the thermodynamics of line energy and entropy to make this connection. In the longer run, LSM will be exploited to give us further information about line structure. I have also extended the technique by testing it on domains within the curved surface of a bilayer vesicle. I also note that in the same way that the presence of surface-active agents, known as surfactants, affects surface energy, the addiction of line active agents alters the inter-phase line energy. Thus my results set to stage to systematically study the influence of line active agents ---'linactants' --- on the inter-phase line energy. Hierarchal self-assembled chiral patterns were observed as a function of temperature. I found that the appearance of these domains could be explained with a simple uniaxial optical axis in the underlying structure, which is the first critical step to understanding the origin of these patterns.

  7. Behavior of lysozyme adsorbed onto biological liquid crystal lipid monolayer at the air/water interface

    NASA Astrophysics Data System (ADS)

    Lu, Xiaolong; Shi, Ruixin; Hao, Changchun; Chen, Huan; Zhang, Lei; Li, Junhua; Xu, Guoqing; Sun, Runguang

    2016-09-01

    The interaction between proteins and lipids is one of the basic problems of modern biochemistry and biophysics. The purpose of this study is to compare the penetration degree of lysozyme into 1,2-diapalmitoyl-sn-glycero-3-phosphocholine (DPPC) and 1,2-dipalmitoyl-sn-glycero-3-phosphoethano-lamine (DPPE) by analyzing the data of surface pressure–area (π–A) isotherms and surface pressure–time (π–T) curves. Lysozyme can penetrate into both DPPC and DPPE monolayers because of the increase of surface pressure at an initial pressure of 15 mN/m. However, the changes of DPPE are larger than DPPC, indicating stronger interaction of lysozyme with DPPE than DPPC. The reason may be due to the different head groups and phase state of DPPC and DPPE monolayers at the surface pressure of 15 mN/m. Atomic force microscopy reveals that lysozyme was absorbed by DPPC and DPPE monolayers, which leads to self-aggregation and self-assembly, forming irregular multimers and conical multimeric. Through analysis, we think that the process of polymer formation is similar to the aggregation mechanism of amyloid fibers. Project supported by the National Natural Science Foundation of China (Grant Nos. 21402114 and 11544009), the Natural Science Basic Research Plan in Shaanxi Province of China (Grant No. 2016JM2010), the Fundamental Research Funds for the Central Universities of China (Grant No. GK201603026), and the National University Science and Technology Innovation Project of China (Grant No. 201610718013).

  8. Polymerization of a diacetylenic phospholipid monolayer at the air-water interface

    NASA Astrophysics Data System (ADS)

    Bourdieu, L.; Chatenay, D.; Daillant, J.; Luzet, D.

    1994-01-01

    Monolayers of a polymerizable phospholipid on water have been studied both before and after polymerization. Before polymerization, the phase diagram is established by isotherm measurements and optical microscopy (epifluorescence and direct observation between crossed polarizer and analyzer). This allows us to bring into evidence a coexistence region between a condensed and an expanded phase, above a triple point temperature T_t = 20 ^{circ}C. The dramatic influence of impurities on the size of coexistence domains between the condensed phase and the expanded one is clearly demonstrated, even at a very low concentration of impurities. Structural and morphological modifications during the polymerization where investigated using X-ray surface scattering together with atomic force microscopy. Whatever the polymerization conditions (constant area or constant pressure), X-ray reflectivity clearly shows the reorientation of the diacetylenic links. Only constant area polymerization leads to a viscoelastic behavior of the film, as shown by talcum decoration. The topochemical nature of the polymerization of diacetylenic groups induces strong constraints on the monolayers and, when the polymerization is achieved at constant area, leads to the collapse of the films evidenced by both techniques.

  9. Bifurcations of a creeping air-water flow in a conical container

    NASA Astrophysics Data System (ADS)

    Balci, Adnan; Brøns, Morten; Herrada, Miguel A.; Shtern, Vladimir N.

    2016-04-01

    This numerical study describes the eddy emergence and transformations in a slow steady axisymmetric air-water flow, driven by a rotating top disk in a vertical conical container. As water height Hw and cone half-angle β vary, numerous flow metamorphoses occur. They are investigated for β =30°, 45°, and 60°. For small Hw , the air flow is multi-cellular with clockwise meridional circulation near the disk. The air flow becomes one cellular as Hw exceeds a threshold depending on β . For all β , the water flow has an unbounded number of eddies whose size and strength diminish as the cone apex is approached. As the water level becomes close to the disk, the outmost water eddy with clockwise meridional circulation expands, reaches the interface, and induces a thin layer with anticlockwise circulation in the air. Then this layer expands and occupies the entire air domain. The physical reasons for the flow transformations are provided. The results are of fundamental interest and can be relevant for aerial bioreactors.

  10. Bifurcations of a creeping air-water flow in a conical container

    NASA Astrophysics Data System (ADS)

    Balci, Adnan; Brøns, Morten; Herrada, Miguel A.; Shtern, Vladimir N.

    2016-10-01

    This numerical study describes the eddy emergence and transformations in a slow steady axisymmetric air-water flow, driven by a rotating top disk in a vertical conical container. As water height Hw and cone half-angle β vary, numerous flow metamorphoses occur. They are investigated for β =30°, 45°, and 60°. For small Hw, the air flow is multi-cellular with clockwise meridional circulation near the disk. The air flow becomes one cellular as Hw exceeds a threshold depending on β . For all β , the water flow has an unbounded number of eddies whose size and strength diminish as the cone apex is approached. As the water level becomes close to the disk, the outmost water eddy with clockwise meridional circulation expands, reaches the interface, and induces a thin layer with anticlockwise circulation in the air. Then this layer expands and occupies the entire air domain. The physical reasons for the flow transformations are provided. The results are of fundamental interest and can be relevant for aerial bioreactors.

  11. Cross-comparison of the IRS-P6 AWiFS sensor with the L5 TM, L7 ETM+, & Terra MODIS sensors

    USGS Publications Warehouse

    Chander, G.; Xiong, X.; Angal, A.; Choi, T.; Malla, R.

    2009-01-01

    As scientists and decision makers increasingly rely on multiple Earth-observing satellites to address urgent global issues, it is imperative that they can rely on the accuracy of Earth-observing data products. This paper focuses on the crosscomparison of the Indian Remote Sensing (IRS-P6) Advanced Wide Field Sensor (AWiFS) with the Landsat 5 (L5) Thematic Mapper (TM), Landsat 7 (L7) Enhanced Thematic Mapper Plus (ETM+), and Terra Moderate Resolution Imaging Spectroradiometer (MODIS) sensors. The cross-comparison was performed using image statistics based on large common areas observed by the sensors within 30 minutes. Because of the limited availability of simultaneous observations between the AWiFS and the Landsat and MODIS sensors, only a few images were analyzed. These initial results are presented. Regression curves and coefficients of determination for the top-of-atmosphere (TOA) trends from these sensors were generated to quantify the uncertainty in these relationships and to provide an assessment of the calibration differences between these sensors. ?? 2009 SPIE.

  12. Air-water oxygen exchange in a large whitewater river

    USGS Publications Warehouse

    Hall, Robert O.; Kennedy, Theodore A.; Rosi-Marshall, Emma J.

    2012-01-01

    Air-water gas exchange governs fluxes of gas into and out of aquatic ecosystems. Knowing this flux is necessary to calculate gas budgets (i.e., O2) to estimate whole-ecosystem metabolism and basin-scale carbon budgets. Empirical data on rates of gas exchange for streams, estuaries, and oceans are readily available. However, there are few data from large rivers and no data from whitewater rapids. We measured gas transfer velocity in the Colorado River, Grand Canyon, as decline in O2 saturation deficit, 7 times in a 28-km segment spanning 7 rapids. The O2 saturation deficit exists because of hypolimnetic discharge from Glen Canyon Dam, located 25 km upriver from Lees Ferry. Gas transfer velocity (k600) increased with slope of the immediate reach. k600 was -1 in flat reaches, while k600 for the steepest rapid ranged 3600-7700 cm h-1, an extremely high value of k600. Using the rate of gas exchange per unit length of water surface elevation (Kdrop, m-1), segment-integrated k600 varied between 74 and 101 cm h-1. Using Kdrop we scaled k600 to the remainder of the Colorado River in Grand Canyon. At the scale corresponding to the segment length where 80% of the O2 exchanged with the atmosphere (mean length = 26.1 km), k600 varied 4.5-fold between 56 and 272 cm h-1 with a mean of 113 cm h-1. Gas transfer velocity for the Colorado River was higher than those from other aquatic ecosystems because of large rapids. Our approach of scaling k600 based on Kdrop allows comparing gas transfer velocity across rivers with spatially heterogeneous morphology.

  13. A CRITICAL ASSESSMENT OF ELEMENTAL MERCURY AIR/WATER EXCHANGE PARTNERS

    EPA Science Inventory

    Although evasion of elemental mercury from aquatic systems can significantly deplete net mercury accumulation resulting from atmospheric deposition, the current ability to model elemental mercury air/water exchange is limited by uncertainties in our understanding of all gaseous a...

  14. Application of a laser Doppler vibrometer for air-water to subsurface signature detection

    NASA Astrophysics Data System (ADS)

    Land, Phillip; Roeder, James; Robinson, Dennis; Majumdar, Arun

    2015-05-01

    There is much interest in detecting a target and optical communications from an airborne platform to a platform submerged under water. Accurate detection and communications between underwater and aerial platforms would increase the capabilities of surface, subsurface, and air, manned and unmanned vehicles engaged in oversea and undersea activities. The technique introduced in this paper involves a Laser Doppler Vibrometer (LDV) for acousto-optic sensing for detecting acoustic information propagated towards the water surface from a submerged platform inside a 12 gallon water tank. The LDV probes and penetrates the water surface from an aerial platform to detect air-water surface interface vibrations caused by an amplifier to a speaker generating a signal generated from underneath the water surface (varied water depth from 1" to 8"), ranging between 50Hz to 5kHz. As a comparison tool, a hydrophone was used simultaneously inside the water tank for recording the acoustic signature of the signal generated between 50Hz to 5kHz. For a signal generated by a submerged platform, the LDV can detect the signal. The LDV detects the signal via surface perturbations caused by the impinging acoustic pressure field; proving a technique of transmitting/sending information/messages from a submerged platform acoustically to the surface of the water and optically receiving the information/message using the LDV, via the Doppler Effect, allowing the LDV to become a high sensitivity optical-acoustic device. The technique developed has much potential usage in commercial oceanography applications. The present work is focused on the reception of acoustic information from an object located underwater.

  15. Monitoring of Western Corn Rootworm Damage in Maize Fields by Using Integrated Radar (ALOS PALSAR) and Optical (IRS LISS, AWiFS) Satellite Data

    NASA Astrophysics Data System (ADS)

    Nador, Gizella; Fenyes, Diana; Surek, Gyorgy; Vasas, Laszlo

    2008-11-01

    The gradual dispersion of western corn rootworm (WCR) is becoming a serious maize pest in Europe, and all over the world. In 2008 using remote sensing data, the Remote Sensing Centre of Institute of Geodesy, Cartography and Remote Sensing (FÖMI RSC) carried out this project to identify WCR larval damage. Our goal with the present project is to assess and identify the disorder and structural changes caused by WCR larvae using optical (IRS-P6 AWiFS, IRS-P6 LISS, SPOT4 and SPOT5) and polarimetic radar (ALOS PALSAR) satellite images. The project aims to identify the extent of WCR damaged cornfields using both polarimetic radar images and optical satellite data time series. Findings were tested against on-the-spot ground assessments. Using radar polarimetry increased the accuracy significantly. The final results have implications for plant protection strategy, farming practices, pesticide producers, state authorities and research institutes.

  16. Monitoring seasonal progress of rice stubble burning in major rice growing districts of Haryana, India, using multidate AWiFS data

    NASA Astrophysics Data System (ADS)

    Yadav, M.; Prawasi, R.; Jangra, S.; Rana, P.; Kumari, K.; Lal, S.; Jakhar, K.; Sharma, S.; Hooda, R. S.

    2014-11-01

    The present paper describes the methodology and results of assessment of seasonal progress of rice stubble burning for 10 major rice growing districts of Haryana state in India. These 10 districts contribute about 84 per cent of total rice area of the state. As the rice fields are immediately required to be vacated for the sowing of next crop the farmers opt for mechanized harvesting and easy way out of burning the stubbles in the field. Such burning result in release of polluting gases and aerosols. Besides, the heating of the soil kills the useful micro-flora of the soil causing soil degradation. Multi-date AWiFS data from Resourcesat 1 and 2 satellites acquired between October 16, 2013 to November 26, 2013 were used for estimating paddy stubble burning areas at different intervals for the year 2013 crop growing season. In season collected ground truth data using hand held GPS along with field photographs were used to identify paddy stubble burning areas and other land features. Complete enumeration approach and Iterative Self-organizing Data Analysis Technique (ISODATA) unsupervised classifier was used for digital analysis. Normalized Difference Vegetation Index (NDVI) of each date was also used with other spectral bands of temporal images. To improve the classification accuracy the non-agricultural areas were masked out. The area was estimated by computing pixels under the classified image mask. Progress of paddy stubble burning was estimated at different intervals for the year 2013 using available cloud free multi-date IRS-P6 AWiFS data to identify the crucial period when stubbles burning takes place in major area so that preventive measures can be taken to curb the menace.

  17. On the coefficients of small eddy and surface divergence models for the air-water gas transfer velocity

    NASA Astrophysics Data System (ADS)

    Wang, Binbin; Liao, Qian; Fillingham, Joseph H.; Bootsma, Harvey A.

    2015-03-01

    Recent studies suggested that under low to moderate wind conditions without bubble entraining wave breaking, the air-water gas transfer velocity k+ can be mechanistically parameterized by the near-surface turbulence, following the small eddy model (SEM). Field measurements have supported this model in a variety of environmental forcing systems. Alternatively, surface divergence model (SDM) has also been shown to predict the gas transfer velocity across the air-water interface in laboratory settings. However, the empirically determined model coefficients (α in SEM and c1 in SDM) scattered over a wide range. Here we present the first field measurement of the near-surface turbulence with a novel floating PIV system on Lake Michigan, which allows us to evaluate the SEM and SDM in situ in the natural environment. k+ was derived from the CO2 flux that was measured simultaneously with a floating gas chamber. Measured results indicate that α and c1 are not universal constants. Regression analysis showed that α˜log>(ɛ>) while the near-surface turbulence dissipation rate ɛ is approximately greater than 10-6 m2 s-3 according to data measured for this study as well as from other published results measured in similar environments or in laboratory settings. It also showed that α scales linearly with the turbulent Reynolds number. Similarly, coefficient c1 in the SDM was found to linearly scale with the Reynolds number. These findings suggest that larger eddies are also important parameters, and the dissipation rate in the SEM or the surface divergence β' in the SDM alone may not be adequate to determine k+ completely.

  18. Two-phase air-water stratified flow measurement using ultrasonic techniques

    SciTech Connect

    Fan, Shiwei; Yan, Tinghu; Yeung, Hoi

    2014-04-11

    In this paper, a time resolved ultrasound system was developed for investigating two-phase air-water stratified flow. The hardware of the system includes a pulsed wave transducer, a pulser/receiver, and a digital oscilloscope. The time domain cross correlation method is used to calculate the velocity profile along ultrasonic beam. The system is able to provide velocities with spatial resolution of around 1mm and the temporal resolution of 200μs. Experiments were carried out on single phase water flow and two-phase air-water stratified flow. For single phase water flow, the flow rates from ultrasound system were compared with those from electromagnetic flow (EM) meter, which showed good agreement. Then, the experiments were conducted on two-phase air-water stratified flow and the results were given. Compared with liquid height measurement from conductance probe, it indicated that the measured velocities were explainable.

  19. Air-water gas exchange of chlorinated pesticides in four lakes spanning a 1,205 meter elevation range in the Canadian Rocky Mountains.

    PubMed

    Wilkinson, Andrew C; Kimpe, Lynda E; Blais, Jules M

    2005-01-01

    Concentrations of selected persistent organic pollutants (POPs) in air and water were measured from four lakes that transect the Canadian Rocky Mountains. These data were used in combination with wind velocity and temperature-adjusted Henry's law constants to estimate the direction and magnitude of chemical exchange across the air-water interface of these lakes. Bow Lake (1,975 m above sea level [masl]) was studied during the summers of 1998 through 2000; Donald (770 masl) was studied during the summer of 1999; Dixon Dam Lake (946 masl) and Kananaskis Lake (1,667 masl) were studied during the summer of 2000. Hexachlorobenzene (HCB) and dieldrin volatilized from Bow Lake in spring and summer of 1998 to 2000 at a rate of 0.92 +/-1.1 and 0.55+/-0.37 ng m(-2) d(-1), respectively. The alpha-endosulfan deposited to Bow Lake at a rate of 3.4+/-2.2 ng m(-2) d(-1). Direction of gas exchange for gamma-hexachlorocyclohexane (gamma-HCH) changed from net deposition in 1998 to net volatilization in 1999, partly because of a surge in y-HCH concentrations in the water at Bow Lake in 1999. Average gamma-HCH concentrations in air declined steadily over the three-year period, from 0.021 ng m(-3) in 1998, to 0.0023 ng m(-3) in 2000, and to volatilization in 1999 and 2000. Neither the concentrations of organochlorine compounds (OCs) in air and water, nor the direction and rate of air-water gas exchange correlate with temperature or elevation. In general, losses of pesticides by outflow were greater than the amount exchanged across the air-water interface in these lakes. PMID:15683168

  20. THE EFFECT OF SALINITY ON RATES OF ELEMENTAL MERCURY AIR/WATER EXCHANGE

    EPA Science Inventory

    The U.S. EPA laboratory in Athens, Georgia i spursuing the goal of developing a model for describing toxicant vapor phase air/water exchange under all relevant environmental conditions. To date, the two-layer exchange model (suitable for low wind speed conditions) has been modif...

  1. Molecular Design of Branched and Binary Molecules at Ordered Interfaces

    SciTech Connect

    Genson, Kirsten Larson

    2005-01-01

    This study examined five different branched molecular architectures to discern the effect of design on the ability of molecules to form ordered structures at interfaces. Photochromic monodendrons formed kinked packing structures at the air-water interface due to the cross-sectional area mismatch created by varying number of alkyl tails and the hydrophilic polar head group. The lower generations formed orthorhombic unit cell with long range ordering despite the alkyl tails tilted to a large degree. Favorable interactions between liquid crystalline terminal groups and the underlying substrate were observed to compel a flexible carbosilane dendrimer core to form a compressed elliptical conformation which packed stagger within lamellae domains with limited short range ordering. A twelve arm binary star polymer was observed to form two dimensional micelles at the air-water interface attributed to the higher polystyrene block composition. Linear rod-coil molecules formed a multitude of packing structures at the air-water interface due to the varying composition. Tree-like rod-coil molecules demonstrated the ability to form one-dimensional structures at the air-water interface and at the air-solvent interface caused by the preferential ordering of the rigid rod cores. The role of molecular architecture and composition was examined and the influence chemically competing fragments was shown to exert on the packing structure. The amphiphilic balance of the different molecular series exhibited control on the ordering behavior at the air-water interface and within bulk structures. The shell nature and tail type was determined to dictate the preferential ordering structure and molecular reorganization at interfaces with the core nature effect secondary.

  2. The Effect of Polarizability for the Understanding the Molecular Structure of Aqueous Interfaces

    SciTech Connect

    Wick, Collin D.; Kuo, I-F W.; Mundy, Christopher J.; Dang, Liem X.

    2007-11-01

    A review is presented on recent progress of the application of molecular dynamics simulation methods with the inclusion of polarizability for the understanding of aqueous interfaces. Comparisons among a variety of models, including Car-Parinello simulations, for the modeling of neat air-water interfaces are given. These results are used to describe the effect of polarizability on modeling the microscopic structure of the neat air-water interface, including comparisons with recent spectroscopic studies. Also, the understanding of the contribution of polarization to the electrostatic potential across the air-water interface is elucidated. Finally, the importance of polarizability for understanding anion transfer across an organic-water interface is shown. This work was performed at Pacific Northwest National Laboratory (PNNL) under the auspices of the Division of Chemical Sciences, Office of Basic Energy Sciences, U.S. Department of Energy. PNNL is operated by Battelle.

  3. Understand the limitations of air/water testing of distillation equipment

    SciTech Connect

    Bennett, D.L.; Ludwig, K.A. )

    1994-04-01

    Distillation continues to be a unit operation of major importance--and a dynamic area for technical development. The designs of trays and packings are rapidly evolving, and the application of equipment also is changing. As chemical processes are pushed to become more efficient and lower cost, a general reduction in the traditional values for equipment safety factors are being seen. The net results is that one now has a greater need for a more thorough and fundamental understanding of distillation equipment. One technique to improve the understanding of distillation equipment is air/water testing. Such testing of distillation trays has become very common, and air/water test results for packed columns also are being reported. In this article, the authors will provide some guidance on how to assess the validity of such tests to industrial applications. In addition, they will discuss several possible approaches to test--and develop confidence in--the design of distillation equipment.

  4. WETAIR: A computer code for calculating thermodynamic and transport properties of air-water mixtures

    NASA Technical Reports Server (NTRS)

    Fessler, T. E.

    1979-01-01

    A computer program subroutine, WETAIR, was developed to calculate the thermodynamic and transport properties of air water mixtures. It determines the thermodynamic state from assigned values of temperature and density, pressure and density, temperature and pressure, pressure and entropy, or pressure and enthalpy. The WETAIR calculates the properties of dry air and water (steam) by interpolating to obtain values from property tables. Then it uses simple mixing laws to calculate the properties of air water mixtures. Properties of mixtures with water contents below 40 percent (by mass) can be calculated at temperatures from 273.2 to 1497 K and pressures to 450 MN/sq m. Dry air properties can be calculated at temperatures as low as 150 K. Water properties can be calculated at temperatures to 1747 K and pressures to 100 MN/sq m. The WETAIR is available in both SFTRAN and FORTRAN.

  5. Interaction between heterogeneous environmental quality domains (air, water, land, socio-demographic and built environment) on preterm birth.

    EPA Science Inventory

    Environmental exposures are often measured individually, though many occur in tandem. To address aggregate exposures, a county-level Environmental Quality Index (EQI) representing five environmental domains (air, water, land, built and sociodemographic) was constructed. Recent st...

  6. Influence of eutrophication on air-water exchange, vertical fluxes, and phytoplankton concentrations of persistent organic pollutants

    SciTech Connect

    Dachs, J.; Eisenreich, S.J.; Hoff, R.M.

    2000-03-15

    The influence of eutrophication on the biogeochemical cycles of persistent organic pollutants (POPs) such as polychlorinated biphenyls (PCBs) is largely unknown. In this paper, the application of a dynamic air-water-phytoplankton exchange model to Lake Ontario is used as a framework to study the influence of eutrophication on air-water exchange, vertical fluxes, and phytoplankton concentrations of POPs. The results of these simulations demonstrate that air-water exchange controls phytoplankton concentrations in remote aquatic environments with little influence from land-based sources of pollutants and supports levels in even historically contaminated systems. Furthermore, eutrophication or high biomass leads to a disequilibrium between the gas and dissolved phase, enhanced air-water exchange, and vertical sinking fluxes of PCBs. Increasing biomass also depletes the water concentrations leading to lower than equilibrium PCB concentrations in phytoplankton. Implications to future trends in PCB pollution in Lake Ontario are also discussed.

  7. Miscibility behavior of two-component monolayers at the air-water interface: perfluorocarboxylic acids and DMPE.

    PubMed

    Yokoyama, Hiroki; Nakahara, Hiromichi; Nakagawa, Takahiro; Shimono, Satoshi; Sueishi, Kunihiko; Shibata, Osamu

    2009-09-01

    Surface pressure (pi)-molecular area (A) and surface potential (DeltaV)-A isotherms have been measured for two-component monolayers of four different perfluorocarboxylic acids [FCn; perfluorododecanoic acid (FC12), perfluorotetradecanoic acid (FC14), perfluorohexadecanoic acid (FC16), and perfluorooctadecanoic acid (FC18)] and dimyristoylphosphatidylethanolamine (DMPE) on 0.15M NaCl (pH 2) at 298.2K. The present study is focused on the miscibility and the interfacial behavior for the binary DMPE/FCn monolayers upon compression. From the isotherms, the miscibility has been elucidated in terms of the additivity rule, the interaction parameter, and the interaction energy. The interaction parameter (or energy) is compared with that for the previous dipalmitoylphosphatidylcholine (DPPC)/FCn systems [Colloids Surf. B 41 (2005) 285-298] to understand the effect of phospholipids' polar headgroup on the binary miscibility. Furthermore, the phase behavior of the DMPE/FCn systems has been morphologically examined using fluorescence microscopy (FM) and atomic force microscopy (AFM). These images reveal the different interaction modes among the four systems; DMPE can be miscible with FC12 and FC14 and immiscible with FC16 and FC18 in the monolayer state. These systematic examinations indicate that the miscibility of perfluorocarboxylic acids and phospholipids depends on combination of hydrocarbon and fluorocarbon chain lengths and on phospholipids' polar headgroups within a monolayer.

  8. The Turbulent Boundary Layer Near the Air-Water Interface on a Surface-Piercing Flat Plate

    NASA Astrophysics Data System (ADS)

    Washuta, Nathan; Masnadi, Naeem; Duncan, James H.

    2015-11-01

    Turbulent fluctuations in the vicinity of the water free surface along a flat, vertically oriented surface-piercing plate are studied experimentally using a laboratory-scale experiment. In this experiment, a meter-wide stainless steel belt travels horizontally in a loop around two rollers with vertically oriented axes, which are separated by 7.5 meters. This belt device is mounted inside a large water tank with the water level set just below the top edge of the belt. The belt, rollers, and supporting frame are contained within a sheet metal box to keep the device dry except for one 6-meter-long straight test section between rollers. The belt is launched from rest with a 3- g acceleration in order to quickly reach steady state velocity. This creates a temporally evolving boundary layer analogous to the spatially evolving boundary layer created along a flat-sided ship moving at the same velocity, with a length equivalent to the length of belt that has passed the measurement region since the belt motion began. Cinematic Stereo PIV measurements are performed in planes parallel to the free surface by imaging the flow from underneath the tank in order to study the modification of the boundary layer flow field due to the effects of the water free surface. The support of the Office of Naval Research under grant N000141110029 is gratefully acknowledged.

  9. Interaction between a growth-hormone releasing hexapeptide and phospholipids spread as monolayers at the air/water interface.

    PubMed

    Issaurat, B; Teissié, J

    1988-10-20

    The interaction between a growth-hormone releasing hexapeptide and phospholipids was studied on mixed monolayers models by means of surface fluorescence. When in a monolayer this hexapeptide which contains two tryptophan molecules was observed to fluoresce. Isothermal compression experiments showed that the complex was destroyed upon compression in the case of phosphatidylethanolamine. With phosphatidylglycerol it was observed to be stable but a dramatic reversible decrease in emission was observed at high surface pressure. This is indicative of a reversible change in the organization of the peptide-phospholipid complex. These observations indicate that, in the complex, hydrophobic interactions were weak but electrostatic ones, when present, were strong enough to maintain the GHRP attached to the monolayer and not to destabilize it. The integrity of the lipid monolayer appeared not to be affected by the peptide. PMID:3179304

  10. Spatial and seasonal variability of CO2 flux at the air-water interface of the Three Gorges Reservoir.

    PubMed

    Le, Yang; Lu, Fei; Wang, Xiaoke; Duan, Xiaonan; Tong, Lei; Ouyang, Zhiyun; Li, Hepeng

    2013-11-01

    Diffusive carbon dioxide (CO2) emissions from the water surface of the Three Gorges Reservoir, currently the largest hydroelectric reservoir in the world, were measured using floating static chambers over the course of a yearlong survey. The results showed that the average annual CO2 flux was (163.3 +/- 117.4) mg CO2/(m2.hr) at the reservoir surface, which was larger than the CO2 flux in most boreal and temperate reservoirs but lower than that in tropical reservoirs. Significant spatial variations in CO2 flux were observed at four measured sites, with the largest flux measured at Wushan (221.9 mg CO2/(m2.hr)) and the smallest flux measured at Zigui (88.6 mg CO2/(m(2).hr)); these differences were probably related to the average water velocities at different sites. Seasonal variations in CO2 flux were also observed at four sites, starting to increase in January, continuously rising until peaking in the summer (June-August) and gradually decreasing thereafter. Seasonal variations in CO2 flux could reflect seasonal dynamics in pH, water velocity, and temperature. Since the spatial and temporal variations in CO2 flux were significant and dependent on multiple physical, chemical, and hydrological factors, it is suggested that long-term measurements should be made on a large spatial scale to assess the climatic influence of hydropower in China, as well as the rest of the world.

  11. Sea spray production by bag breakup mode of fragmentation of the air-water interface at strong and hurricane wind

    NASA Astrophysics Data System (ADS)

    Troitskaya, Yuliya; Kandaurov, Alexander; Ermakova, Olga; Kozlov, Dmitry; Sergeev, Daniil; Zilitinkevich, Sergej

    2016-04-01

    Sea sprays is a typical element of the marine atmospheric boundary layer (MABL) of large importance for marine meteorology, atmospheric chemistry and climate studies. They are considered as a crucial factor in the development of hurricanes and severe extratropical storms, since they can significantly enhance exchange of mass, heat and momentum between the ocean and the atmosphere. This exchange is directly provided by spume droplets with the sizes from 10 microns to a few millimeters mechanically torn off the crests of a breaking waves and fall down to the ocean due to gravity. The fluxes associated with the spray are determined by the rate of droplet production at the surface quantified by the sea spray generation function (SSGF), defined as the number of spray particles of radius r produced from the unit area of water surface in unit time. However, the mechanism of spume droplets' formation is unknown and empirical estimates of SSGF varied over six orders of magnitude; therefore, the production rate of large sea spray droplets is not adequately described and there are significant uncertainties in estimations of exchange processes in hurricanes. Experimental core of our work comprise laboratory experiments employing high-speed video-filming, which have made it possible to disclose how water surface looks like at extremely strong winds and how exactly droplets are torn off wave crests. We classified events responsible for spume droplet, including bursting of submerged bubbles, generation and breakup of "projections" or liquid filaments (Koa, 1981) and "bag breakup", namely, inflating and consequent blowing of short-lived, sail-like pieces of the water-surface film, "bags". The process is similar to "bag-breakup" mode of fragmentation of liquid droplets and jets in gaseous flows. Basing on statistical analysis of results of these experiments we show that the main mechanism of spray-generation is attributed to "bag-breakup mechanism On the base of general principles of statistical physics (model of a canonical ensemble) we developed statistics of the "bag-breakup" events and constructed sea spray generation function (SSGF) for the mechanism of "bag-breakup". The "bag breakup" SSGF is shown to be in reasonable agreement in magnitude with SSFGs considered as the most reliable source function for spume droplets. The new SSGF is employed for estimate of the new"bag-breakup" mechanism to momentum and energy exchange in marine atmospheric boundary layer at hurricane conditions. This work was supported by the Russian Foundation of Basic Research (14-05-91767, 13-05-12093, 16-05-00839, 14-05-91767, 16-55-52025) and experiment and equipment was supported by Russian Science Foundation (Agreements 14-17-00667 and 15-17-20009 respectively), Yu.Troitskaya, A.Kandaurov and D.Sergeev were partially supported by FP7 collaborative Project No. 612610.

  12. Point-spread function associated with underwater imaging through a wavy air-water interface: theory and laboratory tank experiment.

    PubMed

    Brown, W C; Majumdar, A K

    1992-12-20

    The point-spread function needed for imaging underwater objects is theoretically derived and compared with experimental results. The theoretical development is based on the emergent-ray model, in which the Gram-Charlier series for the non-Gaussian probability-density function for emergent angles through a wavy water surface was assumed. To arrive at the point-spread model, we used a finite-element methodology with emergent-ray angular probability distributions as fundamental building functions. The model is in good agreement with the experiment for downwind conditions. A slight deviation between theory and experiment was observed for the crosswind case; this deviation may be caused by the possible interaction of standing waves with the original air-ruffled capillary waves that were not taken into account in the model.

  13. Extraordinary cohesiveness of a boronic acid-based calix[6]arene monolayer at the air-water interface

    SciTech Connect

    Hendel, R.A.; Janout, V.; Lee, W.; Regen, S.L.

    1996-11-13

    In this paper, we describe the design and synthesis of calix[6]arene. We also report our unexpected finding that monolayers of the surfactant exhibit extraordinary cohesiveness while in intimate contact with water; i.e., dehydration is not essential for stabilizing the film. The specific molecule that was chosen as a synthetic target was 5,11,17,23,29, 35-hexakis(3-dihydroxybora-1-propyl)-37,38,39,40,41, 42-hexakis(hexadecycloxy)calix[6]-arene, I. The synthesis of I proved to be straightforward using methods that have previously been developed for calix[6]arene and alkylboronic acids synthesis. 10 refs., 2 figs.

  14. Supramolecular control of photochemical and electrochemical properties of two oligothiophene derivatives at the air/water interface.

    PubMed

    Selector, Sophiya; Fedorova, Olga; Lukovskaya, Elena; Anisimov, Alexander; Fedorov, Yuri; Tarasova, Nina; Raitman, Oleg; Fages, Frederic; Arslanov, Vladimir

    2012-02-01

    Two geometric isomers of oligothiophene derivatives containing two crowned styryl fragments in 2- or 3-positions of thiophene rings are able to form stable monolayers on the water subphase. The organizing of crown-containing oligothiophenes in monolayers is guided by the π-stacking interaction of hydrophobic styrylthiophene fragments and interaction of hydrophilic macrocycles with the water subphase. The difference in structure of oligothiophene molecules leads to the formation of distinct monolayer architectures with various electrochemical and optical characteristics.

  15. Sensitivity study of poisson corruption in tomographic measurements for air-water flows

    SciTech Connect

    Munshi, P. ); Vaidya, M.S. )

    1993-01-01

    An application of computerized tomography (CT) for measuring void fraction profiles in two-phase air-water flows was reported earlier. Those attempts involved some special radial methods for tomographic reconstruction and the popular convolution backprojection (CBP) method. The CBP method is capable of reconstructing void profiles for nonsymmetric flows also. In this paper, we investigate the effect of corrupted CT data for gamma-ray sources and aCBP algorithm. The corruption in such a case is due to the statistical (Poisson) nature of the source.

  16. Air-Water Exchange of Legacy and Emerging Organic Pollutants across the Great Lakes

    NASA Astrophysics Data System (ADS)

    Lohmann, R.; Ruge, Z.; Khairy, M.; Muir, D.; Helm, P.

    2014-12-01

    Organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) are transported to great water bodies via long-range atmospheric transport and released from the surface water as air concentrations continue to diminish. As the largest fresh water bodies in North America, the Great Lakes have both the potential to accumulate and serve as a secondary source of persistent bioaccumulative toxins. OCP and PCB concentrations were sampled at 30+ sites across Lake Superior, Ontario and Erie in the summer of 2011. Polyethylene passive samplers (PEs) were simultaneously deployed in surface water and near surface atmosphere to determine air-water gaseous exchange of OCPs and PCBs. In Lake Superior, surface water and atmospheric concentrations were dominated by α-HCH (average 250 pg/L and 4.2 pg/m3, respectively), followed by HCB (average 17 pg/L and 89 pg/m3, respectively). Air-water exchange varied greatly between sites and individual OCPs, however α-endosulfan was consistently deposited into the surface water (average 19 pg/m2/day). PCBs in the air and water were characterized by penta- and hexachlorobiphenyls with distribution along the coast correlated with proximity to developed areas. Air-water exchange gradients generally yielded net volatilization of PCBs out of Lake Superior. Gaseous concentrations of hexachlorobenzene, dieldrin and chlordanes were significantly higher (p < 0.05) at Lake Erie than Lake Ontario. A multiple linear regression that incorporated meteorological, landuse and population data was used to explain variability in the atmospheric concentrations. Results indicated that landuse (urban and/or cropland) greatly explained the variability in the data. Freely dissolved concentrations of OCPs (

  17. Determining Spatial Distribution And Air-Water Exchange Of Polycyclic Aromatic Hydrocarbons In Stormwater Runoff Catchment Basins

    NASA Astrophysics Data System (ADS)

    Kasaraneni, V. K.; Schifman, L. A.; Craver, V.; Boving, T. B.

    2014-12-01

    Stormwater runoff is a conduit for several pollutants such as polycyclic aromatic hydrocarbons (PAHs) in to surface and ground water bodies. The control of runoff and pollutants is typically addressed by best management practices (BMPs), such as retention/detention ponds or catchment basins in general. The effectiveness of catchment basins in reducing the volume of runoff and removal of some contaminants has been established. However, very little is known about the fate of the contaminants settled within these structures. In coastal regions and places with shallow groundwater tables accumulation of high concentrations of PAHs in the bottom sediments poses a potential threat for groundwater contamination. The concentrations of PAHs accumulated in the sediments of these catchment basins will primarily depend on the sources of runoff origin and the surrounding land use. Due to the physico-chemical characteristics of PAHs, their transport not only can occur in the liquid and solid phase, but it is also possible that gaseous emissions can be produced from BMP systems. For the purpose of this study, five stormwater catchment basins along the I-95 corridor in Rhode Island were selected based on the stormwater runoff origin and covering (industrial, urban, highway, and commercial) land uses. To study the stratification of PAHs sediment cores one foot were collected and analyzed for 31PAHs (16 EPA parent PAH and 15 methylated PAHs). In order to determine whether the catchment basins are a source of atmospheric pollution polyethylene passive samplers were deployed to determine the freely dissolved PAHs in the water column and gas phase PAHs at the air-water interface. This presentation will describe how PAH fluxes move between three environmental compartments (sediments, water column, atmosphere) within the five stormwater catchment basins. Further, it will be investigated whether these BMP structures can act as contaminant sources rather than sinks and whether BMP

  18. Changing Pattern of Crop Fraction in Late Blight Induced Potato Crops in Potato Bowl of West Bengal by using Multi-temporal Time Series AWiFs Data

    NASA Astrophysics Data System (ADS)

    Chakrabarty, Abhisek

    2016-07-01

    Crop fraction is the ratio of crop occupying a unit area in ground pixel, is very important for monitoring crop growth. One of the most important variables in crop growth monitoring is the fraction of available solar radiation intercepted by foliage. Late blight of potato (Solanum tuberosum), caused by the oomycete pathogen Phytophthora infestans, is considered to be the most destructive crop diseases of potato worldwide. Under favourable climatic conditions, and without intervention (i.e. fungicide sprays), the disease can destroy potato crop within few weeks. Therefore it is important to evaluate the crop fraction for monitoring the healthy and late blight affected potato crops. This study was conducted in potato bowl of West Bengal, which consists of districts of Hooghly, Howrah, Burdwan, Bankuara, and Paschim Medinipur. In this study different crop fraction estimation method like linear spectral un-mixing, Normalized difference vegetation index (NDVI) based DPM model (Zhang et al. 2013), Ratio vegetation index based DPM model, improved Pixel Dichotomy Model (Li et al. 2014) ware evaluated using multi-temporal IRS AWiFs data in two successive potato growing season of 2012-13 and 2013-14 over the study area and compared with measured crop fraction. The comparative study based on measured healthy and late blight affected potato crop fraction showed that improved Pixel Dichotomy Model maintain the high coefficient of determination (R2= 0.835) with low root mean square error (RMSE=0.21) whereas the correlation values of NDVI based DPM model and RVI based DPM model is 0.763 and 0.694 respectively. The changing pattern of crop fraction profile of late blight affected potato crop was studied in respect of healthy potato crop fraction which was extracted from the 269 GPS points of potato field. It showed that the healthy potato crop fraction profile maintained the normal phenological trend whereas the late blight affected potato crop fraction profile suddenly fallen

  19. Cross-calibration of the Landsat-7 ETM+ and Landsat-5 TM with the ResourceSat-1 (IRS-P6) AWiFS and LISS-III sensors

    USGS Publications Warehouse

    Chander, G.; Scaramuzza, P.L.

    2006-01-01

    Increasingly, data from multiple sensors are used to gain a more complete understanding of land surface processes at a variety of scales. The Landsat suite of satellites has collected the longest continuous archive of multispectral data. The ResourceSat-1 Satellite (also called as IRS-P6) was launched into the polar sunsynchronous orbit on Oct 17, 2003. It carries three remote sensing sensors: the High Resolution Linear Imaging Self-Scanner (LISS-IV), Medium Resolution Linear Imaging Self-Scanner (LISS-III), and the Advanced Wide Field Sensor (AWiFS). These three sensors are used together to provide images with different resolution and coverage. To understand the absolute radiometric calibration accuracy of IRS-P6 AWiFS and LISS-III sensors, image pairs from these sensors were compared to the Landsat-5 TM and Landsat-7 ETM+ sensors. The approach involved the calibration of nearly simultaneous surface observations based on image statistics from areas observed simultaneously by the two sensors.

  20. Cross-calibration of the Landsat-7 ETM+ and Landsat-5 TM with the ResourceSat-1 (IRS-P6) AWiFS and LISS-III sensors

    NASA Astrophysics Data System (ADS)

    Chander, Gyanesh; Scaramuzza, Pat L.

    2006-12-01

    Increasingly, data from multiple sensors are used to gain a more complete understanding of land surface processes at a variety of scales. The Landsat suite of satellites has collected the longest continuous archive of multispectral data. The ResourceSat-1 Satellite (also called as IRS-P6) was launched into the polar sun-synchronous orbit on Oct 17, 2003. It carries three remote sensing sensors: the High Resolution Linear Imaging Self-Scanner (LISS-IV), Medium Resolution Linear Imaging Self-Scanner (LISS-III), and the Advanced Wide Field Sensor (AWiFS). These three sensors are used together to provide images with different resolution and coverage. To understand the absolute radiometric calibration accuracy of IRS-P6 AWiFS and LISS-III sensors, image pairs from these sensors were compared to the Landsat-5 TM and Landsat-7 ETM+ sensors. The approach involved the calibration of nearly simultaneous surface observations based on image statistics from areas observed simultaneously by the two sensors.

  1. Air-water ‘tornado’-type microwave plasmas applied for sugarcane biomass treatment

    NASA Astrophysics Data System (ADS)

    Bundaleska, N.; Tatarova, E.; Dias, F. M.; Lino da Silva, M.; Ferreira, C. M.; Amorim, J.

    2014-02-01

    The production of cellulosic ethanol from sugarcane biomass is an attractive alternative to the use of fossil fuels. Pretreatment is needed to separate the cellulosic material, which is packed with hemicellulose and lignin in cell wall of sugarcane biomass. A microwave ‘tornado’-type air-water plasma source operating at 2.45 GHz and atmospheric pressure has been applied for this purpose. Samples of dry and wet biomass (˜2 g) have been exposed to the late afterglow plasma stream. The experiments demonstrate that the air-water highly reactive plasma environment provides a number of long-lived active species able to destroy the cellulosic wrapping. Scanning electron microscopy has been applied to analyse the morphological changes occurring due to plasma treatment. The effluent gas streams have been analysed by Fourier-transform infrared spectroscopy (FT-IR). Optical emission spectroscopy and FT-IR have been applied to determine the gas temperature in the discharge and late afterglow plasma zones, respectively. The optimal range of the operational parameters is discussed along with the main active species involved in the treatment process. Synergistic effects can result from the action of singlet O2(a 1Δg) oxygen, NO2, nitrous acid HNO2 and OH hydroxyl radical.

  2. Predicting Air-Water Geysers and Their Implications on Reducing Combined Sewer Overflows

    NASA Astrophysics Data System (ADS)

    Choi, Y.; Leon, A.; Apte, S.

    2014-12-01

    An air-water geyser in a closed conduit system is characterized by an explosive jetting of a mixture of air and water through drop-shafts. In this study, three scenarios of geysers are numerically simulated using a 3D computational fluid dynamics (CFD) model. The three tested scenarios are comprised of a drop shaft that is closed at its bottom and partially or fully open at the top. Initially, the lower section of the drop shaft is filled with pressurized air, the middle section with stagnant water and the upper section with air at atmospheric pressure. The pressure and volume of the pressurized air, and hence the stored energy, is different for all three test cases. The volume of the stagnant water and the air at atmospheric pressure are kept constant in the tests. The numerical simulations aim to identify the correlation between dimensionless energy stored in the pressurized air pocket and dimensionless maximum pressure reached at the outlet. This dimensionless correlation could be used to determine the energy threshold that does not produce air-water geyser, which in turn could be used in the design of combined sewer systems for minimizing geysers.

  3. Spatial Distribution and Air-Water Exchange of Organic Flame Retardants in the Lower Great Lakes.

    PubMed

    McDonough, Carrie A; Puggioni, Gavino; Helm, Paul A; Muir, Derek; Lohmann, Rainer

    2016-09-01

    Organic flame retardants (OFRs) such as polybrominated diphenyl ethers (PBDEs) and novel halogenated flame retardants (NHFRs) are ubiquitous, persistent, and bioaccumulative contaminants that have been used in consumer goods to slow combustion. In this study, polyethylene passive samplers (PEs) were deployed throughout the lower Great Lakes (Lake Erie and Lake Ontario) to measure OFRs in air and water, calculate air-water exchange fluxes, and investigate spatial trends. Dissolved Σ12BDE was greatest in Lake Ontario near Toronto (18 pg/L), whereas gaseous Σ12BDE was greatest on the southern shoreline of Lake Erie (11 pg/m(3)). NHFRs were generally below detection limits. Air-water exchange was dominated by absorption of BDEs 47 and 99, ranging from -964 pg/m(2)/day to -30 pg/m(2)/day. Σ12BDE in air and water was significantly correlated with surrounding population density, suggesting that phased-out PBDEs continued to be emitted from population centers along the Great Lakes shoreline in 2012. Correlation with dissolved Σ12BDE was strongest when considering population within 25 km while correlation with gaseous Σ12BDE was strongest when using population within 3 km to the south of each site. Bayesian kriging was used to predict dissolved Σ12BDE over the lakes, illustrating the utility of relatively highly spatially resolved measurements in identifying potential hot spots for future study.

  4. Spatial Distribution and Air-Water Exchange of Organic Flame Retardants in the Lower Great Lakes.

    PubMed

    McDonough, Carrie A; Puggioni, Gavino; Helm, Paul A; Muir, Derek; Lohmann, Rainer

    2016-09-01

    Organic flame retardants (OFRs) such as polybrominated diphenyl ethers (PBDEs) and novel halogenated flame retardants (NHFRs) are ubiquitous, persistent, and bioaccumulative contaminants that have been used in consumer goods to slow combustion. In this study, polyethylene passive samplers (PEs) were deployed throughout the lower Great Lakes (Lake Erie and Lake Ontario) to measure OFRs in air and water, calculate air-water exchange fluxes, and investigate spatial trends. Dissolved Σ12BDE was greatest in Lake Ontario near Toronto (18 pg/L), whereas gaseous Σ12BDE was greatest on the southern shoreline of Lake Erie (11 pg/m(3)). NHFRs were generally below detection limits. Air-water exchange was dominated by absorption of BDEs 47 and 99, ranging from -964 pg/m(2)/day to -30 pg/m(2)/day. Σ12BDE in air and water was significantly correlated with surrounding population density, suggesting that phased-out PBDEs continued to be emitted from population centers along the Great Lakes shoreline in 2012. Correlation with dissolved Σ12BDE was strongest when considering population within 25 km while correlation with gaseous Σ12BDE was strongest when using population within 3 km to the south of each site. Bayesian kriging was used to predict dissolved Σ12BDE over the lakes, illustrating the utility of relatively highly spatially resolved measurements in identifying potential hot spots for future study. PMID:27458653

  5. Novel methods for measuring air-water interfacial area in unsaturated porous media.

    PubMed

    Brusseau, Mark L; El Ouni, Asma; Araujo, Juliana B; Zhong, Hua

    2015-05-01

    Interfacial partitioning tracer tests (IPTT) are used to measure air-water interfacial area for unsaturated porous media. The standard IPTT method involves conducting tests wherein an aqueous surfactant solution is introduced into a packed column under unsaturated flow conditions. Surfactant-induced drainage has been observed to occur for this method in some cases, which can complicate data analysis and impart uncertainty to the measured values. Two novel alternative approaches for conducting IPTTs are presented herein that are designed in part to prevent surfactant-induced drainage. The two methods are termed the dual-surfactant IPTT (IPTT-DS) and the residual-air IPTT (IPTT-RA). The two methods were used to measure air-water interfacial areas for two natural porous media. System monitoring during the tests revealed no measurable surfactant-induced drainage. The measured interfacial areas compared well to those obtained with the standard IPTT method conducted in such a manner that surfactant-induced drainage was prevented. PMID:25732632

  6. Novel methods for measuring air-water interfacial area in unsaturated porous media.

    PubMed

    Brusseau, Mark L; El Ouni, Asma; Araujo, Juliana B; Zhong, Hua

    2015-05-01

    Interfacial partitioning tracer tests (IPTT) are used to measure air-water interfacial area for unsaturated porous media. The standard IPTT method involves conducting tests wherein an aqueous surfactant solution is introduced into a packed column under unsaturated flow conditions. Surfactant-induced drainage has been observed to occur for this method in some cases, which can complicate data analysis and impart uncertainty to the measured values. Two novel alternative approaches for conducting IPTTs are presented herein that are designed in part to prevent surfactant-induced drainage. The two methods are termed the dual-surfactant IPTT (IPTT-DS) and the residual-air IPTT (IPTT-RA). The two methods were used to measure air-water interfacial areas for two natural porous media. System monitoring during the tests revealed no measurable surfactant-induced drainage. The measured interfacial areas compared well to those obtained with the standard IPTT method conducted in such a manner that surfactant-induced drainage was prevented.

  7. Air-water gas exchange and CO2 flux in a mangrove-dominated estuary

    USGS Publications Warehouse

    Ho, David T.; Ferrón, Sara; Engel, Victor C.; Larsen, Laurel G.; Barr, Jordan G.

    2014-01-01

    Mangrove forests are highly productive ecosystems, but the fate of mangrove-derived carbon remains uncertain. Part of that uncertainty stems from the fact that gas transfer velocities in mangrove-surrounded waters are not well determined, leading to uncertainty in air-water CO2 fluxes. Two SF6 tracer release experiments were conducted to determine gas transfer velocities (k(600) = 8.3 ± 0.4 and 8.1 ± 0.6 cm h−1), along with simultaneous measurements of pCO2 to determine the air-water CO2 fluxes from Shark River, Florida (232.11 ± 23.69 and 171.13 ± 20.28 mmol C m−2 d−1), an estuary within the largest contiguous mangrove forest in North America. The gas transfer velocity results are consistent with turbulent kinetic energy dissipation measurements, indicating a higher rate of turbulence and gas exchange than predicted by commonly used wind speed/gas exchange parameterizations. The results have important implications for carbon fluxes in mangrove ecosystems.

  8. An air-water interfacial area based variable tortuosity model for unsaturated sands

    SciTech Connect

    Khaleel, Raziuddin; Saripalli, Prasad

    2006-05-01

    Based on Kozeny-Carman equation for saturated media permeability, a new model is developed for the prediction of unsaturated hydraulic conductivity, K as a function of moisture content, ?. The K(???) estimates are obtained using laboratory measurements of moisture retention and saturated hydraulic conductivity, and a saturation-dependent tortuosity based on the immiscible fluid (air-water) interfacial area. Tortuosity (?a) for unsaturated media is defined as aaw/aaw,o (ratio of the specific air-water interfacial area of a real and the corresponding idealized porous medium). A correspondence between the real and idealized media is established by using the laboratory-measured soil moisture retention curve to calculate the interfacial area. The general trend in prediction of ?a as a function water saturation is in agreement with similar recent predictions based on diffusion theory. Unsaturated hydraulic conductivities measured for a number of coarse-textured, repacked Hanford sediments agree well with predictions based on the modified Kozeny-Carman relation. Because of the use of saturated hydraulic conductivity, a slight bias is apparent in measured and predicted K at low ?. While the modified Kozeny-Carman relation was found to be reasonably accurate in predicting K(??) for the repacked, sandy soils considered in this study, a further testing of the new model for undisturbed sediments and other soil textures would be useful.

  9. Orientational Dynamics of Water at an Extended Hydrophobic Interface.

    PubMed

    Xiao, Shunhao; Figge, Florian; Stirnemann, Guillaume; Laage, Damien; McGuire, John A

    2016-05-01

    We report on the orientational dynamics of water at an extended hydrophobic interface with an octadecylsilane self-assembled monolayer on fused silica. The interfacial dangling OH stretch mode is excited with a resonant pump, and its evolution followed in time by a surface-specific, vibrationally resonant, infrared-visible sum-frequency probe. High sensitivity pump-probe anisotropy measurements and isotopic dilution clearly reveal that the decay of the dangling OH stretch excitation is almost entirely due to a jump to a hydrogen-bonded configuration that occurs in 1.61 ± 0.10 ps. This is more than twice as fast as the jump time from one hydrogen-bonded configuration to another in bulk H2O but about 50% slower than the reported out-of-plane reorientation at the air/water interface. In contrast, the intrinsic population lifetime of the dangling OH stretch in the absence of such jumps is found to be >10 ps. Molecular dynamics simulations of air/water and hexane/water interfaces reproduce the fast jump dynamics of interfacial dangling OH with calculated jump times of 1.4 and 1.7 ps for the air and hydrophobic interfaces, respectively. The simulations highlight that while the air/water and hydrophobic/water surfaces exhibit great structural similarities, a small stabilization of the OH groups by the hydrophobic interface produces the pronounced difference in the dynamics of dangling bonds. PMID:27045950

  10. Compositions of surface layers formed on amalgams in air, water, and saline.

    PubMed

    Hanawa, T; Gnade, B E; Ferracane, J L; Okabe, T; Watari, F

    1993-12-01

    The surface layers formed on both a zinc-free and a zinc-containing dental amalgam after polishing and aging in air, water, or saline, were characterized using x-ray photoelectron spectroscopy (XPS) to determine the compositions of the surface layers which might govern the release of mercury from amalgam. The XPS data revealed that the formation of the surface layer on the zinc-containing amalgam was affected by the environment in which the amalgam was polished and aged, whereas that on the zinc-free amalgam was not affected. In addition, among the elements contained in amalgam, zinc was the most reactive with the environment, and was preferentially dissolved from amalgam into water or saline. Mercury atoms existed in the metallic state in the surface layer.

  11. Interfacial structures of confined air-water two-phase bubbly flow

    SciTech Connect

    Kim, S.; Ishii, M.; Wu, Q.; McCreary, D.; Beus, S.G.

    2000-08-01

    The interfacial structure of the two-phase flows is of great importance in view of theoretical modeling and practical applications. In the present study, the focus is made on obtaining detailed local two-phase parameters in the air-water bubbly flow in a rectangular vertical duct using the double-sensor conductivity probe. The characteristic wall-peak is observed in the profiles of the interracial area concentration and the void fraction. The development of the interfacial area concentration along the axial direction of the flow is studied in view of the interfacial area transport and bubble interactions. The experimental data is compared with the drift flux model with C{sub 0} = 1.35.

  12. Near-surface physics during convection affecting air-water gas transfer

    NASA Astrophysics Data System (ADS)

    Fredriksson, S. T.; Arneborg, L.; Nilsson, H.; Handler, R. A.

    2016-05-01

    The gas flux at the water surface is affected by physical processes including turbulence from wind shear, microscale wave breaking, large-scale breaking, and convection due to heat loss at the surface. The main route in the parameterizations of the gas flux has been to use the wind speed as a proxy for the gas flux velocity, indirectly taking into account the dependency of the wind shear and the wave processes. The interest in the contributions from convection processes has increased as the gas flux from inland waters (with typically lower wind and sheltered conditions) now is believed to play a substantial role in the air-water gas flux budget. The gas flux is enhanced by convection through the mixing of the mixed layer as well as by decreasing the diffusive boundary layer thickness. The direct numerical simulations performed in this study are shown to be a valuable tool to enhance the understanding of this flow configuration often present in nature.

  13. Measuring Air-water Interfacial Area for Soils Using the Mass Balance Surfactant-tracer Method

    PubMed Central

    Araujo, Juliana B.; Mainhagu, Jon; Brusseau, Mark L.

    2015-01-01

    There are several methods for conducting interfacial partitioning tracer tests to measure air-water interfacial area in porous media. One such approach is the mass balance surfactant tracer method. An advantage of the mass-balance method compared to other tracer-based methods is that a single test can produce multiple interfacial area measurements over a wide range of water saturations. The mass-balance method has been used to date only for glass beads or treated quartz sand. The purpose of this research is to investigate the effectiveness and implementability of the mass-balance method for application to more complex porous media. The results indicate that interfacial areas measured with the mass-balance method are consistent with values obtained with the miscible-displacement method. This includes results for a soil, for which solid-phase adsorption was a significant component of total tracer retention. PMID:25950136

  14. Study of interfacial area transport and sensitivity analysis for air-water bubbly flow

    SciTech Connect

    Kim, S.; Sun, X.; Ishii, M.; Beus, S.G.

    2000-09-01

    The interfacial area transport equation applicable to the bubbly flow is presented. The model is evaluated against the data acquired by the state-of-the-art miniaturized double-sensor conductivity probe in an adiabatic air-water co-current vertical test loop under atmospheric pressure condition. In general, a good agreement, within the measurement error of plus/minus 10%, is observed for a wide range in the bubbly flow regime. The sensitivity analysis on the individual particle interaction mechanisms demonstrates the active interactions between the bubbles and highlights the mechanisms playing the dominant role in interfacial area transport. The analysis employing the drift flux model is also performed for the data acquired. Under the given flow conditions, the distribution parameter of 1.076 yields the best fit to the data.

  15. Measuring air-water interfacial area for soils using the mass balance surfactant-tracer method.

    PubMed

    Araujo, Juliana B; Mainhagu, Jon; Brusseau, Mark L

    2015-09-01

    There are several methods for conducting interfacial partitioning tracer tests to measure air-water interfacial area in porous media. One such approach is the mass balance surfactant tracer method. An advantage of the mass-balance method compared to other tracer-based methods is that a single test can produce multiple interfacial area measurements over a wide range of water saturations. The mass-balance method has been used to date only for glass beads or treated quartz sand. The purpose of this research is to investigate the effectiveness and implementability of the mass-balance method for application to more complex porous media. The results indicate that interfacial areas measured with the mass-balance method are consistent with values obtained with the miscible-displacement method. This includes results for a soil, for which solid-phase adsorption was a significant component of total tracer retention.

  16. Precision cleaning verification of fluid components by air/water impingement and total carbon analysis

    NASA Technical Reports Server (NTRS)

    Barile, Ronald G.; Fogarty, Chris; Cantrell, Chris; Melton, Gregory S.

    1994-01-01

    NASA personnel at Kennedy Space Center's Material Science Laboratory have developed new environmentally sound precision cleaning and verification techniques for systems and components found at the center. This technology is required to replace existing methods traditionally employing CFC-113. The new patent-pending technique of precision cleaning verification is for large components of cryogenic fluid systems. These are stainless steel, sand cast valve bodies with internal surface areas ranging from 0.2 to 0.9 sq m. Extrapolation of this technique to components of even larger sizes (by orders of magnitude) is planned. Currently, the verification process is completely manual. In the new technique, a high velocity, low volume water stream impacts the part to be verified. This process is referred to as Breathing Air/Water Impingement and forms the basis for the Impingement Verification System (IVS). The system is unique in that a gas stream is used to accelerate the water droplets to high speeds. Water is injected into the gas stream in a small, continuous amount. The air/water mixture is then passed through a converging/diverging nozzle where the gas is accelerated to supersonic velocities. These droplets impart sufficient energy to the precision cleaned surface to place non-volatile residue (NVR) contaminants into suspension in the water. The sample water is collected and its NVR level is determined by total organic carbon (TOC) analysis at 880 C. The TOC, in ppm carbon, is used to establish the NVR level. A correlation between the present gravimetric CFC113 NVR and the IVS NVR is found from experimental sensitivity factors measured for various contaminants. The sensitivity has the units of ppm of carbon per mg/sq ft of contaminant. In this paper, the equipment is described and data are presented showing the development of the sensitivity factors from a test set including four NVRs impinged from witness plates of 0.05 to 0.75 sq m.

  17. Air/water oxidative desulfurization of coal and sulfur-containing compounds

    NASA Astrophysics Data System (ADS)

    Warzinski, R. P.; Freidman, S.; LaCount, R. B.

    1981-02-01

    Air/water Oxydesulfurization has been demonstrated in autoclave experiments at the Pittsburgh Energy Technology Center for various coals representative of the major U. S. coal basins. The applicability at present of this treatment for producing an environmentally acceptable coal has been restricted by recently proposed SO2 emission standards for utility boilers. The product would, however, be attractive to the many smaller industrial coal users who cannot afford to operate and maintain flue gas desulfurization systems. It is also possible that the utility industry could realize a benefit by using chemically cleaned coal with partial flue gas scrubbing. The higher cost of the cleaned coal would be offset by the reduction in capital and operating costs resulting from decreased FGD requirements. The susceptibility of sulfur in coal to oxidative removal varies with the nature of the sulfur-containing species. The inorganic sulfur compounds, primarily pyrite, marcasite, and iron sulfate, are more amenable to treatment than the organically bound sulfur which exhibits varying degrees of resistance depending on its chemical environment. Air/water Oxydesulfurization consistently removes in excess of 90 percent of the pyritic sulfur; the extent and efficiency of organic sulfur removal however, depends on the type of coal and severity of treatment used. In general, the organic sulfur of the higher rank coals exhibits more resistance to treatment than that of the lower rank coals; however, the accompanying heating value is greater for the latter. Similar treatment of sulfur-containing model compounds further illustrates the relative susceptibilities of different chemical species to oxidation. Application of these data to the understanding of the complex chemistry involved in the treatment of coal is a preliminary step toward improving the efficiency of Oxydesulfurization.

  18. Precision Cleaning Verification of Fluid Components by Air/Water Impingement and Total Carbon Analysis

    NASA Technical Reports Server (NTRS)

    Barile, Ronald G.; Fogarty, Chris; Cantrell, Chris; Melton, Gregory S.

    1995-01-01

    NASA personnel at Kennedy Space Center's Material Science Laboratory have developed new environmentally sound precision cleaning and verification techniques for systems and components found at the center. This technology is required to replace existing methods traditionally employing CFC-113. The new patent-pending technique of precision cleaning verification is for large components of cryogenic fluid systems. These are stainless steel, sand cast valve bodies with internal surface areas ranging from 0.2 to 0.9 m(exp 2). Extrapolation of this technique to components of even larger sizes (by orders of magnitude) is planned. Currently, the verification process is completely manual. In the new technique, a high velocity, low volume water stream impacts the part to be verified. This process is referred to as Breathing Air/Water Impingement and forms the basis for the Impingement Verification System (IVS). The system is unique in that a gas stream is used to accelerate the water droplets to high speeds. Water is injected into the gas stream in a small, continuous amount. The air/water mixture is then passed through a converging-diverging nozzle where the gas is accelerated to supersonic velocities. These droplets impart sufficient energy to the precision cleaned surface to place non-volatile residue (NVR) contaminants into suspension in the water. The sample water is collected and its NVR level is determined by total organic carbon (TOC) analysis at 880 C. The TOC, in ppm carbon, is used to establish the NVR level. A correlation between the present gravimetric CFC-113 NVR and the IVS NVR is found from experimental sensitivity factors measured for various contaminants. The sensitivity has the units of ppm of carbon per mg-ft(exp 2) of contaminant. In this paper, the equipment is described and data are presented showing the development of the sensitivity factors from a test set including four NVR's impinged from witness plates of 0.05 to 0.75 m(exp 2).

  19. Simulating Urban Tree Effects on Air, Water, and Heat Pollution Mitigation: iTree-Hydro Model

    NASA Astrophysics Data System (ADS)

    Yang, Y.; Endreny, T. A.; Nowak, D.

    2011-12-01

    Urban and suburban development changes land surface thermal, radiative, porous, and roughness properties and pollutant loading rates, with the combined effect leading to increased air, water, and heat pollution (e.g., urban heat islands). In this research we present the USDA Forest Service urban forest ecosystem and hydrology model, iTree Eco and Hydro, used to analyze how tree cover can deliver valuable ecosystem services to mitigate air, water, and heat pollution. Air pollution mitigation is simulated by dry deposition processes based on detected pollutant levels for CO, NO2, SO2, O3 and atmospheric stability and leaf area indices. Water quality mitigation is simulated with event mean concentration loading algorithms for N, P, metals, and TSS, and by green infrastructure pollutant filtering algorithms that consider flow path dispersal areas. Urban cooling considers direct shading and indirect evapotranspiration. Spatially distributed estimates of hourly tree evapotranspiration during the growing season are used to estimate human thermal comfort. Two main factors regulating evapotranspiration are soil moisture and canopy radiation. Spatial variation of soil moisture is represented by a modified urban topographic index and radiation for each tree is modified by considering aspect, slope and shade from surrounding buildings or hills. We compare the urban cooling algorithms used in iTree-Hydro with the urban canopy and land surface physics schemes used in the Weather Research and Forecasting model. We conclude by identifying biophysical feedbacks between tree-modulated air and water quality environmental services and how these may respond to urban heating and cooling. Improvements to this iTree model are intended to assist managers identify valuable tree services for urban living.

  20. Interface-induced disassembly of a self-assembled two-component nanoparticle system.

    PubMed

    Gao, Yan; Duc, Le T; Ali, Affira; Liang, Beverly; Liang, Jenn-Tai; Dhar, Prajnaparamita

    2013-03-19

    We present a study of static and dynamic interfacial properties of self-assembled polyelectrolyte complex nanoparticles (size 110-120 nm) containing entrapped surfactant molecules at a fluid/fluid interface. Surface tension vs time measurements of an aqueous solution of these polyelectrolyte complex nanoparticles (PCNs) show a concentration-dependent biphasic adsorption to the air/water interface while interfacial microrheology data show a concentration-dependent initial increase in the surface viscosity (up to 10(-7) N·m/s), followed by a sharp decrease (10(-9) N·m/s). Direct visualization of the air/water interface shows disappearance of particles from the interface over time. On the basis of these observations, we propose that the PCNs at fluid/fluid interfaces exist in two states: initial accumulation of PCNs at the air/water interface as nanoparticles, followed by interface induced disassembly of the accumulated PCNs into their components. The lack of change in particle size, charge, and viscosity of the bulk aqueous solution of PCNs with time indicates that this disintegration of the self-assembled PCNs is an interfacial phenomenon. Changes in energy encountered by the PCNs at the interface lead to instability of the self-assembled system and dissociation into its components. Such systems can be used for applications requiring directed delivery and triggered release of entrapped surfactants or macromolecules at fluid/fluid interfaces.

  1. Air-water CO2 outgassing in the Lower Lakes (Alexandrina and Albert, Australia) following a millennium drought.

    PubMed

    Li, Siyue; Bush, Richard T; Ward, Nicholas J; Sullivan, Leigh A; Dong, Fangyong

    2016-01-15

    Lakes are an important source and sink of atmospheric CO2, and thus are a vital component of the global carbon cycle. However, with scarce data on potentially important subtropical and tropical areas for whole continents such as Australia, the magnitude of large-scale lake CO2 emissions is unclear. This study presents spatiotemporal changes of dissolved inorganic carbon and water - to - air interface CO2 flux in the two of Australia's largest connected, yet geomorphically different freshwater lakes (Lake Alexandrina and Lake Albert, South Australia), during drought (2007 to September-2010) and post-drought (October 2010 to 2013). Lake levels in the extreme drought were on average approximately 1m lower than long-term average (0.71 m AHD). Drought was associated with an increase in the concentrations of dissolved inorganic species, organic carbon, nitrogen, Chl-a and major ions, as well as water acidification as a consequence of acid sulfate soil (ASS) exposure, and hence, had profound effects on lake pCO2 concentrations. Lakes Alexandrina and Albert were a source of CO2 to the atmosphere during the drought period, with efflux ranging from 0.3 to 7.0 mmol/m(2)/d. The lake air-water CO2 flux was negative in the post-drought, ranging between -16.4 and 0.9 mmol/m(2)/d. The average annual CO2 emission was estimated at 615.5×10(6) mol CO2/y during the drought period. These calculated emission rates are in the lower range for lakes, despite the potential for drought conditions that shift the lakes from sink to net source for atmospheric CO2. These observations have significant implications in the context of predicted increasing frequency and intensity of drought as a result of climate change. Further information on the spatial and temporal variability in CO2 flux from Australian lakes is urgently warranted to revise the global carbon budget for lakes. PMID:26520269

  2. Air-water CO2 outgassing in the Lower Lakes (Alexandrina and Albert, Australia) following a millennium drought.

    PubMed

    Li, Siyue; Bush, Richard T; Ward, Nicholas J; Sullivan, Leigh A; Dong, Fangyong

    2016-01-15

    Lakes are an important source and sink of atmospheric CO2, and thus are a vital component of the global carbon cycle. However, with scarce data on potentially important subtropical and tropical areas for whole continents such as Australia, the magnitude of large-scale lake CO2 emissions is unclear. This study presents spatiotemporal changes of dissolved inorganic carbon and water - to - air interface CO2 flux in the two of Australia's largest connected, yet geomorphically different freshwater lakes (Lake Alexandrina and Lake Albert, South Australia), during drought (2007 to September-2010) and post-drought (October 2010 to 2013). Lake levels in the extreme drought were on average approximately 1m lower than long-term average (0.71 m AHD). Drought was associated with an increase in the concentrations of dissolved inorganic species, organic carbon, nitrogen, Chl-a and major ions, as well as water acidification as a consequence of acid sulfate soil (ASS) exposure, and hence, had profound effects on lake pCO2 concentrations. Lakes Alexandrina and Albert were a source of CO2 to the atmosphere during the drought period, with efflux ranging from 0.3 to 7.0 mmol/m(2)/d. The lake air-water CO2 flux was negative in the post-drought, ranging between -16.4 and 0.9 mmol/m(2)/d. The average annual CO2 emission was estimated at 615.5×10(6) mol CO2/y during the drought period. These calculated emission rates are in the lower range for lakes, despite the potential for drought conditions that shift the lakes from sink to net source for atmospheric CO2. These observations have significant implications in the context of predicted increasing frequency and intensity of drought as a result of climate change. Further information on the spatial and temporal variability in CO2 flux from Australian lakes is urgently warranted to revise the global carbon budget for lakes.

  3. Hydrodynamical entrapment of ciliates at the air-liquid interface

    NASA Astrophysics Data System (ADS)

    Ferracci, Jonathan; Ueno, Hironori; Numayama-Tsuruta, Keiko; Imai, Yohsuke; Yamaguchi, Takami; Ishikawa, Takuji

    2012-11-01

    We found the new phenomenon of the entrapment of ciliates at the air-water interface, though they are not trapped by a solid interface. We first characterize the behaviours of cells at the interface by comparing it to those away from interfaces. The results showed that the cell's swimming velocity is considerably reduced at the air-water interface. In order to experimentally verify the possible physiological causes of the entrapment, we observed their behaviours in absence of positive chemotaxis for oxygen and the negative geotaxis. The results illustrated that the entrapment phenomenon was not dependent on these physiological conditions. The experiments using surfactant revealed that the entrapment phenomenon was strongly affected by the velocity-stress conditions at the interface. This fact was confirmed numerically by a boundary element method, i.e. the stress-free condition at the air-liquid interface is one of the main mechanisms of the entrapment phenomenon found in the experiments. Since the entrapment phenomenon found in this study affects the cell-cell interactions and the mass transport at the interface, the knowledge obtained in this study is useful for better understanding the complex behaviours of swimming microorganisms in nature. PhD student in the Physiological Flow Studies Laboratory.

  4. Estimating Riverine Air-Water Gas Exchange and Metabolism from Long Oxygen Time Series

    NASA Astrophysics Data System (ADS)

    Hall, R. O., Jr.; Appling, A.; Yackulic, C. B.; Arroita, M.

    2015-12-01

    To accurately depict the role of streams and rivers in carbon cycling requires estimating air- water gas exchange, productivity, and respiration. It is possible to estimate gas exchange and metabolism (gross primary production and ecosystem respiration) simultaneously from oxygen data themselves, but estimates from any single day often contain a substantial (and unknown) amount of parameter error. Here we developed a statistical method to leverage the extra information in a long time series to better estimate daily rates of gas exchange and metabolism. Such time series are ubiquitous in water quality monitoring programs, and these data are readily available over broad spatial scales. We developed a hierarchical model that estimates gas exchange as a function of discharge for a year-long time series of dissolved oxygen data. Gas exchange, and therefore metabolism, had much lower temporal variability than if we estimated parameters on separate days. Rates of gas exchange were positively related with discharge, but the relationship was river specific and often nonlinear. Our approach provides a robust means to estimate gas exchange and metabolism from the many rivers that have oxygen time series collected as part of water quality monitoring.

  5. Air - water temperature relationships in the trout streams of southeastern Minnesota’s carbonate - sandstone landscape

    USGS Publications Warehouse

    Krider, Lori A.; Magner, Joseph A.; Perry, Jim; Vondracek, Bruce C.; Ferrington, Leonard C.

    2013-01-01

    Carbonate-sandstone geology in southeastern Minnesota creates a heterogeneous landscape of springs, seeps, and sinkholes that supply groundwater into streams. Air temperatures are effective predictors of water temperature in surface-water dominated streams. However, no published work investigates the relationship between air and water temperatures in groundwater-fed streams (GWFS) across watersheds. We used simple linear regressions to examine weekly air-water temperature relationships for 40 GWFS in southeastern Minnesota. A 40-stream, composite linear regression model has a slope of 0.38, an intercept of 6.63, and R2 of 0.83. The regression models for GWFS have lower slopes and higher intercepts in comparison to surface-water dominated streams. Regression models for streams with high R2 values offer promise for use as predictive tools for future climate conditions. Climate change is expected to alter the thermal regime of groundwater-fed systems, but will do so at a slower rate than surface-water dominated systems. A regression model of intercept vs. slope can be used to identify streams for which water temperatures are more meteorologically than groundwater controlled, and thus more vulnerable to climate change. Such relationships can be used to guide restoration vs. management strategies to protect trout streams.

  6. Reliable quantification of phthalates in environmental matrices (air, water, sludge, sediment and soil): a review.

    PubMed

    Net, Sopheak; Delmont, Anne; Sempéré, Richard; Paluselli, Andrea; Ouddane, Baghdad

    2015-05-15

    Because of their widespread application, phthalates or phthalic acid esters (PAEs) are ubiquitous in the environment. Their presence has attracted considerable attention due to their potential impacts on ecosystem functioning and on public health, so their quantification has become a necessity. Various extraction procedures as well as gas/liquid chromatography and mass spectrometry detection techniques are found as suitable for reliable detection of such compounds. However, PAEs are ubiquitous in the laboratory environment including ambient air, reagents, sampling equipment, and various analytical devices, that induces difficult analysis of real samples with a low PAE background. Therefore, accurate PAE analysis in environmental matrices is a challenging task. This paper reviews the extensive literature data on the techniques for PAE quantification in natural media. Sampling, sample extraction/pretreatment and detection for quantifying PAEs in different environmental matrices (air, water, sludge, sediment and soil) have been reviewed and compared. The concept of "green analytical chemistry" for PAE determination is also discussed. Moreover useful information about the material preparation and the procedures of quality control and quality assurance are presented to overcome the problem of sample contamination and these encountered due to matrix effects in order to avoid overestimating PAE concentrations in the environment. PMID:25723871

  7. THE ROLE OF AQUEOUS THIN FILM EVAPORATIVE COOLING ON RATES OF ELEMENTAL MERCURY AIR-WATER EXCHANGE UNDER TEMPERATURE DISEQUILIBRIUM CONDITIONS

    EPA Science Inventory

    The technical conununity has only recently addressed the role of atmospheric temperature variations on rates of air-water vapor phase toxicant exchange. The technical literature has documented that: 1) day time rates of elemental mercury vapor phase air-water exchange can exceed ...

  8. Computational investigation of the influence of organic-aqueous interfaces on NaCl dissociation dynamics

    SciTech Connect

    Wick, Collin D.; Dang, Liem X.

    2010-01-26

    NaCl pairing and dissociation was investigated at the CCl4-water and 1,2-dichloroethane (DCE)-water interfaces, and compared with dissociation results in the bulk and at the air-water interface utilizing polarizable potentials. The transition path sampling methodology was used to calculate the rate constant for dissociation, while umbrella sampling was used to map out a free energy profile for NaCl dissociation. The results found that ion pairing was weakest at the organic-water interfaces, even weaker than in the water bulk. This is in contrast to what has been observed previously for the air-water interface, in which NaCl ion paring is stronger than in the bulk [Wick, C.D. J. Phys. Chem. C, 2009, 113, 6356]. The consequence of the weaker binding at the organic-water interfaces was that ion dissociation was faster than in the other systems studied. Interactions of the organic phase with the ions influenced the magnitude of the Cl- dipole moment, and at the organic-water interfaces, the average Cl- dipole was found to be lower than at the air-water interface, weakening interactions with Na+. Work was performed at the Pacific Northwest National Laboratory (PNNL) was supported by the Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy (DOE). PNNL is operated by Battelle for the DOE.

  9. 20 Years of Air-Water Gas Exchange Observations for Pesticides in the Western Arctic Ocean.

    PubMed

    Jantunen, Liisa M; Wong, Fiona; Gawor, Anya; Kylin, Henrik; Helm, Paul A; Stern, Gary A; Strachan, William M J; Burniston, Deborah A; Bidleman, Terry F

    2015-12-01

    The Arctic has been contaminated by legacy organochlorine pesticides (OCPs) and currently used pesticides (CUPs) through atmospheric transport and oceanic currents. Here we report the time trends and air-water exchange of OCPs and CUPs from research expeditions conducted between 1993 and 2013. Compounds determined in both air and water were trans- and cis-chlordanes (TC, CC), trans- and cis-nonachlors (TN, CN), heptachlor exo-epoxide (HEPX), dieldrin (DIEL), chlorobornanes (ΣCHBs and toxaphene), dacthal (DAC), endosulfans and metabolite endosulfan sulfate (ENDO-I, ENDO-II, and ENDO SUL), chlorothalonil (CHT), chlorpyrifos (CPF), and trifluralin (TFN). Pentachloronitrobenzene (PCNB and quintozene) and its soil metabolite pentachlorothianisole (PCTA) were also found in air. Concentrations of most OCPs declined in surface water, whereas some CUPs increased (ENDO-I, CHT, and TFN) or showed no significant change (CPF and DAC), and most compounds declined in air. Chlordane compound fractions TC/(TC + CC) and TC/(TC + CC + TN) decreased in water and air, while CC/(TC + CC + TN) increased. TN/(TC + CC + TN) also increased in air and slightly, but not significantly, in water. These changes suggest selective removal of more labile TC and/or a shift in chlordane sources. Water-air fugacity ratios indicated net volatilization (FR > 1.0) or near equilibrium (FR not significantly different from 1.0) for most OCPs but net deposition (FR < 1.0) for ΣCHBs. Net deposition was shown for ENDO-I on all expeditions, while the net exchange direction of other CUPs varied. Understanding the processes and current state of air-surface exchange helps to interpret environmental exposure and evaluate the effectiveness of international protocols and provides insights for the environmental fate of new and emerging chemicals. PMID:26196214

  10. 20 Years of Air-Water Gas Exchange Observations for Pesticides in the Western Arctic Ocean.

    PubMed

    Jantunen, Liisa M; Wong, Fiona; Gawor, Anya; Kylin, Henrik; Helm, Paul A; Stern, Gary A; Strachan, William M J; Burniston, Deborah A; Bidleman, Terry F

    2015-12-01

    The Arctic has been contaminated by legacy organochlorine pesticides (OCPs) and currently used pesticides (CUPs) through atmospheric transport and oceanic currents. Here we report the time trends and air-water exchange of OCPs and CUPs from research expeditions conducted between 1993 and 2013. Compounds determined in both air and water were trans- and cis-chlordanes (TC, CC), trans- and cis-nonachlors (TN, CN), heptachlor exo-epoxide (HEPX), dieldrin (DIEL), chlorobornanes (ΣCHBs and toxaphene), dacthal (DAC), endosulfans and metabolite endosulfan sulfate (ENDO-I, ENDO-II, and ENDO SUL), chlorothalonil (CHT), chlorpyrifos (CPF), and trifluralin (TFN). Pentachloronitrobenzene (PCNB and quintozene) and its soil metabolite pentachlorothianisole (PCTA) were also found in air. Concentrations of most OCPs declined in surface water, whereas some CUPs increased (ENDO-I, CHT, and TFN) or showed no significant change (CPF and DAC), and most compounds declined in air. Chlordane compound fractions TC/(TC + CC) and TC/(TC + CC + TN) decreased in water and air, while CC/(TC + CC + TN) increased. TN/(TC + CC + TN) also increased in air and slightly, but not significantly, in water. These changes suggest selective removal of more labile TC and/or a shift in chlordane sources. Water-air fugacity ratios indicated net volatilization (FR > 1.0) or near equilibrium (FR not significantly different from 1.0) for most OCPs but net deposition (FR < 1.0) for ΣCHBs. Net deposition was shown for ENDO-I on all expeditions, while the net exchange direction of other CUPs varied. Understanding the processes and current state of air-surface exchange helps to interpret environmental exposure and evaluate the effectiveness of international protocols and provides insights for the environmental fate of new and emerging chemicals.

  11. Microwave plasma source operating with atmospheric pressure air-water mixtures

    NASA Astrophysics Data System (ADS)

    Tatarova, E.; Henriques, J. P.; Felizardo, E.; Lino da Silva, M.; Ferreira, C. M.; Gordiets, B.

    2012-11-01

    The overall performance of a surface wave driven air-water plasma source operating at atmospheric pressure and 2.45 GHz has been analyzed. A 1D model previously developed has been improved in order to describe in detail the creation and loss processes of active species of interest. This model provides a complete characterization of the axial structure of the source, including the discharge and the afterglow zones. The main electron creation channel was found to be the associative ionization process N + O → NO+ + e. The NO(X) relative density in the afterglow plasma jet ranges from 1.2% to 1.6% depending on power and water percentage, according to the model predictions and the measurements. Other types of species such as NO2 and nitrous acid HNO2 have also been detected by mass and Fourier Transform Infrared spectroscopy. The relative population density of O(3P) ground state atoms increases from 8% to 10% in the discharge zone when the input microwave power increases from 200 to 400 W and the water percentage from 1% to 10%. Furthermore, high densities of O2(a1Δg) singlet delta oxygen molecules and OH radicals (1% and 5%, respectively) can be achieved in the discharge zone. In the late afterglow the O2(a1Δg) density is about 0.1% of the total density. This plasma source has a flexible operation and potential for channeling the energy in ways that maximize the density of active species of interest.

  12. Surfactant-Induced Flow in Unsaturated Porous Media: Implications for Air-Water Interfacial Area Determination

    NASA Astrophysics Data System (ADS)

    Costanza-Robinson, M. S.; Zheng, Z.; Estabrook, B.; Henry, E. J.; Littlefield, M. H.

    2011-12-01

    Air-water interfacial area (AI) in porous media is an important factor governing equilibrium contaminant retention, as well as the kinetics of interphase mass transfer. Interfacial-partitioning tracer (IPT) tests are a common technique for measuring AI at a given moisture saturation (SW), where AI is calculated based on the ratio of arrival times of a surfactant and a non-reactive tracer. At surfactant concentrations often used, the aqueous surface tension of the interfacial tracer solution is ~30% lower than that of the resident porewater in the system, creating transient surface tension gradients during the IPT measurement. Because surface tension gradients create capillary pressure gradients, surfactant-induced unsaturated flow may occur during IPT tests, a process that would violate fundamental assumptions of constant SW, of steady-state flow, and of nonreactive and surfactant tracers experiencing the same transport conditions. To examine the occurrence and magnitude of surfactant-induced flow, we conducted IPT tests for unsaturated systems at ~84% initial SW using surfactant input concentrations that bracket concentrations commonly used. Despite constant boundary conditions (constant inlet flux and outlet pressure), the introduction of the surfactant solution induced considerable transience in column effluent flowrate and SW. Real-time system mass measurements revealed drainage of 20-40% SW, with the amount of drainage and the maximum rate of drainage proportional to the influent surfactant concentration, as would be expected. Because AI is inversely related to SW, the use of higher surfactant concentrations should yield larger AI estimates. Measured AI values, however, showed no clear relationship to surfactant concentration or the time-averaged SW of the system. These findings cast doubt on the reliability of IPT for AI determination.

  13. Humidity-dependent compression-induced glass transition of the air-water interfacial Langmuir films of poly(D,L-lactic acid-ran-glycolic acid) (PLGA).

    PubMed

    Kim, Hyun Chang; Lee, Hoyoung; Jung, Hyunjung; Choi, Yun Hwa; Meron, Mati; Lin, Binhua; Bang, Joona; Won, You-Yeon

    2015-07-28

    Constant rate compression isotherms of the air-water interfacial Langmuir films of poly(D,L-lactic acid-ran-glycolic acid) (PLGA) show a distinct feature of an exponential increase in surface pressure in the high surface polymer concentration regime. We have previously demonstrated that this abrupt increase in surface pressure is linked to the glass transition of the polymer film, but the detailed mechanism of this process is not fully understood. In order to obtain a molecular-level understanding of this behavior, we performed extensive characterizations of the surface mechanical, structural and rheological properties of Langmuir PLGA films at the air-water interface, using combined experimental techniques including the Langmuir film balance, X-ray reflectivity and double-wall-ring interfacial rheometry methods. We observed that the mechanical and structural responses of the Langmuir PLGA films are significantly dependent on the rate of film compression; the glass transition was induced in the PLGA film only at fast compression rates. Surprisingly, we found that this deformation rate dependence is also dependent on the humidity of the environment. With water acting as a plasticizer for the PLGA material, the diffusion of water molecules through the PLGA film seems to be the key factor in the determination of the glass transformation properties and thus the mechanical response of the PLGA film against lateral compression. Based on our combined results, we hypothesize the following mechanism for the compression-induced glass transformation of the Langmuir PLGA film; (1) initially, a humidified/non-glassy PLGA film is formed in the full surface-coverage region (where the surface pressure shows a plateau) during compression; (2) further compression leads to the collapse of the PLGA chains and the formation of new surfaces on the air side of the film, and this newly formed top layer of the PLGA film is transiently glassy in character because the water evaporation rate

  14. Humidity-dependent compression-induced glass transition of the air-water interfacial Langmuir films of poly(D,L-lactic acid-ran-glycolic acid) (PLGA).

    PubMed

    Kim, Hyun Chang; Lee, Hoyoung; Jung, Hyunjung; Choi, Yun Hwa; Meron, Mati; Lin, Binhua; Bang, Joona; Won, You-Yeon

    2015-07-28

    Constant rate compression isotherms of the air-water interfacial Langmuir films of poly(D,L-lactic acid-ran-glycolic acid) (PLGA) show a distinct feature of an exponential increase in surface pressure in the high surface polymer concentration regime. We have previously demonstrated that this abrupt increase in surface pressure is linked to the glass transition of the polymer film, but the detailed mechanism of this process is not fully understood. In order to obtain a molecular-level understanding of this behavior, we performed extensive characterizations of the surface mechanical, structural and rheological properties of Langmuir PLGA films at the air-water interface, using combined experimental techniques including the Langmuir film balance, X-ray reflectivity and double-wall-ring interfacial rheometry methods. We observed that the mechanical and structural responses of the Langmuir PLGA films are significantly dependent on the rate of film compression; the glass transition was induced in the PLGA film only at fast compression rates. Surprisingly, we found that this deformation rate dependence is also dependent on the humidity of the environment. With water acting as a plasticizer for the PLGA material, the diffusion of water molecules through the PLGA film seems to be the key factor in the determination of the glass transformation properties and thus the mechanical response of the PLGA film against lateral compression. Based on our combined results, we hypothesize the following mechanism for the compression-induced glass transformation of the Langmuir PLGA film; (1) initially, a humidified/non-glassy PLGA film is formed in the full surface-coverage region (where the surface pressure shows a plateau) during compression; (2) further compression leads to the collapse of the PLGA chains and the formation of new surfaces on the air side of the film, and this newly formed top layer of the PLGA film is transiently glassy in character because the water evaporation rate

  15. Ordering of solid microparticles at liquid crystal-water interfaces.

    PubMed

    Lin, I-Hsin; Koenig, Gary M; de Pablo, Juan J; Abbott, Nicholas L

    2008-12-25

    We report a study of the organization of solid microparticles at oil-water interfaces, where the oil is a thermotropic liquid crystal (LC). The study was motivated by the proposition that microparticle organization and LC ordering would be coupled at these interfaces. Surfactant-functionalized polystyrene microparticles were spread at air-water interfaces at prescribed densities and then raised into contact with supported films of nematic 4-pentyl-4'-cyanobiphenyl (5CB). Whereas this method of sample preparation led to quantitative transfer of microparticles from the air-water interface to an isotropic oil-water interface, forces mediated by the nematic order of 5CB were observed to rapidly displace microparticles laterally across the interface of the water upon contact with nematic 5CB, thus leading to a 65% decrease in the density of microparticles at the LC-water interface. These lateral forces were determined to be caused by microparticle-induced deformation of the LC, the energy of which was estimated to be approximately 10(4) kT. We also observed microparticles transferred to the LC-water interface to assemble into chainlike structures that were not seen when using isotropic oils, indicating the presence of LC-mediated interparticle interactions at this interface. Optical textures of the LC in the vicinity of the microparticles were consistent with formation of topological defects with dipolar symmetry capable of promoting the chaining of the microparticles. The presence of microparticles at the interface also impacted the ordering of the LCs, including a transition from parallel to perpendicular ordering of the LC with increasing microparticle density. These observations, when combined, demonstrate that LC-mediated interactions can direct the assembly of solid microparticles at LC-water interfaces and that the ordering of the LC is also strongly coupled to the presence of microparticles.

  16. Measurement of interfacial structures in horizontal air-water bubbly flows

    SciTech Connect

    Talley, J. D.; Worosz, T.; Dodds, M. R.; Kim, S.

    2012-07-01

    In order to predict multi-dimensional phenomena in nuclear reactor systems, methods relying on computational fluid dynamics (CFD) codes are essential. However, to be applicable in assessing thermal-hydraulic safety, these codes must be able to accurately predict the development of two-phase flows. Therefore, before practical application these codes must be assessed using experimental databases that capture multi-dimensional phenomena. While a large database exists that can be employed to assess predictions in vertical flows, the available database for horizontal flows is significantly lacking. Therefore, the current work seeks to develop an additional database in air-water horizontal bubbly flow through a 38.1 mm ID test section with a total development length of approximately 250 diameters. The experimental conditions are chosen to cover a wide range of the bubbly flow regime based upon flow visualization using a high-speed video camera. A database of local time-averaged void fraction, bubble velocity, interfacial area concentration, and bubble Sauter mean diameter are acquired throughout the pipe cross-section using a four-sensor conductivity probe. To investigate the evolution of the flow, measurements are made at axial locations of 44, 116, and 244 diameters downstream of the inlet. In the current work, only measurements obtained at L/D = 244 are presented. It is found that increasing the liquid superficial velocity tends to reduce both the bubble size and the degree of bubble packing near the upper wall. However, it is observed that the position of the maximum void fraction value remains nearly constant and is located approximately one bubble diameter away from the upper wall. It is also found that the bubble velocity exhibits a power law behavior resembling a single phase liquid turbulent velocity profile. Moreover, the local bubble velocity tends to decrease as the local void fraction increases. Conversely, increasing the gas superficial velocity is found to

  17. Impact of the tsunami and earthquake of 26th December 2004 on the vital coastal ecosystems of the Andaman and Nicobar Islands assessed using RESOURCESAT AWiFS data

    NASA Astrophysics Data System (ADS)

    Bahuguna, Anjali; Nayak, Shailesh; Roy, Dam

    2008-06-01

    Tsunami waves struck the Indian coast on 26th December 2004 affecting the Andaman and Nicobar group of islands. A quick assessment of the status of the vital coastal ecosystems has been made using pre- and post-tsunami Advance Wide Field Sensor (AWiFS) data of Indian satellite RESOURCESAT with an accuracy of 87-90% and the Kappa ranging from 0.8696 to 0.9053. Among the coastal ecosystems the coral reefs have suffered the maximum with the Nicobar reefs (69% eroded and 29% degraded) bearing the brunt more than the Andaman reefs (54% eroded and 22% degraded). Significant improvement to the condition of the reef damaged due to backwash has been noted. About 41% of the Sentinel reef area has undergone significant improvement. The continuance of the erosion of the southwestern Andaman reefs is due to the impact of recurring earthquakes. The impact on mangroves of both the groups of islands has been due to uprooting as well as inundation of seawater and resulting stagnation. Changes are expected in community structure of mangroves as a result of tsunami.

  18. Ecosystem Metabolism and Air-Water Fluxes of Greenhouse Gases in High Arctic Wetland Ponds

    NASA Astrophysics Data System (ADS)

    Lehnherr, I.; Venkiteswaran, J.; St. Louis, V. L.; Emmerton, C.; Schiff, S. L.

    2012-12-01

    Freshwater lakes and wetlands can be very productive systems on the Arctic landscape compared to terrestrial tundra ecosystems and provide valuable resources to many organisms, including waterfowl, fish and humans. Rates of ecosystem productivity dictate how much energy flows through food webs, impacting the abundance of higher-level organisms (e.g., fish), as well as the net carbon balance, which determines whether a particular ecosystem is a source or sink of carbon. Climate change is predicted to result in warmer temperatures, increased precipitation and permafrost melting in the Arctic and is already altering northern ecosystems at unprecedented rates; however, it is not known how freshwater systems are responding to these changes. To predict how freshwater systems will respond to complex environmental changes, it is necessary to understand the key processes, such as primary production and ecosystem respiration, that are driving these systems. We sampled wetland ponds (n=8) and lakes (n=2) on northern Ellesmere Island (81° N, Nunavut, Canada) during the open water season for a suite of biogeochemical parameters, including concentrations of dissolved gases (O2, CO2, CH4, N2O) as well as stable-isotope ratios of dissolved inorganic carbon (δ13C-DIC), dissolved oxygen (δ18O-DO), and water (δ18O-H2O). We will present rates of primary production and ecosystem respiration, modeled from the concentration and stable isotope ratios of DIC and DO, as well as air-water gas exchange of greenhouse gases in these high Arctic ponds and lakes. Preliminary results demonstrate that ecosystem metabolism in these ponds was high enough to result in significant deviations in the isotope ratios of DIC and DO from atmospheric equilibrium conditions. In other words ecosystem rates of primary production and respiration were faster than gas exchange even in these small, shallow, well-mixed ponds. Furthermore, primary production was elevated enough at all sites except Lake Hazen, a

  19. Air-water fluxes of N₂O and CH₄ during microalgae (Staurosira sp.) cultivation in an open raceway pond.

    PubMed

    Ferrón, Sara; Ho, David T; Johnson, Zackary I; Huntley, Mark E

    2012-10-01

    The industrial-scale production of biofuels from cultivated microalgae has gained considerable interest in the last several decades. While the climate benefits of microalgae cultivation that result from the capture of atmospheric CO(2) are known, the counteracting effect from the potential emission of other greenhouse gases has not been well quantified. Here, we report the results of a study conducted at an industrial pilot facility in Hawaii to determine the air-water fluxes of N(2)O and CH(4) from open raceway ponds used to grow the marine diatom Staurosira sp. as a feedstock for biofuel. Dissolved O(2), CH(4), and N(2)O concentrations were measured over a 24 h cycle. During this time, four SF(6) tracer release experiments were conducted to quantify gas transfer velocities in the ponds, and these were then used to calculate air-water fluxes. Our results show that pond waters were consistently supersaturated with CH(4) (up to 725%) resulting in an average emission of 19.9 ± 5.6 μmol CH(4) m(-2) d(-1). Upon NO(3)(-) depletion, the pond shifted from being a source to being a sink of N(2)O, with an overall net uptake during the experimental period of 3.4 ± 3.5 μmol N(2)O m(-2) d(-1). The air-water fluxes of N(2)O and CH(4) expressed as CO(2) equivalents of global warming potential were 2 orders of magnitude smaller than the overall CO(2) uptake by the microalgae.

  20. Interaction of L-Phenylalanine with a Phospholipid Monolayer at the Water-Air Interface.

    PubMed

    Griffith, Elizabeth C; Perkins, Russell J; Telesford, Dana-Marie; Adams, Ellen M; Cwiklik, Lukasz; Allen, Heather C; Roeselová, Martina; Vaida, Veronica

    2015-07-23

    The interaction of L-phenylalanine with a 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) monolayer at the air-water interface was explored using a combination of experimental techniques and molecular dynamics (MD) simulations. By means of Langmuir trough methods and Brewster angle microscopy, L-phenylalanine was shown to significantly alter the interfacial tension and the surface domain morphology of the DPPC film. In addition, confocal microscopy was used to explore the aggregation state of L-phenylalanine in the bulk aqueous phase. Finally, MD simulations were performed to gain molecular-level information on the interactions of L-phenylalanine and DPPC at the interface. Taken together, these results show that L-phenylalanine intercalates into a DPPC film at the air-water interface, thereby affecting the surface tension, phase morphology, and ordering of the DPPC film. The results are discussed in the context of biological systems and the mechanism of diseases such as phenylketonuria.

  1. Vibrational spectroscopy of water interfaces

    SciTech Connect

    Du, Q.

    1994-12-01

    The second order nonlinear optical processes of second harmonic generation and sum frequency generation are powerful and versatile tools for studying all kinds of surfaces. They possess unusual surface sensitivity due to the symmetry properties of the second order nonlinear susceptibility. The technique of infrared-visible sum frequency generation (SFG) is particularly attractive because it offers a viable way to do vibrational spectroscopy on any surfaces accessible to light with submonolayer sensitivity. In this thesis, the author applies SFG to study a number of important water interfaces. At the air/water interface, hydrophobic solid/water and liquid/water interfaces, it was found that approximately 25% of surface water molecules have one of their hydrogen pointing away from the liquid water. The large number of unsatisfied hydrogen bonds contributes significantly to the large interfacial energy of the hydrophobic surfaces. At the hydrophilic fused quartz/water interface and a fatty acid monolayer covered water surface, the structure and orientation of surface water molecules are controlled by the hydrogen bonding of water molecules with the surface OH groups and the electrostatic interaction with the surface field from the ionization of surface groups. A change of pH value in the bulk water can significantly change the relative importance of the two interactions and cause a drastic change in orientation of the surface water molecules. SFG has also been applied to study the tribological response of some model lubricant films. Monolayers of Langmuir-Blodgett films were found to disorder orientationaly under mildly high pressure and recover promptly upon removal of the applied pressure.

  2. Reorientation of the helix of the tryptophan-rich gp41W peptide from HIV-1 at interfaces

    NASA Astrophysics Data System (ADS)

    Matar, Gladys; Benichou, Emmanuel; Nasir, Mehmet Nail; Harfouch, Yara El; Brevet, Pierre-François; Besson, Françoise

    2013-12-01

    The glycoprotein gp41 from the Human Immunodeficiency Virus type 1 (HIV-1) has an amino acid sequence enriched in tryptophan residues, the so-called gp41W peptide (i.e., KWASLWNWFNITNWLWYIK) and plays a crucial role in HIV-1 host cell infection. Using the coupling of Second Harmonic Generation targeting the tryptophan residues with lateral surface tension measurements, we investigate the interaction of gp41W with a neat air/water and a lipid/water interfaces. At the air/water interface, gp41W presents a well-defined orientation and this orientation is strongly modified at the lipid/water interface, depending on the surface pressure. These results show that this strategy is well suited to monitor tryptophan containing α-helices orientation at lipid/water interfaces.

  3. Development of Interfacial Structure in a Confined Air-Water Cap-Turbulent and Churn-Turbulent Flow

    SciTech Connect

    Xiaodong Sun; Seungjin Kim; Ling Cheng; Mamoru Ishii; Beus, Stephen G.

    2002-07-01

    The objective of the present work is to study and model the interfacial structure development of air-water two-phase flow in a confined test section. Experiments of a total of 9 flow conditions in cap-turbulent and churn-turbulent flow regimes are carried out in a vertical air-water upward two-phase flow experimental loop with a test section of 200-mm in width and 10-mm in gap. Miniaturized four-sensor conductivity probes are used to measure local two-phase parameters at three different elevations for each flow condition. The bubbles captured by the probes are categorized into two groups in view of the two-group interfacial area transport equation, i.e., spherical/distorted bubbles as Group 1 and cap/churn-turbulent bubbles as Group 2. The acquired parameters are time-averaged local void fraction, interfacial velocity, bubble number frequency, interfacial area concentration, and bubble Sauter mean diameter for both groups of bubbles. Also, the line-averaged and area-averaged data are presented and discussed. The comparisons of these parameters at different elevations demonstrate the development of interfacial structure along the flow direction due to bubble interactions. (authors)

  4. Development of Interfacial Structure in a Confined Air-Water Cap-Turbulent and Churn-Turbulent Flow

    SciTech Connect

    X. Sun; S. Kim; L. Cheng; M. Ishii; S.G. Beus

    2001-10-31

    The objective of the present work is to study and model the interfacial structure development of air-water two-phase flow in a confined test section. Experiments of a total of 9 flow conditions in a cap-turbulent and churn-turbulent flow regimes are carried out in a vertical air-water upward two-phase flow experimental loop with a test section of 20-cm in width and 1-cm in gap. The miniaturized four-sensor conductivity probes are used to measure local two-phase parameters at three different elevations for each flow condition. The bubbles captured by the probes are categorized into two groups in view of the two-group interfacial area transport equation, i.e., spherical/distorted bubbles as Group 1 and cap/churn-turbulent bubbles as Group 2. The acquired parameters are time-averaged local void fraction, interfacial velocity, bubble number frequency, interfacial area concentration, and bubble Sauter mean diameter for both groups of bubbles. Also, the line-averaged and area-averaged data are presented and discussed. The comparisons of these parameters at different elevations demonstrate the development of interfacial structure along the flow direction due to bubble interactions.

  5. Forced convective flow and heat transfer of upward cocurrent air-water slug flow in vertical plain and swirl tubes

    SciTech Connect

    Chang, Shyy Woei; Yang, Tsun Lirng

    2009-10-15

    This experimental study comparatively examined the two-phase flow structures, pressured drops and heat transfer performances for the cocurrent air-water slug flows in the vertical tubes with and without the spiky twisted tape insert. The two-phase flow structures in the plain and swirl tubes were imaged using the computerized high frame-rate videography with the Taylor bubble velocity measured. Superficial liquid Reynolds number (Re{sub L}) and air-to-water mass flow ratio (AW), which were respectively in the ranges of 4000-10000 and 0.003-0.02 were selected as the controlling parameters to specify the flow condition and derive the heat transfer correlations. Tube-wise averaged void fraction and Taylor bubble velocity were well correlated by the modified drift flux models for both plain and swirl tubes at the slug flow condition. A set of selected data obtained from the plain and swirl tubes was comparatively examined to highlight the impacts of the spiky twisted tape on the air-water interfacial structure and the pressure drop and heat transfer performances. Empirical heat transfer correlations that permitted the evaluation of individual and interdependent Re{sub L} and AW impacts on heat transfer in the developed flow regions of the plain and swirl tubes at the slug flow condition were derived. (author)

  6. Using aliphatic alcohols as gaseous tracers in determination of water contents and air-water interfacial areas in unsaturated sands

    NASA Astrophysics Data System (ADS)

    Sung, Menghau; Chen, Bi-Hsiang

    2011-11-01

    A new type of gaseous tracer utilizing nontoxic aliphatic alcohols for the determination of water content and air-water interfacial area is tested on unsaturated sands of low water content. Alcohol vapors are generated at room temperature and passed through the experimental sand column. Breakthrough curves (BTCs) of these vapors are obtained by monitoring their effluent concentrations using GC-FID. The retardation factor with respect to each vapor transport process is obtained by optimizing BTCs data using the CXTFIT program in the reverse problem mode. The water content and the interfacial area are subsequently calculated from their retardation factors by both equilibrium and nonequilibrium transport models. Experimental results indicate that the pentanol tracer is feasible in the determination of water content at conditions when the degree of water saturation is low. In the determination of air-water interfacial area, decanol is selected due to its interfacial adsorption characteristics. By comparing to interfacial areas from theoretical predictions as well as other conventional tarcer methods, the ones determined from the decanol tracer tests are found to be close to the true interfacial areas when the water content is low.

  7. Image processing analysis on the air-water slug two-phase flow in a horizontal pipe

    NASA Astrophysics Data System (ADS)

    Dinaryanto, Okto; Widyatama, Arif; Majid, Akmal Irfan; Deendarlianto, Indarto

    2016-06-01

    Slug flow is a part of intermittent flow which is avoided in industrial application because of its irregularity and high pressure fluctuation. Those characteristics cause some problems such as internal corrosion and the damage of the pipeline construction. In order to understand the slug characteristics, some of the measurement techniques can be applied such as wire-mesh sensors, CECM, and high speed camera. The present study was aimed to determine slug characteristics by using image processing techniques. Experiment has been carried out in 26 mm i.d. acrylic horizontal pipe with 9 m long. Air-water flow was recorded 5 m from the air-water mixer using high speed video camera. Each of image sequence was processed using MATLAB. There are some steps including image complement, background subtraction, and image filtering that used in this algorithm to produce binary images. Special treatments also were applied to reduce the disturbance effect of dispersed bubble around the bubble. Furthermore, binary images were used to describe bubble contour and calculate slug parameter such as gas slug length, gas slug velocity, and slug frequency. As a result the effect of superficial gas velocity and superficial liquid velocity on the fundamental parameters can be understood. After comparing the results to the previous experimental results, the image processing techniques is a useful and potential technique to explain the slug characteristics.

  8. Verification and Validation of Numerical Models for Air/Water Flow on Coastal and Navigation Fluid-Structure Interaction Applications

    NASA Astrophysics Data System (ADS)

    Kees, C. E.; Farthing, M.; Dimakopoulos, A.; DeLataillade, T.

    2015-12-01

    Performance analysis and optimization of coastal and navigation structures is becoming feasible due to recent improvements in numerical methods for multiphase flows and the steady increase in capacity and availability of high performance computing resources. Now that the concept of fully three-dimensional air/water flow modelling for real world engineering analysis is achieving acceptance by the wider engineering community, it is critical to expand careful comparative studies on verification,validation, benchmarking, and uncertainty quantification for the variety of competing numerical methods that are continuing to evolve. Furthermore, uncertainty still remains about the relevance of secondary processes such as surface tension, air compressibility, air entrainment, and solid phase (structure) modelling so that questions about continuum mechanical theory and mathematical analysis of multiphase flow are still required. Two of the most popular and practical numerical approaches for large-scale engineering analysis are the Volume-Of-Fluid (VOF) and Level Set (LS) approaches. In this work we will present a publically available verification and validation test set for air-water-structure interaction problems as well as computational and physical model results including a hybrid VOF-LS method, traditional VOF methods, and Smoothed Particle Hydrodynamics (SPH) results. The test set repository and test problem formats will also be presented in order to facilitate future comparative studies and reproduction of scientific results.

  9. Statistical characterization of the optical interaction at a supercavitating interface

    NASA Astrophysics Data System (ADS)

    Walters, Gage; Kane, Tim; Jefferies, Rhett; Antonelli, Lynn

    2016-05-01

    The optical characteristics of an air/water interface have been widely studied for natural interface formations. However, the creation and management of artificial cavities creates a complicated interaction of gas and liquid that makes optical sensing and communication through the interface challenging. A ventilated cavity can reduce friction in underwater vehicles, but the resulting bubble drastically impedes optical and acoustic communication propagation. The complicated interaction at the air/water boundary yields surface waves and turbulence that make modeling and compensating of the optical properties difficult. Our experimental approach uses a narrow laser beam to probe the surface of the interface and measure the beam deflection and lensing effects. Using a vehicle model with a cavitator in a water tunnel, a laser beam is propagated outward from the model through the boundary and projected onto a target grid. The beam projection is captured using a high-speed camera, allowing us to measure and analyze beam shape and deflection. This approach has enabled us to quantify the temporal and spatial periodic variations in the beam propagation through the cavity boundary and fluid.

  10. Analytical model for radiative transfer including the effects of a rough material interface.

    PubMed

    Giddings, Thomas E; Kellems, Anthony R

    2016-08-20

    The reflected and transmitted radiance due to a source located above a water surface is computed based on models for radiative transfer in continuous optical media separated by a discontinuous air-water interface with random surface roughness. The air-water interface is described as the superposition of random, unresolved roughness on a deterministic realization of a stochastic wave surface at resolved scales. Under the geometric optics assumption, the bidirectional reflection and transmission functions for the air-water interface are approximated by applying regular perturbation methods to Snell's law and including the effects of a random surface roughness component. Formal analytical solutions to the radiative transfer problem under the small-angle scattering approximation account for the effects of scattering and absorption as light propagates through the atmosphere and water and also capture the diffusive effects due to the interaction of light with the rough material interface that separates the two optical media. Results of the analytical models are validated against Monte Carlo simulations, and the approximation to the bidirectional reflection function is also compared to another well-known analytical model.

  11. Analytical model for radiative transfer including the effects of a rough material interface.

    PubMed

    Giddings, Thomas E; Kellems, Anthony R

    2016-08-20

    The reflected and transmitted radiance due to a source located above a water surface is computed based on models for radiative transfer in continuous optical media separated by a discontinuous air-water interface with random surface roughness. The air-water interface is described as the superposition of random, unresolved roughness on a deterministic realization of a stochastic wave surface at resolved scales. Under the geometric optics assumption, the bidirectional reflection and transmission functions for the air-water interface are approximated by applying regular perturbation methods to Snell's law and including the effects of a random surface roughness component. Formal analytical solutions to the radiative transfer problem under the small-angle scattering approximation account for the effects of scattering and absorption as light propagates through the atmosphere and water and also capture the diffusive effects due to the interaction of light with the rough material interface that separates the two optical media. Results of the analytical models are validated against Monte Carlo simulations, and the approximation to the bidirectional reflection function is also compared to another well-known analytical model. PMID:27556978

  12. Hyperbolic interfaces.

    PubMed

    Giomi, Luca

    2012-09-28

    Fluid interfaces, such as soap films, liquid droplets, or lipid membranes, are known to give rise to several special geometries, whose complexity and beauty continue to fascinate us, as observers of the natural world, and challenge us as scientists. Here I show that a special class of surfaces of constant negative Gaussian curvature can be obtained in fluid interfaces equipped with an orientational ordered phase. These arise in various soft and biological materials, such as nematic liquid crystals, cytoskeletal assemblies, or hexatic colloidal suspensions. The purely hyperbolic morphology originates from the competition between surface tension, that reduces the area of the interface at the expense of increasing its Gaussian curvature, and the orientational elasticity of the ordered phase, that in turn suffers for the distortion induced by the underlying curvature. PMID:23030106

  13. Hyperbolic Interfaces

    NASA Astrophysics Data System (ADS)

    Giomi, Luca

    2012-09-01

    Fluid interfaces, such as soap films, liquid droplets, or lipid membranes, are known to give rise to several special geometries, whose complexity and beauty continue to fascinate us, as observers of the natural world, and challenge us as scientists. Here I show that a special class of surfaces of constant negative Gaussian curvature can be obtained in fluid interfaces equipped with an orientational ordered phase. These arise in various soft and biological materials, such as nematic liquid crystals, cytoskeletal assemblies, or hexatic colloidal suspensions. The purely hyperbolic morphology originates from the competition between surface tension, that reduces the area of the interface at the expense of increasing its Gaussian curvature, and the orientational elasticity of the ordered phase, that in turn suffers for the distortion induced by the underlying curvature.

  14. A modeling procedure to evaluate the coherence of independently derived environmental quality objectives for air, water and soil

    SciTech Connect

    Meent, D. van de . Lab. for Ecotoxicology); Bruijn, J.H.M. de . Directorate for Chemicals, Safety and Radiation Protection)

    1995-01-01

    Sets of independently derived environmental quality objectives (EQOs) for air, water, and soil may not be coherent in that maintaining the concentration at EQO level in one compartment may lead to exceeding EQO levels in other compartments. A methodology to evaluate this coherence is suggested. Starting from a steady concentration in the compartment of focus (the primary compartment), steady-state concentrations in the adjacent (secondary) compartments are estimated using a multimedia fate model. If air is the primary compartment, steady-state concentrations in water and soil close to the equilibrium concentrations can be expected, and coherence of EQOs can be evaluated easily by means of an extended equilibrium partitioning procedure. If water or soil is the primary compartment, the steady-state concentrate in air is usually well below the equilibrium concentration. Subequilibrium steady-state concentrations are sensitive to assumed model parameters. The procedure is illustrated with the results of a coherence analysis for seven chemicals for The Netherlands.

  15. Influence of current velocity and wind speed on air-water gas exchange in a mangrove estuary

    NASA Astrophysics Data System (ADS)

    Ho, David T.; Coffineau, Nathalie; Hickman, Benjamin; Chow, Nicholas; Koffman, Tobias; Schlosser, Peter

    2016-04-01

    Knowledge of air-water gas transfer velocities and water residence times is necessary to study the fate of mangrove derived carbon exported into surrounding estuaries and ultimately to determine carbon balances in mangrove ecosystems. For the first time, the 3He/SF6 dual tracer technique, which has been proven to be a powerful tool to determine gas transfer velocities in the ocean, is applied to Shark River, an estuary situated in the largest contiguous mangrove forest in North America. The mean gas transfer velocity was 3.3 ± 0.2 cm h-1 during the experiment, with a water residence time of 16.5 ± 2.0 days. We propose a gas exchange parameterization that takes into account the major sources of turbulence in the estuary (i.e., bottom generated shear and wind stress).

  16. A Designed A. vinelandii-S. elongatus Coculture for Chemical Photoproduction from Air, Water, Phosphate, and Trace Metals.

    PubMed

    Smith, Matthew J; Francis, Matthew B

    2016-09-16

    Microbial mutualisms play critical roles in a diverse number of ecosystems and have the potential to improve the efficiency of bioproduction for desirable chemicals. We investigate the growth of a photosynthetic cyanobacterium, Synechococcus elongatus PCC 7942, and a diazotroph, Azotobacter vinelandii, in coculture. From initial studies of the coculture grown in media with glutamate, we proposed a model of cross-feeding between these organisms. We then engineer a new microbial mutualism between Azotobacter vinelandii AV3 and cscB Synechococcus elongatus that grows in the absence of fixed carbon or nitrogen. The coculture cannot grow in the absence of a sucrose-exporting S. elongatus, and neither organism can grow alone without fixed carbon or nitrogen. This new system has the potential to produce industrially relevant products, such as polyhydroxybutyrate (PHB) and alginate, from air, water, phosphate, trace metals, and sunlight. We demonstrate the ability of the coculture to produce PHB in this work. PMID:27232890

  17. Spiers Memorial Lecture. Ions at aqueous interfaces.

    PubMed

    Jungwirth, Pavel

    2009-01-01

    Studies of aqueous interfaces and of the behavior of ions therein have been profiting from a recent remarkable progress in surface selective spectroscopies, as well as from developments in molecular simulations. Here, we summarize and place in context our investigations of ions at aqueous interfaces employing molecular dynamics simulations and electronic structure methods, performed in close contact with experiment. For the simplest of these interfaces, i.e. the open water surface, we demonstrate that the traditional picture of an ion-free surface is not valid for large, soft (polarizable) ions such as the heavier halides. Both simulations and spectroscopic measurements indicate that these ions can be present and even enhanced at surface of water. In addition we show that the ionic product of water exhibits a peculiar surface behavior with hydronium but not hydroxide accumulating at the air/water and alkane/water interfaces. This result is supported by surface-selective spectroscopic experiments and surface tension measurements. However, it contradicts the interpretation of electrophoretic and titration experiments in terms of strong surface adsorption of hydroxide; an issue which is further discussed here. The applicability of the observed behavior of ions at the water surface to investigations of their affinity for the interface between proteins and aqueous solutions is explored. Simulations show that for alkali cations the dominant mechanism of specific interactions with the surface of hydrated proteins is via ion pairing with negatively charged amino acid residues and with the backbone amide groups. As far as halide anions are concerned, the lighter ones tend to pair with positively charged amino acid residues, while heavier halides exhibit affinity to the amide group and to non-polar protein patches, the latter resembling their behavior at the air/water interface. These findings, together with results for more complex molecular ions, allow us to formulate a

  18. Numerical and experimental study of dissociation in an air-water single-bubble sonoluminescence system.

    PubMed

    Puente, Gabriela F; Urteaga, Raúl; Bonetto, Fabián J

    2005-10-01

    We performed a comprehensive numerical and experimental analysis of dissociation effects in an air bubble in water acoustically levitated in a spherical resonator. Our numerical approach is based on suitable models for the different effects considered. We compared model predictions with experimental results obtained in our laboratory in the whole phase parameter space, for acoustic pressures from the bubble dissolution limit up to bubble extinction. The effects were taken into account simultaneously to consider the transition from nonsonoluminescence to sonoluminescence bubbles. The model includes (1) inside the bubble, transient and spatially nonuniform heat transfer using a collocation points method, dissociation of O2 and N2, and mass diffusion of vapor in the noncondensable gases; (2) at the bubble interface, nonequilibrium evaporation and condensation of water and a temperature jump due to the accommodation coefficient; (3) in the liquid, transient and spatially nonuniform heat transfer using a collocation points method, and mass diffusion of the gas in the liquid. The model is completed with a Rayleigh-Plesset equation with liquid compressible terms and vapor mass transfer. We computed the boundary for the shape instability based on the temporal evolution of the computed radius. The model is valid for an arbitrary number of dissociable gases dissolved in the liquid. We also obtained absolute measurements for R(t) using two photodetectors and Mie scattering calculations. The robust technique used allows the estimation of experimental results of absolute R0 and P(a). The technique is based on identifying the bubble dissolution limit coincident with the parametric instability in (P(a),R0) parameter space. We take advantage of the fact that this point can be determined experimentally with high precision and replicability. We computed the equilibrium concentration of the different gaseous species and water vapor during collapse as a function of P(a) and R0. The

  19. Water temperature effect on upward air-water flow in a vertical pipe: Local measurements database using four-sensor conductivity probes and LDA

    NASA Astrophysics Data System (ADS)

    Monrós-Andreu, G.; Chiva, S.; Martínez-Cuenca, R.; Torró, S.; Juliá, J. E.; Hernández, L.; Mondragón, R.

    2013-04-01

    Experimental work was carried out to study the effects of temperature variation in bubbly, bubbly to slug transition. Experiments were carried out in an upward air-water flow configuration. Four sensor conductivity probes and LDA techniques was used together for the measurement of bubble parameters. The aim of this paper is to provide a bubble parameter experimental database using four-sensor conductivity probes and LDA technique for upward air-water flow at different temperatures and also show transition effect in different temperatures under the boiling point.

  20. Holographic optical tweezers: manipulations at an air-liquid interface

    NASA Astrophysics Data System (ADS)

    Jesacher, Alexander; Fürhapter, Severin; Maurer, Christian; Bernet, Stefan; Ritsch-Marte, Monika

    2006-08-01

    By performing experiments at an air-water interface, we operate Holographic Optical Tweezers in a qualitatively new environment. In this regime, trapping and moving of micro particles may allow access to parameters like local viscosity and surface tension. Polystyrene micro beads are naturally stabilized in the interface due to a minimum in surface energy. For this reason, they can also be manipulated by light patterns with small axial field gradients, without causing the particles to escape due to scattering forces. In this manner, the interface provides a true two-dimensional "working environment", where particles can be manipulated with high effciency. For example, we demonstrate different optical "micro tools", which utilize scattering and gradient forces to enable controlled transport of matter within the surface.

  1. Surface tension dominates insect flight on fluid interfaces.

    PubMed

    Mukundarajan, Haripriya; Bardon, Thibaut C; Kim, Dong Hyun; Prakash, Manu

    2016-03-01

    Flight on the 2D air-water interface, with body weight supported by surface tension, is a unique locomotion strategy well adapted for the environmental niche on the surface of water. Although previously described in aquatic insects like stoneflies, the biomechanics of interfacial flight has never been analysed. Here, we report interfacial flight as an adapted behaviour in waterlily beetles (Galerucella nymphaeae) which are also dexterous airborne fliers. We present the first quantitative biomechanical model of interfacial flight in insects, uncovering an intricate interplay of capillary, aerodynamic and neuromuscular forces. We show that waterlily beetles use their tarsal claws to attach themselves to the interface, via a fluid contact line pinned at the claw. We investigate the kinematics of interfacial flight trajectories using high-speed imaging and construct a mathematical model describing the flight dynamics. Our results show that non-linear surface tension forces make interfacial flight energetically expensive compared with airborne flight at the relatively high speeds characteristic of waterlily beetles, and cause chaotic dynamics to arise naturally in these regimes. We identify the crucial roles of capillary-gravity wave drag and oscillatory surface tension forces which dominate interfacial flight, showing that the air-water interface presents a radically modified force landscape for flapping wing flight compared with air. PMID:26936640

  2. Surface tension dominates insect flight on fluid interfaces.

    PubMed

    Mukundarajan, Haripriya; Bardon, Thibaut C; Kim, Dong Hyun; Prakash, Manu

    2016-03-01

    Flight on the 2D air-water interface, with body weight supported by surface tension, is a unique locomotion strategy well adapted for the environmental niche on the surface of water. Although previously described in aquatic insects like stoneflies, the biomechanics of interfacial flight has never been analysed. Here, we report interfacial flight as an adapted behaviour in waterlily beetles (Galerucella nymphaeae) which are also dexterous airborne fliers. We present the first quantitative biomechanical model of interfacial flight in insects, uncovering an intricate interplay of capillary, aerodynamic and neuromuscular forces. We show that waterlily beetles use their tarsal claws to attach themselves to the interface, via a fluid contact line pinned at the claw. We investigate the kinematics of interfacial flight trajectories using high-speed imaging and construct a mathematical model describing the flight dynamics. Our results show that non-linear surface tension forces make interfacial flight energetically expensive compared with airborne flight at the relatively high speeds characteristic of waterlily beetles, and cause chaotic dynamics to arise naturally in these regimes. We identify the crucial roles of capillary-gravity wave drag and oscillatory surface tension forces which dominate interfacial flight, showing that the air-water interface presents a radically modified force landscape for flapping wing flight compared with air.

  3. Monolayers of long-chain alcohols, fatty acids, and fatty acid esters at the air/water interface: a comparison by external infrared reflection-absorption spectrometry

    NASA Astrophysics Data System (ADS)

    Gericke, Arne; Huehnerfuss, Heinrich

    1994-01-01

    The properties of C15, C16, C18 and C20-alcohols, fatty acids and fatty acid esters are investigated by external infrared reflection-absorption spectrometry in the range 3000 - 1000 cm-1. Analysis of the methylene stretching vibration shows that an increasing space requirement of the hydrophilic headgroup (fatty acid ester > fatty acid >= alcohol) for the same chain length leads to higher chain disorder (i.e., more gauche conformers). However, for a given headgroup the prolongation of the alkyl-chain generally results in an increased hydrophobic interaction and thus in a higher chain-order, i.e., the molecules attain a more transconformation.

  4. CdSe magic-sized quantum dots incorporated in biomembrane models at the air-water interface composed of components of tumorigenic and non-tumorigenic cells.

    PubMed

    Goto, Thiago E; Lopes, Carla C; Nader, Helena B; Silva, Anielle C A; Dantas, Noelio O; Siqueira, José R; Caseli, Luciano

    2016-07-01

    Cadmium selenide (CdSe) magic-sized quantum dots (MSQDs) are semiconductor nanocrystals with stable luminescence that are feasible for biomedical applications, especially for in vivo and in vitro imaging of tumor cells. In this work, we investigated the specific interaction of CdSe MSQDs with tumorigenic and non-tumorigenic cells using Langmuir monolayers and Langmuir-Blodgett (LB) films of lipids as membrane models for diagnosis of cancerous cells. Surface pressure-area isotherms and polarization modulation reflection-absorption spectroscopy (PM-IRRAS) showed an intrinsic interaction between the quantum dots, inserted in the aqueous subphase, and Langmuir monolayers constituted either of selected lipids or of tumorigenic and non-tumorigenic cell extracts. The films were transferred to solid supports to obtain microscopic images, providing information on their morphology. Similarity between films with different compositions representing cell membranes, with or without the quantum dots, was evaluated by atomic force microscopy (AFM) and confocal microscopy. This study demonstrates that the affinity of quantum dots for models representing cancer cells permits the use of these systems as devices for cancer diagnosis. PMID:27107554

  5. The trade-off between heat tolerance and metabolic cost drives the bimodal life strategy at the air-water interface

    PubMed Central

    Fusi, Marco; Cannicci, Stefano; Daffonchio, Daniele; Mostert, Bruce; Pörtner, Hans-Otto; Giomi, Folco

    2016-01-01

    The principle of oxygen and capacity limitation of thermal tolerance in ectotherms suggests that the long-term upper limits of an organism's thermal niche are equivalent to the upper limits of the organism's functional capacity for oxygen provision to tissues. Air-breathing ectotherms show wider thermal tolerances, since they can take advantage of the higher availability of oxygen in air than in water. Bimodal species move from aquatic to aerial media and switch between habitats in response to environmental variations such as cyclical or anomalous temperature fluctuations. Here we tested the prediction that bimodal species cope better with thermal stress than truly aquatic species using the crab Pachygrapsus marmoratus as a model species. When in water, oxygen consumption rates of P. marmoratus acutely rise during warming. Beyond a temperature threshold of 23 °C the crab's aerobic metabolism in air remains lower than in water. In parallel, the haemolymph oxygen partial pressure of submerged animals progressive decreases during warming, while it remains low but constant during emersion. Our results demonstrate the ability of a bimodal breathing ectotherm to extend its thermal tolerance during air-breathing, suggesting that there are temperature-related physiological benefits during the evolution of the bimodal life style. PMID:26758742

  6. The trade-off between heat tolerance and metabolic cost drives the bimodal life strategy at the air-water interface.

    PubMed

    Fusi, Marco; Cannicci, Stefano; Daffonchio, Daniele; Mostert, Bruce; Pörtner, Hans-Otto; Giomi, Folco

    2016-01-13

    The principle of oxygen and capacity limitation of thermal tolerance in ectotherms suggests that the long-term upper limits of an organism's thermal niche are equivalent to the upper limits of the organism's functional capacity for oxygen provision to tissues. Air-breathing ectotherms show wider thermal tolerances, since they can take advantage of the higher availability of oxygen in air than in water. Bimodal species move from aquatic to aerial media and switch between habitats in response to environmental variations such as cyclical or anomalous temperature fluctuations. Here we tested the prediction that bimodal species cope better with thermal stress than truly aquatic species using the crab Pachygrapsus marmoratus as a model species. When in water, oxygen consumption rates of P. marmoratus acutely rise during warming. Beyond a temperature threshold of 23 °C the crab's aerobic metabolism in air remains lower than in water. In parallel, the haemolymph oxygen partial pressure of submerged animals progressive decreases during warming, while it remains low but constant during emersion. Our results demonstrate the ability of a bimodal breathing ectotherm to extend its thermal tolerance during air-breathing, suggesting that there are temperature-related physiological benefits during the evolution of the bimodal life style.

  7. The adsorption behavior of ionic surfactants and their mixtures with nonionic polymers and with polyelectrolytes of opposite charge at the air-water interface.

    PubMed

    Bahramian, Alireza; Thomas, Robert K; Penfold, Jeffrey

    2014-03-13

    The surface phase approach of Butler has been used to derive a model of the surface tension (ST) of surfactant solutions in terms of the ST of the surfactant in the absence of water, an area parameter corresponding approximately to the limiting area per molecule, and the critical micelle concentration (CMC). This isotherm is then used to account for the ST behavior of aqueous solutions of weakly interacting polymer-surfactant (P-S) and strongly interacting polyelectrolyte-surfactant (PE-S) mixtures. For P-S systems, no additional parameters are required other than the critical aggregation concentration (CAC) and the onset of the ST plateau at micellization (T3). The model accounts for experimental isotherms for sodium dodecyl sulfate (SDS) with poly(ethylene oxide) or poly(vinylpyrrolidone). For PE-S systems, the initial CAC has no effect on the ST and is well below the decrease in ST that leads to the first ST plateau at T1. This decrease is modeled approximately using a Langmuir isotherm. The remaining ST behavior is analyzed with the model surfactant isotherm and includes modeling the ST when there is separation into two phases. The behavior in the phase separation region depends on the dissociability of the PE-S complex. Loss of surface activity accompanied by a peak in the ST may occur when there is part formation of a nondissociable complex (neutral with segment/surfactant = 1). The model successfully explains the ST of several experimental systems with and without ST peaks, including poly(dimethyldiallylammonium chloride)-SDS and poly(sodium styrenesulfonate)-alkyltrimethylammonium bromide (C(n)TAB) with n = 12, 14, and 16.

  8. The adsorption behavior of ionic surfactants and their mixtures with nonionic polymers and with polyelectrolytes of opposite charge at the air-water interface.

    PubMed

    Bahramian, Alireza; Thomas, Robert K; Penfold, Jeffrey

    2014-03-13

    The surface phase approach of Butler has been used to derive a model of the surface tension (ST) of surfactant solutions in terms of the ST of the surfactant in the absence of water, an area parameter corresponding approximately to the limiting area per molecule, and the critical micelle concentration (CMC). This isotherm is then used to account for the ST behavior of aqueous solutions of weakly interacting polymer-surfactant (P-S) and strongly interacting polyelectrolyte-surfactant (PE-S) mixtures. For P-S systems, no additional parameters are required other than the critical aggregation concentration (CAC) and the onset of the ST plateau at micellization (T3). The model accounts for experimental isotherms for sodium dodecyl sulfate (SDS) with poly(ethylene oxide) or poly(vinylpyrrolidone). For PE-S systems, the initial CAC has no effect on the ST and is well below the decrease in ST that leads to the first ST plateau at T1. This decrease is modeled approximately using a Langmuir isotherm. The remaining ST behavior is analyzed with the model surfactant isotherm and includes modeling the ST when there is separation into two phases. The behavior in the phase separation region depends on the dissociability of the PE-S complex. Loss of surface activity accompanied by a peak in the ST may occur when there is part formation of a nondissociable complex (neutral with segment/surfactant = 1). The model successfully explains the ST of several experimental systems with and without ST peaks, including poly(dimethyldiallylammonium chloride)-SDS and poly(sodium styrenesulfonate)-alkyltrimethylammonium bromide (C(n)TAB) with n = 12, 14, and 16. PMID:24552283

  9. CdSe magic-sized quantum dots incorporated in biomembrane models at the air-water interface composed of components of tumorigenic and non-tumorigenic cells.

    PubMed

    Goto, Thiago E; Lopes, Carla C; Nader, Helena B; Silva, Anielle C A; Dantas, Noelio O; Siqueira, José R; Caseli, Luciano

    2016-07-01

    Cadmium selenide (CdSe) magic-sized quantum dots (MSQDs) are semiconductor nanocrystals with stable luminescence that are feasible for biomedical applications, especially for in vivo and in vitro imaging of tumor cells. In this work, we investigated the specific interaction of CdSe MSQDs with tumorigenic and non-tumorigenic cells using Langmuir monolayers and Langmuir-Blodgett (LB) films of lipids as membrane models for diagnosis of cancerous cells. Surface pressure-area isotherms and polarization modulation reflection-absorption spectroscopy (PM-IRRAS) showed an intrinsic interaction between the quantum dots, inserted in the aqueous subphase, and Langmuir monolayers constituted either of selected lipids or of tumorigenic and non-tumorigenic cell extracts. The films were transferred to solid supports to obtain microscopic images, providing information on their morphology. Similarity between films with different compositions representing cell membranes, with or without the quantum dots, was evaluated by atomic force microscopy (AFM) and confocal microscopy. This study demonstrates that the affinity of quantum dots for models representing cancer cells permits the use of these systems as devices for cancer diagnosis.

  10. Phospholipids at the Interface: Current Trends and Challenges

    PubMed Central

    Pichot, Roman; Watson, Richard L.; Norton, Ian T.

    2013-01-01

    Phospholipids are one of the major structural elements of biological membranes. Due to their amphiphilic character, they can adopt various molecular assemblies when dispersed in water, such as bilayer vesicles or micelles, which give them unique interfacial properties and render them very attractive in terms of foam or emulsion stabilization. This article aims at reviewing the properties of phospholipids at the air/water and oil/water interfaces, as well as the recent advances in using these natural components as stabilizers, alone or in combination with other compounds such as proteins. A discussion regarding the challenges and opportunities offered by phospholipids-stabilized structure concludes the review. PMID:23736688

  11. Translational viscous drags of an ellipsoid straddling an interface between two fluids.

    PubMed

    Boniello, Giuseppe; Stocco, Antonio; Gross, Michel; In, Martin; Blanc, Christophe; Nobili, Maurizio

    2016-07-01

    We study the dynamics of individual polystyrene ellipsoids of different aspect ratios trapped at the air-water interface. Using particle tracking and in situ vertical scanning interferometry techniques we are able to measure translational drags and the protrusion in air of the ellipsoids. We report that translational drags on the ellipsoid are unexpectedly enhanced: despite the fact that a noticeable part of the ellipsoid is in air, drags are found larger than the bulk one in water. PMID:27575174

  12. Translational viscous drags of an ellipsoid straddling an interface between two fluids

    NASA Astrophysics Data System (ADS)

    Boniello, Giuseppe; Stocco, Antonio; Gross, Michel; In, Martin; Blanc, Christophe; Nobili, Maurizio

    2016-07-01

    We study the dynamics of individual polystyrene ellipsoids of different aspect ratios trapped at the air-water interface. Using particle tracking and in situ vertical scanning interferometry techniques we are able to measure translational drags and the protrusion in air of the ellipsoids. We report that translational drags on the ellipsoid are unexpectedly enhanced: despite the fact that a noticeable part of the ellipsoid is in air, drags are found larger than the bulk one in water.

  13. Soft Interfaces

    NASA Astrophysics Data System (ADS)

    Gilles de Gennes, Pierre; Edwards, Introduction By Sam

    1997-04-01

    Paul Adrien Maurice Dirac, one of the greatest physicists of the twentieth century, died in 1984. Dirac's college, St. John's of Cambridge, generously endowed annual lectures to be held at Cambridge University in his memory. This volume contains a much expanded version of the 1994 Dirac Lecture by Nobel Laureate Pierre Gilles de Gennes. The book presents an impressionistic tour of the physics of soft interfaces. Full of insight and interesting asides, it not only provides an accessible introduction to this topic, but also lays down many markers and signposts that will be of interest to researchers in physics or chemistry. Features discussions of wetting and dewetting, the dynamics of different types of interface and adhesion and polymer/polymer welding.

  14. Simulating the Vapour Phase Air/Water Exchange of p,p′-DDE, p,p′-DDT, Lindane, and 2,3,7,8-Tetrachlorodibenzodioxin

    EPA Science Inventory

    Uncertainties in our understanding of gaseous air/water exchange have emerged as major sources of concern in efforts to construct global and regional mass balances of both the green house gas carbon dioxide and semi-volatile persistent, bioaccumulative and toxic chemicals. Hoff e...

  15. Gaseous and Freely-Dissolved PCBs in the Lower Great Lakes Based on Passive Sampling: Spatial Trends and Air-Water Exchange.

    PubMed

    Liu, Ying; Wang, Siyao; McDonough, Carrie A; Khairy, Mohammed; Muir, Derek C G; Helm, Paul A; Lohmann, Rainer

    2016-05-17

    Polyethylene passive sampling was performed to quantify gaseous and freely dissolved polychlorinated biphenyls (PCBs) in the air and water of Lakes Erie and Ontario during 2011-2012. In view of differing physical characteristics and the impacts of historical contamination by PCBs within these lakes, spatial variation of PCB concentrations and air-water exchange across these lakes may be expected. Both lakes displayed statistically similar aqueous and atmospheric PCB concentrations. Total aqueous concentrations of 29 PCBs ranged from 1.5 pg L(-1) in the open lake of Lake Erie (site E02) in 2011 spring to 105 pg L(-1) in Niagara (site On05) in 2012 summer, while total atmospheric concentrations were 7.7-634 pg m(-3) across both lakes. A west-to-east gradient was observed for aqueous PCBs in Lake Erie. River discharge and localized influences (e.g., sediment resuspension and regional alongshore transport) likely dominated spatial trends of aqueous PCBs in both lakes. Air-water exchange fluxes of Σ7PCBs ranged from -2.4 (±1.9) ng m(-2) day(-1) (deposition) in Sheffield (site E03) to 9.0 (±3.1) ng m(-2) day(-1) (volatilization) in Niagara (site On05). Net volatilization of PCBs was the primary trend across most sites and periods. Almost half of variation in air-water exchange fluxes was attributed to the difference in aqueous concentrations of PCBs. Uncertainty analysis in fugacity ratios and mass fluxes in air-water exchange of PCBs indicated that PCBs have reached or approached equilibrium only at the eastern Lake Erie and along the Canadian shore of Lake Ontario sites, where air-water exchange fluxes dominated atmospheric concentrations.

  16. Gaseous and Freely-Dissolved PCBs in the Lower Great Lakes Based on Passive Sampling: Spatial Trends and Air-Water Exchange.

    PubMed

    Liu, Ying; Wang, Siyao; McDonough, Carrie A; Khairy, Mohammed; Muir, Derek C G; Helm, Paul A; Lohmann, Rainer

    2016-05-17

    Polyethylene passive sampling was performed to quantify gaseous and freely dissolved polychlorinated biphenyls (PCBs) in the air and water of Lakes Erie and Ontario during 2011-2012. In view of differing physical characteristics and the impacts of historical contamination by PCBs within these lakes, spatial variation of PCB concentrations and air-water exchange across these lakes may be expected. Both lakes displayed statistically similar aqueous and atmospheric PCB concentrations. Total aqueous concentrations of 29 PCBs ranged from 1.5 pg L(-1) in the open lake of Lake Erie (site E02) in 2011 spring to 105 pg L(-1) in Niagara (site On05) in 2012 summer, while total atmospheric concentrations were 7.7-634 pg m(-3) across both lakes. A west-to-east gradient was observed for aqueous PCBs in Lake Erie. River discharge and localized influences (e.g., sediment resuspension and regional alongshore transport) likely dominated spatial trends of aqueous PCBs in both lakes. Air-water exchange fluxes of Σ7PCBs ranged from -2.4 (±1.9) ng m(-2) day(-1) (deposition) in Sheffield (site E03) to 9.0 (±3.1) ng m(-2) day(-1) (volatilization) in Niagara (site On05). Net volatilization of PCBs was the primary trend across most sites and periods. Almost half of variation in air-water exchange fluxes was attributed to the difference in aqueous concentrations of PCBs. Uncertainty analysis in fugacity ratios and mass fluxes in air-water exchange of PCBs indicated that PCBs have reached or approached equilibrium only at the eastern Lake Erie and along the Canadian shore of Lake Ontario sites, where air-water exchange fluxes dominated atmospheric concentrations. PMID:26642083

  17. Concentrations, Trends, and Air-Water Exchange of PAHs and PBDEs Derived from Passive Samplers in Lake Superior in 2011.

    PubMed

    Ruge, Zoe; Muir, Derek; Helm, Paul; Lohmann, Rainer

    2015-12-01

    Polycyclic aromatic hydrocarbons (PAHs) and polybrominated diphenylethers (PBDEs) are both currently released into the environment from anthropogenic activity. Both are hence primarily associated with populated or industrial areas, although wildfires can be an important source of PAHs, as well. Polyethylene passive samplers (PEs) were simultaneously deployed in surface water and near surface atmosphere to determine spatial trends and air-water gaseous exchange of 21 PAHs and 11 PBDEs at 19 sites across Lake Superior in 2011. Surface water and atmospheric PAH concentrations were greatest at urban sites (up to 65 ng L(-1) and 140 ng m(-3), respectively, averaged from June to October). Near populated regions, PAHs displayed net air-to-water deposition, but were near equilibrium off-shore. Retene, probably depositing following major wildfires in the region, dominated dissolved PAH concentrations at most Lake Superior sites. Atmospheric and dissolved PBDEs were greatest near urban and populated sites (up to 6.8 pg L(-1) and 15 pg m(-3), respectively, averaged from June to October), dominated by BDE-47. At most coastal sites, there was net gaseous deposition of BDE-47, with less brominated congeners contributing to Sault Ste. Marie and eastern open lake fluxes. Conversely, the central open lake and Eagle Harbor sites generally displayed volatilization of PBDEs into the atmosphere, mainly BDE-47. PMID:26436513

  18. Spatial Distribution, Air-Water Fugacity Ratios and Source Apportionment of Polychlorinated Biphenyls in the Lower Great Lakes Basin.

    PubMed

    Khairy, Mohammed; Muir, Derek; Teixeira, Camilla; Lohmann, Rainer

    2015-12-01

    Polychlorinated biphenyls (PCBs) continue to be contaminants of concern across the Great Lakes. It is unclear whether current concentrations are driven by ongoing primary emissions from their original uses, or whether ambient PCBs are dominated by their environmental cycling. Freely dissolved PCBs in air and water were measured using polyethylene passive samplers across Lakes Erie and Ontario during summer and fall, 2011, to investigate their spatial distribution, determine and apportion their sources and to asses their air-water exchange gradients. Average gaseous and freely dissolved ∑29 PCB concentrations ranged from 5.0 to 160 pg/m(3) and 2.0 to 55 pg/L respectively. Gaseous concentrations were significantly correlated (R(2) = 0.80) with the urban area within a 3-20 km radius. Fugacity ratios indicated that the majority of PCBs are volatilizing from the water thus acting as a secondary source for the atmosphere. Dissolved PCBs were probably linked to PCB emissions from contaminated sites and areas of concern. Positive matrix factorization indicated that although volatilized Aroclors (gaseous PCBs) and unaltered Aroclors (dissolved PCBs) dominate in some samples, ongoing non-Aroclor sources such as paints/pigments (PCB 11) and coal/wood combustion showed significant contributions across the lower Great Lakes. Accordingly, control strategies should give further attention to PCBs emitted from current use sources. PMID:25915412

  19. Anisotropic effective permittivity of an ultrathin gold coating on optical fiber in air, water and saline solutions.

    PubMed

    Zhou, Wenjun; Mandia, David J; Barry, Seán T; Albert, Jacques

    2014-12-29

    The optical properties of an ultrathin discontinuous gold film in different dielectric surroundings are investigated experimentally by measuring the polarization-dependent wavelength shifts and amplitudes of the cladding mode resonances of a tilted fiber Bragg grating. The gold film was prepared by electron-beam evaporation and had an average thickness of 5.5 nm ( ± 1 nm). Scanning electron imaging was used to determine that the film is actually formed of individual particles with average lateral dimensions of 28 nm ( ± 8 nm). The complex refractive indices of the equivalent uniform film in air at a wavelength of 1570 nm were calculated from the measurements to be 4.84-i0.74 and 3.97-i0.85 for TM and TE polarizations respectively (compared to the value for bulk gold: 0.54-i10.9). Additionally, changes in the birefringence and dichroism of the films were measured as a function of the surrounding medium, in air, water and a saturated NaCl (salt) solution. These results show that the film has stronger dielectric behavior for TM light than for TE, a trend that increases with increasing surrounding index. Finally, the experimental results are compared to predictions from two widely used effective medium approximations, the generalized Maxwell-Garnett and Bruggeman theories for gold particles in a surrounding matrix. It is found that both of these methods fail to predict the observed behavior for the film considered. PMID:25607137

  20. Spatial Distribution, Air-Water Fugacity Ratios and Source Apportionment of Polychlorinated Biphenyls in the Lower Great Lakes Basin.

    PubMed

    Khairy, Mohammed; Muir, Derek; Teixeira, Camilla; Lohmann, Rainer

    2015-12-01

    Polychlorinated biphenyls (PCBs) continue to be contaminants of concern across the Great Lakes. It is unclear whether current concentrations are driven by ongoing primary emissions from their original uses, or whether ambient PCBs are dominated by their environmental cycling. Freely dissolved PCBs in air and water were measured using polyethylene passive samplers across Lakes Erie and Ontario during summer and fall, 2011, to investigate their spatial distribution, determine and apportion their sources and to asses their air-water exchange gradients. Average gaseous and freely dissolved ∑29 PCB concentrations ranged from 5.0 to 160 pg/m(3) and 2.0 to 55 pg/L respectively. Gaseous concentrations were significantly correlated (R(2) = 0.80) with the urban area within a 3-20 km radius. Fugacity ratios indicated that the majority of PCBs are volatilizing from the water thus acting as a secondary source for the atmosphere. Dissolved PCBs were probably linked to PCB emissions from contaminated sites and areas of concern. Positive matrix factorization indicated that although volatilized Aroclors (gaseous PCBs) and unaltered Aroclors (dissolved PCBs) dominate in some samples, ongoing non-Aroclor sources such as paints/pigments (PCB 11) and coal/wood combustion showed significant contributions across the lower Great Lakes. Accordingly, control strategies should give further attention to PCBs emitted from current use sources.

  1. Experimental study on the void fraction of air-water two-phase flow in a horizontal circular minichannel

    NASA Astrophysics Data System (ADS)

    Sudarja, Indarto, Deendarlianto, Haq, Aqli

    2016-06-01

    Void fraction is an important parameter in two-phase flow. In the present work, the adiabatic two-phase air-water flow void fraction in a horizontal minichannel has been studied experimentally. A transparent circular channel with 1.6 mm inner diameter was employed as the test section. Superficial gas and liquid velocities were varied in the range of 1.25 - 66.3 m/s and 0.033 - 4.935 m/s, respectively. Void fraction data were obtained by analyzing the flow images being captured by using a high-speed camera. Here, the homogeneous (β) and the measured void fractions (ɛ), respectively, were compared to the existing correlations. It was found that: (1) for the bubbly and slug flows, the void fractions increases with the increase of JG, (2) for churn, slug-annular, and annular flow patterns, there is no specific correlation between JG and void fraction was observed due to effect of the slip between gas and liquid, and (3) whilst for bubbly and slug flows the void fractions are close to homogeneous line, for churn, annular, and slug-annular flows are far below the homogeneous line. It indicates that the slip ratios for the second group of flow patterns are higher than unity.

  2. Distribution of air-water mixtures in parallel vertical channels as an effect of the header geometry

    SciTech Connect

    Marchitto, Annalisa; Fossa, Marco; Guglielmini, Giovanni

    2009-07-15

    Uneven phase distribution in heat exchangers is a cause of severe reductions in thermal performances of refrigeration equipment. To date, no general design rules are available to avoid phase separation in manifolds with several outlet channels, and even predicting the phase and mass distribution in parallel channels is a demanding task. In the present paper, measurements of two-phase air-water distributions are reported with reference to a horizontal header supplying 16 vertical upward channels. The effects of the operating conditions, the header geometry and the inlet port nozzle were investigated in the ranges of liquid and gas superficial velocities of 0.2-1.2 and 1.5-16.5 m/s, respectively. Among the fitting devices used, the insertion of a co-axial, multi-hole distributor inside the header confirmed the possibility of greatly improving the liquid and gas flow distribution by the proper selection of position, diameter and number of the flow openings between the supplying distributor and the system of parallel channels connected to the header. (author)

  3. Air-water partition coefficients for a suite of polycyclic aromatic and other C10 through C20 unsaturated hydrocarbons.

    PubMed

    Rayne, Sierra; Forest, Kaya

    2016-09-18

    The air-water partition coefficients (Kaw) for 86 large polycyclic aromatic hydrocarbons and their unsaturated relatives were estimated using high-level G4(MP2) gas and aqueous phase calculations with the SMD, IEFPCM-UFF, and CPCM solvation models. An extensive method validation effort was undertaken which involved confirming that, via comparisons to experimental enthalpies of formation, gas-phase energies at the G4(MP2) level for the compounds of interest were at or near thermochemical accuracy. Investigations of the three solvation models using a range of neutral and ionic compounds suggested that while no clear preferential solvation model could be chosen in advance for accurate Kaw estimates of the target compounds, the employment of increasingly higher levels of theory would result in lower Kaw errors. Subsequent calculations on the polycyclic aromatic and unsaturated hydrocarbons at the G4(MP2) level revealed excellent agreement for the IEFPCM-UFF and CPCM models against limited available experimental data. The IEFPCM-UFF-G4(MP2) and CPCM-G4(MP2) solvation energy calculation approaches are anticipated to give Kaw estimates within typical experimental ranges, each having general Kaw errors of less than 0.5 log10 units. When applied to other large organic compounds, the method should allow development of a broad and reliable Kaw database for multimedia environmental modeling efforts on various contaminants. PMID:27336293

  4. Experimental investigation on the interfacial characteristics of stratified air-water two-phase flow in a horizontal pipe

    NASA Astrophysics Data System (ADS)

    Hudaya, Akhmad Zidni; Kuntoro, Hadiyan Yusuf; Dinaryanto, Okto; Deendarlianto, Indarto

    2016-06-01

    The interfacial wave characteristics of stratified air-water two-phase flow in a horizontal pipe were experimentally investigated by using the flush-mounted constant electric current method (CECM) sensors. The experiments were conducted in a horizontal two-phase flow loop 9.5 m long (L) consisting of transparent acrylic pipe of 26 mm i.d. (D). To obtain the stratified flow pattern, the superficial gas and liquid velocities were set to 1.02 - 3.77 m/s and 0.016 - 0.92 m/s, respectively. Several interfacial wave patterns as described by several investigators were identified. The common parameters such as liquid hold-up, probability distribution function, wave velocity and wave frequency were investigated as the function of the liquid and gas flow rates. The interfacial curvature was calculated on the basis of the liquid hold-up data from the CECM sensors and the liquid film thickness data from the image processing technique in the previous work. As a result, it was found that the mean liquid hold-up decreases with the increase of the superficial gas velocity. In the same sub flow pattern, the wave velocity increases as the superficial gas velocity increases. On the other hand, in the two-dimensional wave region, the dominant frequency decreases with the increase of the superficial liquid velocity.

  5. Thermal characteristics of air-water spray impingement cooling of hot metallic surface under controlled parametric conditions

    NASA Astrophysics Data System (ADS)

    Nayak, Santosh Kumar; Mishra, Purna Chandra

    2016-06-01

    Experimental results on the thermal characteristics of air-water spray impingement cooling of hot metallic surface are presented and discussed in this paper. The controlling input parameters investigated were the combined air and water pressures, plate thickness, water flow rate, nozzle height from the target surface and initial temperature of the hot surface. The effects of these input parameters on the important thermal characteristics such as heat transfer rate, heat transfer coefficient and wetting front movement were measured and examined. Hot flat plate samples of mild steel with dimension 120 mm in length, 120 mm breadth and thickness of 4 mm, 6 mm, and 8 mm respectively were tested. The air assisted water spray was found to be an effective cooling media and method to achieve very high heat transfer rate from the surface. Higher heat transfer rate and heat transfer coefficients were obtained for the lesser i.e, 4 mm thick plates. Increase in the nozzle height reduced the heat transfer efficiency of spray cooling. At an inlet water pressure of 4 bar and air pressure of 3 bar, maximum cooling rates 670°C/s and average cooling rate of 305.23°C/s were achieved for a temperature of 850°C of the steel plate.

  6. Nonlinear optical studies of aqueous interfaces, polymers, and nanowires

    NASA Astrophysics Data System (ADS)

    Onorato, Robert Michael

    Understanding the structure and composition of aqueous interfaces is one of the most important current problems in modern science. Aqueous interfaces are ubiquitous in Nature, ranging from aerosols to cellular structures. Aerosol chemistry is presently the most significant unknown factor in predicting climate change, and an understanding of the chemistry that occurs at aerosol interfaces would significantly improve climate models. Similarly, the nature of aqueous biological interfaces has a profound effect on the structure and function of proteins and other biological structures. Despite the importance of these problems, aqueous interfaces remain incompletely understood due to the challenges of experimentally probing them. Recent experimental and theoretical results have firmly established the existence of enhanced concentrations of selected ions at the air/water interface. In this dissertation, I use an interface-specific technique, UV second harmonic generation (SHG), to further investigate the adsorption of ions to the air/water interface and to extend the study of ion adsorption towards more biologically relevant systems, alcohol/water interfaces. In Chapter 2, I describe resonant UV-SHG studies of the strongly chaotropic thiocyanate ion adsorbed to the interface formed by water and a monolayer of dodecanol, wherein the Gibbs free energy of adsorption was determined to be -6.7 +/- 1.1 and -6.3 +/- 1.8 kJ/mol for sodium and potassium thiocyanate, respectively, coincident with the value determined for thiocyanate at the air/water interface. Interestingly, at concentrations near and above 4 M, the resonant SHG signal increases discontinuously, indicating a structural change in the interfacial region. Recent experimental and theoretical work has demonstrated that the adsorption of bromide is particularly important for chemical reactions on atmospheric aerosols, including the depletion of ozone. In Chapter 3, UV-SHG resonant with the bromide charge

  7. Role of hydration forces in the properties of electrolyte solutions in the bulk and at interfaces

    SciTech Connect

    Sushko, Maria L.; Rosso, Kevin M.

    2015-03-01

    We present a theoretical approach for modeling electrolyte solutions at interfaces that reaches into the mesoscale while retaining molecular detail. The total Hamiltonian of the system includes interactions arising from density and charge density (ion correlation) fluctuations, direct Coulomb interactions between ions, and at interfaces the image interactions, ion-solid and ion-water dispersion interactions. The model was validated against its ability to reproduce ion activity in 1:1 and 2:1 electrolyte solutions in the 0-2 M concentration range, its ability to capture the ion-specific effect in 1:1 electrolytes at the air-water interface, and solvent structure in a confined environment between hydrophobic surfaces, revealing the central role of ion hydration interactions in specific ion thermodynamic properties in the bulk solutions and at interfaces. The model is readily extensible to treat electrolyte interactions and forces across charged solid-water interfaces.

  8. Tunable sound transmission at an impedance-mismatched fluidic interface assisted by a composite waveguide

    PubMed Central

    Zhang, Hui; Wei, Zhi; Fan, Li; Qu, Jianmin; Zhang, Shu-yi

    2016-01-01

    We report a composite waveguide fabricated by attaching a coupling aperture to a waveguide. The acoustic impedance of the composite waveguide can be regulated by merely controlling its coupling vibrations, depending on its structure size. By changing the size to adjust the acoustic impedance of the composite waveguide at an impedance-mismatched fluidic interface, tunable sound transmission at the desired frequencies is achieved. The reported composite waveguide provides a new method for sound regulation at a mismatched fluidic interface and has extensive frequency hopping and frequency agility applications in air-water sound communication. PMID:27698379

  9. Tunable sound transmission at an impedance-mismatched fluidic interface assisted by a composite waveguide

    NASA Astrophysics Data System (ADS)

    Zhang, Hui; Wei, Zhi; Fan, Li; Qu, Jianmin; Zhang, Shu-Yi

    2016-10-01

    We report a composite waveguide fabricated by attaching a coupling aperture to a waveguide. The acoustic impedance of the composite waveguide can be regulated by merely controlling its coupling vibrations, depending on its structure size. By changing the size to adjust the acoustic impedance of the composite waveguide at an impedance-mismatched fluidic interface, tunable sound transmission at the desired frequencies is achieved. The reported composite waveguide provides a new method for sound regulation at a mismatched fluidic interface and has extensive frequency hopping and frequency agility applications in air-water sound communication.

  10. Shock wave interaction with interfaces between materials having different acoustic impedances

    NASA Astrophysics Data System (ADS)

    Hosseini, H.; Moosavi-Nejad, S.; Akiyama, H.; Menezes, V.

    2014-03-01

    We experimentally examined interaction of blast waves with water-air/air-water interfaces through high-speed-real-time visualization and measurement of pressure across the waves. The underwater shock wave, which was expected to reflect totally at the water-air interface, was observed transmitting a shock front to air. Transmission of a blast wave from air to water was also visualized and evaluated. Underwater shock waves are used in several medical/biological procedures, where such unforeseen transmissions can result in detriments. The details provide a guideline to evaluate blast wave transmissions, which can induce tissue and brain injuries. The results explain mechanisms behind blast-induced traumatic brain injury.

  11. Dilatational rheology of beta-casein adsorbed layers at liquid-fluid interfaces.

    PubMed

    Maldonado-Valderrama, Julia; Fainerman, Valentin B; Galvez-Ruiz, M José; Martín-Rodriguez, Antonio; Cabrerizo-Vílchez, Miguel A; Miller, Reinhard

    2005-09-22

    The rheological behavior of beta-casein adsorption layers formed at the air-water and tetradecane-water interfaces is studied in detail by means of pendant drop tensiometry. First, its adsorption behavior is briefly summarized at both interfaces, experimentally and also theoretically. Subsequently, the experimental dilatational results obtained for a wide range of frequencies are presented for both interfaces. An interesting dependence with the oscillation frequency is observed via the comparative analysis of the interfacial elasticity (storage part) and the interfacial viscosity (loss part) for the two interfaces. The analysis of the interfacial elasticities provides information on the conformational transitions undergone by the protein upon adsorption at both interfaces. The air-water interface shows a complex behavior in which two maxima merge into one as the frequency increases, whereas only a single maximum is found at the tetradecane interface within the range of frequencies studied. This is interpreted in terms of a decisive interaction between the oil and the protein molecules. Furthermore, the analysis of the interfacial viscosities provides information on the relaxation processes occurring at both interfaces. Similarly, substantial differences arise between the gaseous and liquid interfaces and various possible relaxation mechanisms are discussed. Finally, the experimental elasticities obtained for frequencies higher than 0.1 Hz are further analyzed on the basis of a thermodynamic model. Accordingly, the nature of the conformational transition given by the maximum at these frequencies is discussed in terms of different theoretical considerations. The formation of a protein bilayer at the interface or the limited compressibility of the protein in the adsorbed state are regarded as possible explanations of the maximum.

  12. Carbon budgets for three autotrophic Australian estuaries: Implications for global estimates of the coastal air-water CO2 flux

    NASA Astrophysics Data System (ADS)

    Maher, D. T.; Eyre, B. D.

    2012-03-01

    Estuaries are `hot spots' in the global carbon cycle, yet data on carbon dynamics, in particular air-sea CO2 fluxes, from autotrophic systems are rare. Estuarine carbon budgets were constructed for three geomorphically distinct warm temperate Australian estuaries over an annual cycle. All three estuaries were net autotrophic, with annual net ecosystem metabolism (NEM) ranging from 8 ± 13.4 molC m-2 yr-1 to 10 ± 14 molC m-2 yr-1. There was a net flux of CO2 from the atmosphere to the estuaries of between 0.4 ± 0.6 molC m-2 yr-1 and 2 ± 0.9 molC m-2 yr-1. Loading of dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC) to the estuaries varied markedly within and between the estuaries, and was directly related to freshwater inflow. While NEM was similar in all three estuaries, the ratio of benthic versus pelagic contributions to NEM differed, with NEM dominated by pelagic production in the river dominated system, benthic production dominating in the intermediate estuary, and equal contributions of benthic and pelagic production in the marine dominated lagoon. All three estuaries exported more organic carbon than was imported, fueled by additional organic carbon supplied by NEM. The estuaries essentially acted as bioreactors, transforming DIC to organic carbon. Burial of organic carbon ranged from 1.2 ± 0.3 molC m-2 yr-1 to 4.4 ± 1.2 molC m-2 yr-1 and represented up to half of NEM. The annual net uptake of atmospheric CO2 in these systems, along with previous estimates of the global estuarine CO2flux being based predominantly on heterotrophic, large river dominated estuarine systems, indicates that the global estimate of the estuarine air-water CO2flux may be over-estimated due to the lack of studies from autotrophic marine dominated estuaries.

  13. Air-water transfer of MTBE, its degradation products, and alternative fuel oxygenates: the role of temperature.

    PubMed

    Arp, Hans Peter H; Schmidt, Torsten C

    2004-10-15

    The gasoline oxygenate methyl tert-butyl ether (MTBE) has become one of the world's mostwidespread groundwater and surface water contaminants. As a result, there has been increasing interest in the environmental behavior of MTBE and its degradation products, mainly tert-butyl formate (TBF) and tert-butyl alcohol (TBA). In contrast, the environmental behavior of the proposed alternatives to MTBE, namely ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME), and diisopropyl ether (DIPE) has hardly been studied yet, although some of them are already in substantial use in various countries. A key parameter for the assessment of the fate, transport, and possible remediation of these contaminants is the air-water partitioning constant (KiH). The KiH is highly temperature dependent, and it is therefore necessary to obtain reliable experimental values at relevant temperatures. Hence, the KiH of MTBE, ETBE, TAME, and DIPE, along with the degradation products, TBF and methyl acetate, were determined from 5 degrees C-40 degrees C. The alternatives to MTBE generally had a higher KiH, which implies that, upon emission into the environment, the alternatives partition more readily into the air phase than MTBE. This may favor their use, as it is in the air phase where dilution and degradation are the most effective. The degradation products of MTBE, with the exception of TBF, have much lower KiH values at all temperatures. Hence, the degradation products will have a stronger affinity for the water phase. The temperature dependency of the kinetics of air-watertransfer is discussed using a boundary layer model. Only for TBA but not for the ethers a significant effect of temperature was found.

  14. Spontaneous curvature in chiral polar filaments near interfaces

    NASA Astrophysics Data System (ADS)

    Olmsted, Peter D.; Riley, Emily E.; Jordens, Sophia; Usov, Ivan; Isa, Lucio; Mezzenga, Raffaele

    2015-03-01

    Chiral filaments (actin, DNA, alpha helical strands, ...) are ubiquitous in biology, and they frequently come into contact with interfaces or inhomogeneous environments, either in biology (e.g. actin on membranes) or use and processing of biomaterials (fibrils at solvent boundaries or nanoparticle surfaces). Recent experiments have shown that amyloid fibrils can develop unusual curvatures at the air-water interface. Here we show that spontaneous curvature follows, on symmetry grounds, for chiral polar filaments placed in inhomgeneous environments such as near surfaces. We demonstrate this for simple model surface-fibril interactions, and discuss some of the implications. Financial support is acknowledged from: ETH Zurich (ETHIIRA TH 32-1), SNF (2-77002-11), and SNSF (IZK072_141955, PP00P2_144646/1, PZ00P2_142532/1).

  15. Comparison of the adsorption of linear alkanesulfonate and linear alkylbenzenesulfonate surfactants at liquid interfaces

    SciTech Connect

    Watry, M.R.; Richmond, G.L.

    2000-02-09

    Linear alkanesulfonates and linear alkylbenzenesulfonates constitute a large fraction of the surfactants used in commercial detergents and cleansers. Despite the industrial significance and the possible environmental impact of these compounds, very little in known regarding the molecular properties of these compounds and how they relate to macroscopic properties desired in applications. This study employs vibrational sum frequency spectroscopy (VSFS) to examine and compare the molecular structure of surfactants in these two classes as they adsorb at organic/water and air/water interfaces. The linear alkane- and alkylbenzenesulfonates studied are, respectively, dodecanesulfonate and dodecylbenzenesulfonate. By measurement and comparison of the vibrational spectra of these adsorbed surfactants, changes in the orientation of the aromatic ring and the conformation of the alkyl chains are examined as a function on the number density of surfactant molecules at the interface. The change in aromatic ring orientation as a function of surface concentration is quite different for the dodecylbenzenesulfonate at the air/water interface relative to that at the organic/water interface (CCl{sub 4}/water). The alkyl chains of the dodecylbenzenesulfonate are highly disordered at both interfaces as a function of interfacial concentration, in stark contrast to what is observed for the dodecanesulfonate. The results are discussed in terms of the disruptive nature of the benzene ring and the higher degree of hydrophobicity of the alkyl chain relative to the benzene ring near the ionic sulfonate group.

  16. Fatty-acid monolayers at the nematic/water interface: phases and liquid-crystal alignment.

    PubMed

    Price, Andrew D; Schwartz, Daniel K

    2007-02-01

    The two-dimensional (2D) phases of fatty-acid monolayers (hexadecanoic, octadecanoic, eicosanoic, and docosanoic acids) have been studied at the interface of a nematic liquid crystal (LC) and water. When observed between crossed polarizers, the LC responds to monolayer structure owing to mesoscopic alignment of the LC by the adsorbed molecules. Similar to Langmuir monolayers at the air/water interface, the adsorbed monolayer at the nematic/water interface displays distinct thermodynamic phases. Observed are a 2D gas, isotropic liquid, and two condensed mesophases, each with a characteristic anchoring of the LC zenithal tilt and azimuth. By varying the monolayer temperature and surface concentration we observe reversible first-order phase transitions from vapor to liquid and from liquid to condensed. A temperature-dependent transition between two condensed phases appears to be a reversible swiveling transition in the tilt azimuth of the monolayer. Similar to monolayers at the air/water interface, the temperature of the gas/liquid/condensed triple-point temperature increased by about 10 degrees C for a two methylene group increase in chain length. However, the absolute value of the triple-point temperatures are depressed by about 40 degrees C compared to those of analogous monolayers at the air/water interface. We also observe a direct influence by the LC layer on the mesoscopic and macroscopic structure of the monolayer by analyzing the shapes and internal textures of gas domains in coexistence with a 2D liquid. An effective anisotropic line tension arises from elastic forces owing to deformation of the nematic director across phase boundaries. This results in the deformation of the domain from circular to elongated, with a distinct singularity. The LC elastic energy also gives rise to transition zones displaying mesoscopic realignment of the director tilt or azimuth between adjacent regions with a sudden change in anchoring.

  17. Modeling the co-transport of viruses and colloids in unsaturated porous media.

    PubMed

    Seetha, N; Mohan Kumar, M S; Majid Hassanizadeh, S

    2015-10-01

    A mathematical model is developed to simulate the co-transport of viruses and colloids in unsaturated porous media under steady-state flow conditions. The virus attachment to the mobile and immobile colloids is described using a linear reversible kinetic model. Colloid transport is assumed to be decoupled from virus transport; that is, we assume that colloids are not affected by the presence of attached viruses on their surface. The governing equations are solved numerically using an alternating three-step operator splitting approach. The model is verified by fitting three sets of experimental data published in the literature: (1) Syngouna and Chrysikopoulos (2013) and (2) Walshe et al. (2010), both on the co-transport of viruses and clay colloids under saturated conditions, and (3) Syngouna and Chrysikopoulos (2015) for the co-transport of viruses and clay colloids under unsaturated conditions. We found a good agreement between observed and fitted breakthrough curves (BTCs) under both saturated and unsaturated conditions. Then, the developed model was used to simulate the co-transport of viruses and colloids in porous media under unsaturated conditions, with the aim of understanding the relative importance of various processes on the co-transport of viruses and colloids in unsaturated porous media. The virus retention in porous media in the presence of colloids is greater during unsaturated conditions as compared to the saturated conditions due to: (1) virus attachment to the air-water interface (AWI), and (2) co-deposition of colloids with attached viruses on its surface to the AWI. A sensitivity analysis of the model to various parameters showed that the virus attachment to AWI is the most sensitive parameter affecting the BTCs of both free viruses and total mobile viruses and has a significant effect on all parts of the BTC. The free and the total mobile viruses BTCs are mainly influenced by parameters describing virus attachment to the AWI, virus interaction

  18. Modeling the co-transport of viruses and colloids in unsaturated porous media.

    PubMed

    Seetha, N; Mohan Kumar, M S; Majid Hassanizadeh, S

    2015-10-01

    A mathematical model is developed to simulate the co-transport of viruses and colloids in unsaturated porous media under steady-state flow conditions. The virus attachment to the mobile and immobile colloids is described using a linear reversible kinetic model. Colloid transport is assumed to be decoupled from virus transport; that is, we assume that colloids are not affected by the presence of attached viruses on their surface. The governing equations are solved numerically using an alternating three-step operator splitting approach. The model is verified by fitting three sets of experimental data published in the literature: (1) Syngouna and Chrysikopoulos (2013) and (2) Walshe et al. (2010), both on the co-transport of viruses and clay colloids under saturated conditions, and (3) Syngouna and Chrysikopoulos (2015) for the co-transport of viruses and clay colloids under unsaturated conditions. We found a good agreement between observed and fitted breakthrough curves (BTCs) under both saturated and unsaturated conditions. Then, the developed model was used to simulate the co-transport of viruses and colloids in porous media under unsaturated conditions, with the aim of understanding the relative importance of various processes on the co-transport of viruses and colloids in unsaturated porous media. The virus retention in porous media in the presence of colloids is greater during unsaturated conditions as compared to the saturated conditions due to: (1) virus attachment to the air-water interface (AWI), and (2) co-deposition of colloids with attached viruses on its surface to the AWI. A sensitivity analysis of the model to various parameters showed that the virus attachment to AWI is the most sensitive parameter affecting the BTCs of both free viruses and total mobile viruses and has a significant effect on all parts of the BTC. The free and the total mobile viruses BTCs are mainly influenced by parameters describing virus attachment to the AWI, virus interaction

  19. The air-water exchange of C{sub 15}-C{sub 31} n-alkanes in a precipitation-dominated seepage lake.

    SciTech Connect

    Doskey, P. V.; Environmental Research

    2000-01-01

    The air-water exchange of semivolatile n-alkanes in Crystal Lake, a small precipitation-dominated seepage lake in northern Wisconsin, was investigated with modeling and mass balance approaches. The results suggest that atmospheric deposition contributes approximately 80% of the allochthonous input of n-alkanes to Crystal Lake. Atmospheric deposition accounts for about 50% of the total annual input of n-alkanes to Crystal Lake, and an additional 30% is contributed by in situ production of planktonic n-alkanes ({Sigma}C{sub 15}, C{sub 17}, C{sub 19}). Contributions to the particle dry flux of terrestrial n-alkanes ({Sigma}C{sub 25}, C{sub 27}, C{sub 29}, C{sub 31}) by pine pollen dispersal and by dry deposition of particles containing leaf waxes are similar in magnitude and constitute about 60% of the atmospheric input, with particle wet deposition being responsible for the remainder. Approximately 30% of the atmospheric input of the n-alkanes occurs during a two-week episode of pine pollen dispersal in spring. Concentration gradients between gaseous n-alkanes in the atmosphere and dissolved n-alkanes in the water column of Crystal Lake favor volatilization of n-alkanes from the lake surface; however, distributions of dissolved n-alkanes are characteristic of bacteria, and therefore are contained in organic matter and not available for air-water exchange. The estimated net atmospheric input of terrestrial n-alkanes is about 20% less than the settling sediment flux. Additional allochthonous sources of the terrestrial n-alkanes might include diffuse surface runoff or episodes of coarse-particle deposition. The discrepancies in the results from the modeling and mass balance approaches indicate that direct measurements of air-water exchange rates and measurements of the seasonal variations of particle size distributions in air and rain would greatly improve our ability to quantify air-water exchange rates of n-alkanes.

  20. Quantitative measurement of size and three-dimensional position of fast-moving bubbles in air-water mixture flows using digital holography.

    PubMed

    Tian, Lei; Loomis, Nick; Domínguez-Caballero, José A; Barbastathis, George

    2010-03-20

    We present a digital in-line holographic imaging system for measuring the size and three-dimensional position of fast-moving bubbles in air-water mixture flows. The captured holograms are numerically processed by performing a two-dimensional projection followed by local depth estimation to quickly and efficiently obtain the size and position information of multiple bubbles simultaneously. Statistical analysis on measured bubble size distributions shows that they follow lognormal or gamma distributions.

  1. A study on the characteristics of upward air-water two-phase flow in a large diameter pipe

    SciTech Connect

    Shen, Xiuzhong; Saito, Yasushi; Mishima, Kaichiro; Nakamura, Hideo

    2006-10-15

    An adiabatic upward co-current air-water two-phase flow in a vertical large diameter pipe (inner diameter, D: 0.2m, ratio of pipe length to diameter, L/D: 60.5) was experimentally investigated under various inlet conditions. Flow regimes were visually observed, carefully analyzed and classified into five, i.e. undisturbed bubbly, agitated bubbly, churn bubbly, churn slug and churn froth. Void fraction, bubble frequency, Sauter mean diameter, interfacial area concentration (IAC) and interfacial direction were measured with four-sensor optical probes. Both the measured void fraction and the measured IAC demonstrated radial core-peak distributions in most of the flow regimes and radial wall peak in the undisturbed bubbly flow only. The bubble frequency also showed a wall-peak radial distribution only when the bubbles were small in diameter and the flow was in the undisturbed bubbly flow. The Sauter mean diameter of bubbles did not change much in the radial direction in undisturbed bubbly, agitated bubbly and churn bubbly flows and showed a core-peak radial distribution in the churn slug flow due to the existence of certain amount of large and deformed bubbles in this flow regime. The measurements of interfacial direction showed that the main and the secondary bubbly flow could be displayed by the main flow peak and the secondary flow peak, respectively, in the probability density function (PDF) of the interfacial directional angle between the interfacial direction and the z-axis, {eta}{sub zi}. The local average {eta}{sub zi }at the bubble front or rear hemisphere ({eta}{sub zi}{sup F} and {eta}{sub zi}{sup R}) reflected the local bubble movement and was in direct connection with the flow regimes. Based on the analysis, the authors classified the flow regimes in the vertical large diameter pipe quantitatively by the cross-sectional area-averaged {eta}{sub zi }at bubbly front hemisphere ({eta}{sub zi}{sup F}-bar). Bubbles in the undisturbed bubbly flow moved in a

  2. Wind variability and sheltering effects on measurements and modeling of air-water exchange for a small lake

    NASA Astrophysics Data System (ADS)

    Markfort, Corey D.; Resseger, Emily; Porté-Agel, Fernando; Stefan, Heinz

    2014-05-01

    Lakes with a surface area of less than 10 km2 account for over 50% of the global cumulative lake surface water area, and make up more than 99% of the total number of global lakes, ponds, and wetlands. Within the boreal regions as well as some temperate and tropical areas, a significant proportion of land cover is characterized by lakes or wetlands, which can have a dramatic effect on land-atmosphere fluxes as well as the local and regional energy budget. Many of these small water bodies are surrounded by complex terrain and forest, which cause the wind blowing over a small lake or wetland to be highly variable. Wind mixing of the lake surface layer affects thermal stratification, surface temperature and air-water gas transfer, e.g. O2, CO2, and CH4. As the wind blows from the land to the lake, wake turbulence behind trees and other shoreline obstacles leads to a recirculation zone and enhanced turbulence. This wake flow results in the delay of the development of wind shear stress on the lake surface, and the fetch required for surface shear stress to fully develop may be ~O(1 km). Interpretation of wind measurements made on the lake is hampered by the unknown effect of wake turbulence. We present field measurements designed to quantify wind variability over a sheltered lake. The wind data and water column temperature profiles are used to evaluate a new method to quantify wind sheltering of lakes that takes into account lake size, shape and the surrounding landscape features. The model is validated against field data for 36 Minnesota lakes. Effects of non-uniform sheltering and lake shape are also demonstrated. The effects of wind sheltering must be included in lake models to determine the effect of wind-derived energy inputs on lake stratification, surface gas transfer, lake water quality, and fish habitat. These effects are also important for correctly modeling momentum, heat, moisture and trace gas flux to the atmosphere.

  3. Monovalent counterion distributions at highly charged water interfaces: Proton-transfer and Poisson-Boltzmann theory

    SciTech Connect

    Bu, W.; Vaknin, D.; Travesset, A.

    2010-07-13

    Surface sensitive synchrotron-x-ray scattering studies reveal the distributions of monovalent ions next to highly charged interfaces. A lipid phosphate (dihexadecyl hydrogen phosphate) was spread as a monolayer at the air-water interface, containing CsI at various concentrations. Using anomalous reflectivity off and at the L{sub 3} Cs{sup +} resonance, we provide spatial counterion distributions (Cs{sup +}) next to the negatively charged interface over a wide range of ionic concentrations. We argue that at low salt concentrations and for pure water the enhanced concentration of hydroniums H{sub 3}O{sup +} at the interface leads to proton transfer back to the phosphate group by a high contact potential, whereas high salt concentrations lower the contact potential resulting in proton release and increased surface charge density. The experimental ionic distributions are in excellent agreement with a renormalized-surface-charge Poisson-Boltzmann theory without fitting parameters or additional assumptions.

  4. Simulation and theory of ions at atmospherically relevant aqueous liquid-air interfaces.

    PubMed

    Tobias, Douglas J; Stern, Abraham C; Baer, Marcel D; Levin, Yan; Mundy, Christopher J

    2013-01-01

    Chemistry occurring at or near the surface of aqueous droplets and thin films in the atmosphere influences air quality and climate. Molecular dynamics simulations are becoming increasingly useful for gaining atomic-scale insight into the structure and reactivity of aqueous interfaces in the atmosphere. Here we review simulation studies of atmospherically relevant aqueous liquid-air interfaces, with an emphasis on ions that play important roles in the chemistry of atmospheric aerosols. In addition to surveying results from simulation studies, we discuss challenges to the refinement and experimental validation of the methodology for simulating ion adsorption to the air-water interface and recent advances in elucidating the driving forces for adsorption. We also review the recent development of a dielectric continuum theory capable of reproducing simulation and experimental data on ion behavior at aqueous interfaces.

  5. On NO3-H2O interactions in aqueous solutions and at interfaces

    SciTech Connect

    Dang, Liem X.; Chang, Tsun-Mei; Roeselova, Martina; Garrett, Bruce C.; Tobias, Douglas J.

    2006-02-14

    Constrained molecular dynamics technique was employed to investigate the transport of a nitrate ion across the water liquid/vapor interface. We developed the nitrate ion-water polarizable potential capable of describing well the solvation properties of the hydrated nitrate ion. The computed free energy profile for the transfer of the nitrate ion across the air/water interface increases monotonically as the nitrate ion approaches the Gibbs dividing surface from the bulk liquid side. The computed density profiles of 1M KNO3 salt solution slab indicate that the nitrate and potassium ions are both found below the aqueous interface. Upon analyzing the results, we can conclude that the probability of finding the nitrate anion at the aqueous interface is quite small.

  6. Infrared reflectance spectroscopy as a characterization probe for polymer surfaces and interfaces

    NASA Astrophysics Data System (ADS)

    Riou, Sophie Annick

    1998-12-01

    Only recently has external reflectance infrared spectroscopy been used to acquire structural information at the molecular level at air-liquid interfaces, and particularly to characterize in situ molecular chains adsorbed at the air-water interface. This technique has been applied for the determination of chain orientation, chain conformation and packing density of small molecules such as phospholipids, fatty acids and fatty alcohols on the surface of water, and more recently of macromolecular systems. Vibrational spectroscopy, a nondestructive technique, is especially successful in the determination of the conformational order or disorder of alkyl chains (e.g. trans/gauche ratio) as well as in the evaluation of coil, helical or extended conformations in poly(amino acids). In this thesis work, the construction of a microcomputer controlled Langmuir trough optically coupled to a FT-IR instrument has allowed the direct investigation of molecular films spread at air-liquid interfaces. Order-disorder transitions and relaxation behaviors in vinyl comb-like polymeric Langmuir films have been examined using simultaneously external reflection infrared spectroscopy and surface tensiometry. The structures of several poly(amino acid) films have also been studied as a function of surface packing density at the air-water interface.

  7. Manipulating perfume delivery to the interface using polymer-surfactant interactions.

    PubMed

    Bradbury, Robert; Penfold, Jeffrey; Thomas, Robert K; Tucker, Ian M; Petkov, Jordan T; Jones, Craig

    2016-03-15

    Enhanced delivery of perfumes to interfaces is an important element of their effectiveness in a range of home and personal care products. The role of polyelectrolyte-surfactant mixtures to promote perfume adsorption at interfaces is explored here. Neutron reflectivity, NR, was used to quantify the adsorption of the model perfumes phenylethanol, PE, and linalool, LL, at the air-water interface in the presence of the anionic surfactant sodium dodecylsulfate, SDS, and the cationic polyelectrolytes, poly(dimethyldiallyl ammonium chloride), polydmdaac, and poly(ethyleneimine), PEI. The strong SDS-polydmdaac interaction dominates the surface adsorption in SDS-polymer-perfume (PE, LL) mixtures, such that the PE and LL adsorption is greatly suppressed. For PEI-SDS-perfume mixtures the PEI-LL interaction competes with the SDS-PEI interaction at all pH at the surface and significant LL adsorption occurs, whereas for PE the PEI-SDS interaction dominates and the PE adsorption is greatly reduced. The use of the strong surface polyelectrolyte-ionic surfactant interaction to manipulate perfume adsorption at the air-water interface has been demonstrated. In particular the results show how the competition between polyelectrolyte, surfactant and perfume interactions at the surface and in solution affect the partitioning of perfumes to the surface.

  8. Manipulating perfume delivery to the interface using polymer-surfactant interactions.

    PubMed

    Bradbury, Robert; Penfold, Jeffrey; Thomas, Robert K; Tucker, Ian M; Petkov, Jordan T; Jones, Craig

    2016-03-15

    Enhanced delivery of perfumes to interfaces is an important element of their effectiveness in a range of home and personal care products. The role of polyelectrolyte-surfactant mixtures to promote perfume adsorption at interfaces is explored here. Neutron reflectivity, NR, was used to quantify the adsorption of the model perfumes phenylethanol, PE, and linalool, LL, at the air-water interface in the presence of the anionic surfactant sodium dodecylsulfate, SDS, and the cationic polyelectrolytes, poly(dimethyldiallyl ammonium chloride), polydmdaac, and poly(ethyleneimine), PEI. The strong SDS-polydmdaac interaction dominates the surface adsorption in SDS-polymer-perfume (PE, LL) mixtures, such that the PE and LL adsorption is greatly suppressed. For PEI-SDS-perfume mixtures the PEI-LL interaction competes with the SDS-PEI interaction at all pH at the surface and significant LL adsorption occurs, whereas for PE the PEI-SDS interaction dominates and the PE adsorption is greatly reduced. The use of the strong surface polyelectrolyte-ionic surfactant interaction to manipulate perfume adsorption at the air-water interface has been demonstrated. In particular the results show how the competition between polyelectrolyte, surfactant and perfume interactions at the surface and in solution affect the partitioning of perfumes to the surface. PMID:26724705

  9. Adsorption energies of poly(ethylene oxide)-based surfactants and nanoparticles on an air-water surface.

    PubMed

    Zell, Zachary A; Isa, Lucio; Ilg, Patrick; Leal, L Gary; Squires, Todd M

    2014-01-14

    The self-assembly of polymer-based surfactants and nanoparticles on fluid-fluid interfaces is central to many applications, including dispersion stabilization, creation of novel 2D materials, and surface patterning. Very often these processes involve compressing interfacial monolayers of particles or polymers to obtain a desired material microstructure. At high surface pressures, however, even highly interfacially active objects can desorb from the interface. Methods of directly measuring the energy which keeps the polymer or particles bound to the interface (adsorption/desorption energies) are therefore of high interest for these processes. Moreover, though a geometric description linking adsorption energy and wetting properties through the definition of a contact angle can be established for rigid nano- or microparticles, such a description breaks down for deformable or aggregating objects. Here, we demonstrate a technique to quantify desorption energies directly, by comparing surface pressure-density compression measurements using a Wilhelmy plate and a custom-microfabricated deflection tensiometer. We focus on poly(ethylene oxide)-based polymers and nanoparticles. For PEO-based homo- and copolymers, the adsorption energy of PEO chains scales linearly with molecular weight and can be tuned by changing the subphase composition. Moreover, the desorption surface pressure of PEO-stabilized nanoparticles corresponds to the saturation surface pressure for spontaneously adsorbed monolayers, yielding trapping energies of ∼10(3) k(B)T. PMID:24328531

  10. Molecular Modeling of Water Interfaces: From Molecular Spectroscopy to Thermodynamics.

    PubMed

    Nagata, Yuki; Ohto, Tatsuhiko; Backus, Ellen H G; Bonn, Mischa

    2016-04-28

    Understanding aqueous interfaces at the molecular level is not only fundamentally important, but also highly relevant for a variety of disciplines. For instance, electrode-water interfaces are relevant for electrochemistry, as are mineral-water interfaces for geochemistry and air-water interfaces for environmental chemistry; water-lipid interfaces constitute the boundaries of the cell membrane, and are thus relevant for biochemistry. One of the major challenges in these fields is to link macroscopic properties such as interfacial reactivity, solubility, and permeability as well as macroscopic thermodynamic and spectroscopic observables to the structure, structural changes, and dynamics of molecules at these interfaces. Simulations, by themselves, or in conjunction with appropriate experiments, can provide such molecular-level insights into aqueous interfaces. In this contribution, we review the current state-of-the-art of three levels of molecular dynamics (MD) simulation: ab initio, force field, and coarse-grained. We discuss the advantages, the potential, and the limitations of each approach for studying aqueous interfaces, by assessing computations of the sum-frequency generation spectra and surface tension. The comparison of experimental and simulation data provides information on the challenges of future MD simulations, such as improving the force field models and the van der Waals corrections in ab initio MD simulations. Once good agreement between experimental observables and simulation can be established, the simulation can be used to provide insights into the processes at a level of detail that is generally inaccessible to experiments. As an example we discuss the mechanism of the evaporation of water. We finish by presenting an outlook outlining four future challenges for molecular dynamics simulations of aqueous interfacial systems. PMID:27010817

  11. Correlation of Oil-Water and Air-Water Contact Angles of Diverse Silanized Surfaces and Relationship to Fluid Interfacial Tensions

    SciTech Connect

    Grate, Jay W.; Dehoff, Karl J.; Warner, Marvin G.; Pittman, Jonathan W.; Wietsma, Thomas W.; Zhang, Changyong; Oostrom, Martinus

    2012-02-24

    The use of air-water, {Theta}{sub wa}, or air-liquid contact angles is customary in surface science, while oil-water contact angles {Theta}{sub ow}, are of paramount importance in subsurface multiphase flow phenomena including petroleum reocovery, nonaqueous phase liquid fate and transport, and geological carbon sequestration. In this paper we determine both the air-water and oil-water contact angles of silica surfaces modified with a diverse selection of silanes, using hexadecane as the oil. The silanes included alkylsilanes, alkylarylsilanes, and silanes with alkyl or aryl groups that are functionalized with heteroatoms such as N, O, and S. These silanes yielded surfaces with wettabilities from water-wet to oil wet, including specific silanized surfaces functionalized with heteroatoms that yield intermediate wet surfaces. The oil-water contact angles for clean and silanized surfaces, excluding one partially fluorinated surface, correlate linearly with air-water contact angles with a slope of 1.41 (R = 0.981, n = 13). These data were used to examine a previously untested theoretical treatment relating air-water and oil-water contact angles in terms of fluid interfacial energies. Plotting the cosines of these contact angles against one another, we obtain a linear relationship in excellent agreement with the theoretical treatment; the data fit cos {Theta}{sub ow} = 0.667 cos {Theta}{sub ow} + 0.384 (R = 0.981, n = 13), intercepting cos {Theta}{sub ow} = -1 at -0.284. The theoretical slope, based on the fluid interfacial tensions {Theta}{sub wa}, {Theta}{sub ow}, and {Theta}{sub oa}, is 0.67. We also demonstrate how silanes can be used to alter the wettability of the interior of a pore network micromodel device constructed in silicon/silica with a glass cover plate. Such micromodels are used to study multiphase flow phenomena. The contact angle of the resulting interior was determined in situ. An intermediate wet micromodel gave a contact angle in excellent agreement

  12. Media independent interface. Interface control document

    NASA Technical Reports Server (NTRS)

    1987-01-01

    A Media Independent Interface (MII) is specified, using current standards in the industry. The MII is described in hierarchical fashion. At the base are IEEE/International Standards Organization (ISO) documents (standards) which describe the functionality of the software modules or layers and their interconnection. These documents describe primitives which are to transcent the MII. The intent of the MII is to provide a universal interface to one or more Media Access Contols (MACs) for the Logical Link Controller and Station Manager. This interface includes both a standardized electrical and mechanical interface and a standardized functional specification which defines the services expected from the MAC.

  13. Insect flight on fluid interfaces: a chaotic interfacial oscillator

    NASA Astrophysics Data System (ADS)

    Mukundarajan, Haripriya; Prakash, Manu

    2013-11-01

    Flight is critical to the dominance of insect species on our planet, with about 98 percent of insect species having wings. How complex flight control systems developed in insects is unknown, and arboreal or aquatic origins have been hypothesized. We examine the biomechanics of aquatic origins of flight. We recently reported discovery of a novel mode of ``2D flight'' in Galerucella beetles, which skim along an air-water interface using flapping wing flight. This unique flight mode is characterized by a balance between capillary forces from the interface and biomechanical forces exerted by the flapping wings. Complex interactions on the fluid interface form capillary wave trains behind the insect, and produce vertical oscillations at the surface due to non-linear forces arising from deformation of the fluid meniscus. We present both experimental observations of 2D flight kinematics and a dynamic model explaining the observed phenomena. Careful examination of this interaction predicts the chaotic nature of interfacial flight and takeoff from the interface into airborne flight. The role of wingbeat frequency, stroke plane angle and body angle in determining transition between interfacial and fully airborne flight is highlighted, shedding light on the aquatic theory of flight evolution.

  14. Immersed interface methods for moving interface problems

    NASA Astrophysics Data System (ADS)

    Li, Zhilin

    1997-05-01

    A second order difference method is developed for the nonlinear moving interface problem of the form u_t + λ uu_x = ( {β u_x } )_x - f( {x,t} ),x in [ {0,α } ) \\cup ( {α ,1} ]} }. {d}{α}/{dt} = w( {t,α ;u,u_x } ), , where α (t) is the moving interface. The coefficient β(x,t) and the source term f(x,t) can be discontinuous across α (t) and moreover, f(x,t) may have a delta or/and delta-prime function singularity there. As a result, although the equation is parabolic, the solution u and its derivatives may be discontinuous across α (t). Two typical interface conditions are considered. One condition occurs in Stefan-like problems in which the solution is known on the interface. A new stable interpolation strategy is proposed. The other type occurs in a one-dimensional model of Peskin's immersed boundary method in which only jump conditions are given across the interface. The Crank-Nicolson difference scheme with modifications near the interface is used to solve for the solution u(x,t) and the interface α (t) simultaneously. Several numerical examples, including models of ice-melting and glaciation, are presented. Second order accuracy on uniform grids is confirmed both for the solution and the position of the interface.

  15. Current status of persistent organic pesticides residues in air, water, and soil, and their possible effect on neighboring countries: a comprehensive review of India.

    PubMed

    Yadav, Ishwar Chandra; Devi, Ningombam Linthoingambi; Syed, Jabir Hussain; Cheng, Zhineng; Li, Jun; Zhang, Gan; Jones, Kevin C

    2015-04-01

    Though the use of pesticides has offered significant economic benefits by enhancing the production and yield of food and fibers and the prevention of vector-borne diseases, evidence suggests that their use has adversely affected the health of human populations and the environment. Pesticides have been widely distributed and their traces can be detected in all areas of the environment (air, water and soil). Despite the ban of DDT and HCH in India, they are still in use, both in domestic and agricultural settings. In this comprehensive review, we discuss the production and consumption of persistent organic pesticides, their maximum residual limit (MRL) and the presence of persistent organic pesticides in multicomponent environmental samples (air, water and soil) from India. In order to highlight the global distribution of persistent organic pesticides and their impact on neighboring countries and regions, the role of persistent organic pesticides in Indian region is reviewed. Based on a review of research papers and modeling simulations, it can be concluded that India is one of the major contributors of global persistent organic pesticide distribution. This review also considers the health impacts of persistent organic pesticides, the regulatory measures for persistent organic pesticides, and the status of India's commitment towards the elimination of persistent organic pesticides.

  16. Naturally occurring spore particles at planar fluid interfaces and in emulsions.

    PubMed

    Binks, B P; Clint, J H; Mackenzie, G; Simcock, C; Whitby, C P

    2005-08-30

    We have investigated the potential of utilizing naturally occurring spore particles of Lycopodium clavatum as sole emulsifiers of oil and water mixtures. The preferred emulsions, prepared from either oil-borne or aqueous-borne dispersions of the monodispersed particles of diameter 30 microm, are oil-in-water. The particles act as efficient stabilizers for oils of different polarity. Droplets as large as several millimeters are stable to coalescence indefinitely, despite the low coverage of interfaces by particles observed microscopically. Consistent with the emulsion findings, we discover that particles spontaneously adsorb to bare oil-water interfaces of single drops from oil dispersions, whereas adsorption is less spontaneous and extensive from aqueous dispersions. Monolayers of the spore particles at both air-water and oil-water planar interfaces contain particles in an aggregated state forming clusters and chains. The influence of particle concentration, oil/water ratio, and additives in the aqueous phase is studied.

  17. Enhanced perfume surface delivery to interfaces using surfactant surface multilayer structures.

    PubMed

    Brabury, Robert; Penfold, Jeffrey; Thomas, Robert K; Tucker, Ian M; Petkov, Jordan T; Jones, Craig

    2016-01-01

    Enhanced surface delivery and retention of perfumes at interfaces are the keys to their more effective and efficient deployment in a wide range of home and personal care related formulations. It has been previously demonstrated that the addition of multivalent counterions, notably Ca(2+), induces multilayer adsorption at the air-water interface for the anionic surfactant, sodium dodecyl-6-benzenesulfonate, LAS-6. Neutron reflectivity, NR, measurements are reported here which demonstrate that such surfactant surface multilayer structures are a potentially promising vehicle for enhanced delivery of perfumes to interfaces. The data show that the incorporation of the model perfumes, phenylethanol, PE, and linalool, LL, into the surface multilayer structure formed by LAS-6/Ca(2+) results in the surface structures being retained up to relatively high perfume mole fractions. Furthermore the amount of perfume at the surface is enhanced by at least an order of magnitude, compared to that co-adsorbed with a surfactant monolayer.

  18. Enhanced perfume surface delivery to interfaces using surfactant surface multilayer structures.

    PubMed

    Brabury, Robert; Penfold, Jeffrey; Thomas, Robert K; Tucker, Ian M; Petkov, Jordan T; Jones, Craig

    2016-01-01

    Enhanced surface delivery and retention of perfumes at interfaces are the keys to their more effective and efficient deployment in a wide range of home and personal care related formulations. It has been previously demonstrated that the addition of multivalent counterions, notably Ca(2+), induces multilayer adsorption at the air-water interface for the anionic surfactant, sodium dodecyl-6-benzenesulfonate, LAS-6. Neutron reflectivity, NR, measurements are reported here which demonstrate that such surfactant surface multilayer structures are a potentially promising vehicle for enhanced delivery of perfumes to interfaces. The data show that the incorporation of the model perfumes, phenylethanol, PE, and linalool, LL, into the surface multilayer structure formed by LAS-6/Ca(2+) results in the surface structures being retained up to relatively high perfume mole fractions. Furthermore the amount of perfume at the surface is enhanced by at least an order of magnitude, compared to that co-adsorbed with a surfactant monolayer. PMID:26409782

  19. Charged Diblock Copolymers at Interfaces: Micelle Dissociation Upon Compression

    SciTech Connect

    Checco, A.; Theodoly, O.; Muller, P.

    2010-05-20

    We use grazing incidence X-ray scattering to study the surface micellization of charged amphiphilic diblock copolymers poly(styrene-block-acrylic acid) at the air-water interface. Scattering interference peaks are consistent with the formation of hexagonally packed micelles. The remarkable increase of inter-micelle distance upon compression is explained by a dissociation of micelles into a brush. Hence, surface micelles reorganize, whereas micelles of the same copolymers in solutions are 'frozen'. We show indeed that the energetic cost of unimer extraction from micelles is much lower for surface than for solution. Finally, a model combining electrostatic interactions and micelle/brush equilibrium explains surface pressure vs. area without free parameters. keywords - soft matter, liquids and polymers, biological physics, chemical physics and physical chemistry.

  20. Charged Diblock Copolymers at Interfaces: Micelle Dissociation Upon Compression

    SciTech Connect

    Theodoly, O.; Checco, A; Muller, P

    2010-01-01

    We use grazing incidence X-ray scattering to study the surface micellization of charged amphiphilic diblock copolymers poly(styrene-block-acrylic acid) at the air-water interface. Scattering interference peaks are consistent with the formation of hexagonally packed micelles. The remarkable increase of inter-micelle distance upon compression is explained by a dissociation of micelles into a brush. Hence, surface micelles reorganize, whereas micelles of the same copolymers in solutions are 'frozen'. We show indeed that the energetic cost of unimer extraction from micelles is much lower for surface than for solution. Finally, a model combining electrostatic interactions and micelle/brush equilibrium explains surface pressure vs. area without free parameters.

  1. Alignment and Sensitive Detection of DNA by a Moving Interface

    NASA Astrophysics Data System (ADS)

    Bensimon, A.; Simon, A.; Chiffaudel, A.; Croquette, V.; Heslot, F.; Bensimon, D.

    1994-09-01

    In a process called "molecular combing," DNA molecules attached at one end to a solid surface were extended and aligned by a receding air-water interface and left to dry on the surface. Molecular combing was observed to extend the length of the bacteriophage λ DNA molecule to 21.5 ± 0.5 micrometers (unextended length, 16.2 micrometers). With the combing process, it was possible to (i) extend a chromosomal Escherichia coli DNA fragment (10^6 base pairs) and (ii) detect a minute quantity of DNA (10^3 molecules). These results open the way for a faster physical mapping of the genome and for the detection of small quantities of target DNA from a population of molecules.

  2. Media independent interface

    NASA Technical Reports Server (NTRS)

    1987-01-01

    The work done on the Media Independent Interface (MII) Interface Control Document (ICD) program is described and recommendations based on it were made. Explanations and rationale for the content of the ICD itself are presented.

  3. Water at Interfaces.

    PubMed

    Björneholm, Olle; Hansen, Martin H; Hodgson, Andrew; Liu, Li-Min; Limmer, David T; Michaelides, Angelos; Pedevilla, Philipp; Rossmeisl, Jan; Shen, Huaze; Tocci, Gabriele; Tyrode, Eric; Walz, Marie-Madeleine; Werner, Josephina; Bluhm, Hendrik

    2016-07-13

    The interfaces of neat water and aqueous solutions play a prominent role in many technological processes and in the environment. Examples of aqueous interfaces are ultrathin water films that cover most hydrophilic surfaces under ambient relative humidities, the liquid/solid interface which drives many electrochemical reactions, and the liquid/vapor interface, which governs the uptake and release of trace gases by the oceans and cloud droplets. In this article we review some of the recent experimental and theoretical advances in our knowledge of the properties of aqueous interfaces and discuss open questions and gaps in our understanding. PMID:27232062

  4. Micro bubbles at interfaces

    NASA Astrophysics Data System (ADS)

    Keshavarzi, Gholamreza; Wang, Anna; Barber, Tracie; Manoharan, Vinothan

    2014-03-01

    The behaviour of a small micron sized bubbles close to an interface is vital to various interface interaction applications in several industries. Previous studies have focused on understanding the behaviour of large millimetric bubbles reaching an interface. Some of these millimetric bubbles are shown to bounce back, while others penetrate and burst on the interface resulting in possible small micron sized bubbles. However, small micron sized bubble may act different. It has been observed that small microbubbles can act as if they are stabilized at the interface without merging to the fluid over the interface. The dynamics of the microbubble adsorption close to an interface has yet to be well understood.In this study we used digital holography microscopy to explore detailed information on the behaviour of the air microbubble at the interface. This study investigates the position and shape of a microbubble with respect to the interface. The dynamic behavior close to the interface along with where the small microbubble is positioned near an interface will help us in understanding the probability of penetration and merging back to the fluid on top.

  5. Mechanically Enhanced Liquid Interfaces at Human Body Temperature Using Thermosensitive Methylated Nanocrystalline Cellulose.

    PubMed

    Scheuble, N; Geue, T; Kuster, S; Adamcik, J; Mezzenga, R; Windhab, E J; Fischer, P

    2016-02-01

    The mechanical performance of materials at oil/water interfaces after consumption is a key factor affecting hydrophobic drug release. In this study, we methylated the surface of nanocrystalline cellulose (NCC) by mercerization and dimethyl sulfate exposure to produce thermosensitive biopolymers. These methylated NCC (metNCC) were used to investigate interfacial thermogelation at air/water and medium-chain triglyceride (MCT)/water interfaces at body temperature. In contrast to bulk fluid dynamics, elastic layers were formed at room temperature, and elasticity increased significantly at body temperature, which was measured by interfacial shear and dilatational rheology in situ. This unique phenomenon depends on solvent quality, temperature, and polymer concentration at interfaces. Thus, by adjusting the degree of hydrophobicity of metNCC, the interfacial elasticity and thermogelation of the interfaces could be varied. In general, these new materials (metNCC) formed more brittle interfacial layers compared to commercial methylcellulose (MC A15). Thermogelation of methylcellulose promotes attractive intermolecular forces, which were reflected in a change in self-assembly of metNCC at the interface. As a consequence, layer thickness and density increased as a function of temperature. These effects were measured by atomic force microscopy (AFM) images of the displaced interface and confirmed by neutron reflection. The substantial structural and mechanical change of methylcellulose interfaces at body temperature represents a controllable encapsulation parameter allowing optimization of lipid-based drug formulations.

  6. Mechanically Enhanced Liquid Interfaces at Human Body Temperature Using Thermosensitive Methylated Nanocrystalline Cellulose.

    PubMed

    Scheuble, N; Geue, T; Kuster, S; Adamcik, J; Mezzenga, R; Windhab, E J; Fischer, P

    2016-02-01

    The mechanical performance of materials at oil/water interfaces after consumption is a key factor affecting hydrophobic drug release. In this study, we methylated the surface of nanocrystalline cellulose (NCC) by mercerization and dimethyl sulfate exposure to produce thermosensitive biopolymers. These methylated NCC (metNCC) were used to investigate interfacial thermogelation at air/water and medium-chain triglyceride (MCT)/water interfaces at body temperature. In contrast to bulk fluid dynamics, elastic layers were formed at room temperature, and elasticity increased significantly at body temperature, which was measured by interfacial shear and dilatational rheology in situ. This unique phenomenon depends on solvent quality, temperature, and polymer concentration at interfaces. Thus, by adjusting the degree of hydrophobicity of metNCC, the interfacial elasticity and thermogelation of the interfaces could be varied. In general, these new materials (metNCC) formed more brittle interfacial layers compared to commercial methylcellulose (MC A15). Thermogelation of methylcellulose promotes attractive intermolecular forces, which were reflected in a change in self-assembly of metNCC at the interface. As a consequence, layer thickness and density increased as a function of temperature. These effects were measured by atomic force microscopy (AFM) images of the displaced interface and confirmed by neutron reflection. The substantial structural and mechanical change of methylcellulose interfaces at body temperature represents a controllable encapsulation parameter allowing optimization of lipid-based drug formulations. PMID:26779953

  7. Sum-Frequency Generation from Chiral Media and Interfaces

    SciTech Connect

    Ji, Na

    2006-02-13

    Sum frequency generation (SFG), a second-order nonlinear optical process, is electric-dipole forbidden in systems with inversion symmetry. As a result, it has been used to study chiral media and interfaces, systems intrinsically lacking inversion symmetry. This thesis describes recent progresses in the applications of and new insights into SFG from chiral media and interfaces. SFG from solutions of chiral amino acids is investigated, and a theoretical model explaining the origin and the strength of the chiral signal in electronic-resonance SFG spectroscopy is discussed. An interference scheme that allows us to distinguish enantiomers by measuring both the magnitude and the phase of the chiral SFG response is described, as well as a chiral SFG microscope producing chirality-sensitive images with sub-micron resolution. Exploiting atomic and molecular parity nonconservation, the SFG process is also used to solve the Ozma problems. Sum frequency vibrational spectroscopy is used to obtain the adsorption behavior of leucine molecules at air-water interfaces. With poly(tetrafluoroethylene) as a model system, we extend the application of this surface-sensitive vibrational spectroscopy to fluorine-containing polymers.

  8. Two-photon excitation of surface plasmon and the period-increasing effect of low spatial frequency ripples on a GaP crystal in air/water

    NASA Astrophysics Data System (ADS)

    Liu, Jukun; Jia, Tianqing; Zhao, Hongwei; Huang, Yaoqing

    2016-11-01

    We report the period-increasing effect of low spatial frequency ripples on a GaP crystal irradiated by 1 kHz, 50 fs, 800 nm femtosecond laser pulses. Massive free electrons are excited by a two-photon absorption process and surface plasmon is excited. The Drude model is used to estimate the changing of the dielectric constant of the GaP crystal. The period-increasing effects of low spatial frequency laser-induced ripples are theoretically predicted in air/water, and the experimental results agree well. The experimental and theoretical results indicate that surface plasmon excited by two-photon absorption plays a key role in the formation of low spatial frequency ripples.

  9. Molecular dynamics simulations of SDS, DTAB, and C12E8 monolayers adsorbed at the air/water surface in the presence of DSEP.

    PubMed

    Pang, Jinyu; Wang, Yajing; Xu, Guiying; Han, Tingting; Lv, Xin; Zhang, Jian

    2011-03-24

    The properties of adsorbed monolayers of three hydrocarbon surfactants with the same hydrophobic tail, sodium dodecyl sulfate (SDS), dodecyltrimethylammonium bromide (DTAB) and octaethylene glycol dodecyl ether (C(12)E(8)) at the air/water surface in the absence and presence of a dimethylsiloxane ethoxylate-propoxylate (DSEP) were studied via molecular dynamics simulations to compare the effect of the headgroups on the aggregation behaviors of surfactant mixtures. The structures and dynamical properties of the monolayers were greatly affected after adding DSEP. In the presence of DSEP, SDS monolayer was better ordered and more compact, whereas C(12)E(8) monolayer was relatively disordered. Some DTAB molecules immerged into water, and the others adsorbed at the surface were in less compact but well-ordered arrangement. The reason for the appearance of different types of monolayers was also discussed, with the goal of providing a theoretical approach for their further applications.

  10. Measurement of Air-Water Interfacial Areas in Unsaturated Water-Wet Sandy Porous Media Using Synchrotron X-ray Microtomography

    NASA Astrophysics Data System (ADS)

    Costanza-Robinson, M. S.; Harrold, K. H.; Brusseau, M. L.; Lieb-Lappen, R. M.

    2006-12-01

    Air-water interfacial area (Aia) is a critical parameter in porous media systems that influences equilibrium fluid and contaminant distributions, as well as mass- and energy-transfer kinetics. Despite its importance, methods for quantitative measurement of Aia are not well developed. In this work, innovative synchrotron X-ray microtomography methods were used to measure Aia for a variety of unsaturated water-wet natural silica sands and glass spheres as a function of water saturation (Sw). Individual capillary and smooth-film contributions to Aia were determined for a subset of these media using X-ray absorption edge-difference imaging techniques. Aia values were observed to decrease linearly for all porous media with increasing Sw. A linear relationship was also observed between maximum Aia values, obtained by linear extrapolation to zero water saturation, and smooth-sphere-approximated surface areas for glass spheres (r2 = 0.99) and natural silica sands (r2=0.76). The weaker correlation for natural media is likely due to grain shape variation among the sands and greater uncertainty associated with areas extracted from the more complex natural-sand images. Total measured Aia was further differentiated into individual capillary and smooth-film contributions for select media, indicating that films contribute the majority of air-water interfacial areas measured by this technique. Because the relevance of individual interfacial domains differs widely for various contaminant and remediation scenarios, the ability to experimentally distinguish these domains using X-ray microtomography represents an important advance.

  11. In situ air-water and particle-water partitioning of perfluorocarboxylic acids, perfluorosulfonic acids and perfluorooctyl sulfonamide at a wastewater treatment plant.

    PubMed

    Vierke, Lena; Ahrens, Lutz; Shoeib, Mahiba; Palm, Wolf-Ulrich; Webster, Eva M; Ellis, David A; Ebinghaus, Ralf; Harner, Tom

    2013-08-01

    In situ measurements of air and water phases at a wastewater treatment plant (WWTP) were used to investigate the partitioning behavior of perfluorocarboxylic acids (PFCAs), perfluorosulfonic acids (PFSAs) and perfluorooctyl sulfonamide (HFOSA) and their conjugate bases (PFC(-)s, PFS(-)s, and FOSA(-), respectively). Particle-dissolved (Rd) and air-water (QAW) concentration ratios were determined at different tanks of a WWTP. Sum of concentrations of C4-12,14 PFC(A)s, C4,6,8,10 PFS(A)s and (H)FOSA were as high as 50 pg m(-3) (atmospheric gas phase), 2300 ng L(-1) (aqueous dissolved phase) and 2500 ng L(-1) (aqueous particle phase). Particle-dissolved concentration ratios of total species, log Rd, ranged from -2.9 to 1.3 for PFS(A)s, from -1.9 to 1.1 for PFC(A)s and was 0.71 for (H)FOSA. These field-based values agree well with equilibrium partitioning data reported in the literature, suggesting that any in situ generation from precursors, if they are present in this system, occurs at a slower rate than the rate of approach to equilibrium. Acid QAW were also estimated. Good agreement between the QAW and the air-water equilibrium partition coefficient for C8PFCA suggests that the air above the WWTP tanks is at or near equilibrium with the water. Uncertainties in these QAW values are attributed mainly to variability in pKa values reported in the literature. The WWTP provides a unique environment for investigating environmental fate processes of the PFCAs and PFSAs under 'real' conditions in order to better understand and predict their fate in the environment.

  12. Microconical interface fitting and interface grasping tool

    NASA Technical Reports Server (NTRS)

    Gernhardt, Michael L. (Inventor); Wightman, William D. (Inventor); Johnston, Alistair P. (Inventor)

    1994-01-01

    A small and light weight microconical interface fitting may be attached to the surface of a space vehicle or equipment to provide an attachment device for an astronaut or robot to capture the space vehicle or equipment. The microconical interface fitting of the present invention has an axisymmetrical conical body having a base portion with a torque reaction surface for preventing rotation of the interface grasping tool; a cavitated, sunken or hollowed out intermediate locking portion which has a cavity shaped for receiving the latches of the grasping tool and an upper guiding portion for guiding the grasping tool into axial alignment with the microconical interface fitting. The capture is accomplished with an interface grasping tool. The grasping tool comprises an outer sleeve with a handle attached, an inner sleeve which may be raised and lowered within the outer sleeve with a plurality of latches supported at the lower end and a cam to raise and lower the inner sleeve. When the inner sleeve is at its lowest position, the latches form the largest diameter opening for surrounding the microconical fitting and the latches form the smallest diameter or a locking, grasping position when raised to the highest position within the outer sleeve. The inner sleeve may be at an intermediate, capture position which permits the latches to be biased outwardly when contacting the microconical fitting under very low forces to grasp the fitting and permits capture (soft docking) without exact alignment of the fitting and the tool.

  13. Popeye Project: ROV interface

    SciTech Connect

    Scates, C.R.; Hernandez, D.A.; Hickok, D.D.

    1996-12-31

    This paper discusses the Remote Operated Vehicle (ROV) interface with the Popeye Project Subsea System. It describes the ROV-related plans, design philosophies, intervention tasks, tooling/equipment requirements, testing activities, and offshore installation experiences. Early identification and continuous consideration of the ROV interfaces significantly improved the overall efficiency of equipment designs and offshore operations. The Popeye Project helped advance the technology and standardization of ROV interfaces for deep water subsea production systems.

  14. Turbomachine Interface Sealing

    NASA Technical Reports Server (NTRS)

    Hendricks, Robert C.; Chupp, Raymond E.; Lattime, Scott B.; Steinetz, Bruce M.

    2005-01-01

    Sealing interfaces and coatings, like lubricants, are sacrificial, giving up their integrity for the benefit of the component. Clearance control is a major issue in power systems turbomachine design and operational life. Sealing becomes the most cost-effective way to enhance system performance. Coatings, films, and combined use of both metals and ceramics play a major role in maintaining interface clearances in turbomachine sealing and component life. This paper focuses on conventional and innovative materials and design practices for sealing interfaces.

  15. Multimodal neuroelectric interface development

    NASA Technical Reports Server (NTRS)

    Trejo, Leonard J.; Wheeler, Kevin R.; Jorgensen, Charles C.; Rosipal, Roman; Clanton, Sam T.; Matthews, Bryan; Hibbs, Andrew D.; Matthews, Robert; Krupka, Michael

    2003-01-01

    We are developing electromyographic and electroencephalographic methods, which draw control signals for human-computer interfaces from the human nervous system. We have made progress in four areas: 1) real-time pattern recognition algorithms for decoding sequences of forearm muscle activity associated with control gestures; 2) signal-processing strategies for computer interfaces using electroencephalogram (EEG) signals; 3) a flexible computation framework for neuroelectric interface research; and d) noncontact sensors, which measure electromyogram or EEG signals without resistive contact to the body.

  16. Soft electrostatic repulsion in particle monolayers at liquid interfaces: surface pressure and effect of aggregation.

    PubMed

    Kralchevsky, Peter A; Danov, Krassimir D; Petkov, Plamen V

    2016-07-28

    Non-densely packed interfacial monolayers from charged micrometre-sized colloid particles find applications for producing micropatterned surfaces. The soft electrostatic repulsion between the particles in a monolayer on an air/water (or oil/water) interface is mediated by the non-polar fluid, where Debye screening is absent and the distances between the particles are considerably greater than their diameters. Surface pressure versus area isotherms were measured at the air/water interface. The experiments show that asymptotically the surface pressure is inversely proportional to the third power of the interparticle distance. A theoretical model is developed that predicts not only the aforementioned asymptotic law but also the whole surface pressure versus area dependence. An increase in the surface pressure upon aggregation of charged particles in the interfacial monolayers is experimentally established. This effect is explained by the developed theoretical model, which predicts that the surface pressure should linearly increase with the square root of the particle mean aggregation number. The effect of added electrolyte on the aggregation is also investigated. The data lead to the conclusion that 'limited aggregation' exists in the monolayers of charged particles. In brief, the stronger electrostatic repulsion between the bigger aggregates leads to a higher barrier to their coalescence that, in turn, prevents any further aggregation, i.e. negative feedback is present.This article is part of the themed issue 'Soft interfacial materials: from fundamentals to formulation'. PMID:27298437

  17. Surface tension of electrolyte interfaces: ionic specificity within a field-theory approach.

    PubMed

    Markovich, Tomer; Andelman, David; Podgornik, Rudi

    2015-01-28

    We study the surface tension of ionic solutions at air/water and oil/water interfaces by using field-theoretical methods and including a finite proximal surface-region with ionic-specific interactions. The free energy is expanded to first-order in a loop expansion beyond the mean-field result. We calculate the excess surface tension and obtain analytical predictions that reunite the Onsager-Samaras pioneering result (which does not agree with experimental data), with the ionic specificity of the Hofmeister series. We derive analytically the surface-tension dependence on the ionic strength, ionic size, and ion-surface interaction, and show consequently that the Onsager-Samaras result is consistent with the one-loop correction beyond the mean-field result. Our theory fits well a wide range of salt concentrations for different monovalent ions using one fit parameter per electrolyte and reproduces the reverse Hofmeister series for anions at the air/water and oil/water interfaces.

  18. Contact angle and detachment energy of shape anisotropic particles at fluid-fluid interfaces.

    PubMed

    Anjali, Thriveni G; Basavaraj, Madivala G

    2016-09-15

    The three phase contact angle of particles, a measure of its wettability, is an important factor that greatly influences their behaviour at interfaces. It is one of the principal design parameters for potential applications of particles as emulsion/foam stabilizers, functional coatings and other novel materials. In the present work, the effect of size, shape and surface chemistry of particles on their contact angle is investigated using the gel trapping technique, which facilitates the direct visualization of the equilibrium position of particles at interfaces. The contact angle of hematite particles of spherocylindrical, peanut and cuboidal shapes, hematite-silica core-shell and silica shells is reported at a single particle level. The spherocylindrical and peanut shaped particles are always positioned with their major axis parallel to the interface. However, for cuboidal particles at air-water as well as decane-water interfaces, different orientations namely - face-up, edge-up and the vertex-up - are observed. The influence of gravity on the equilibrium position of the colloidal particles at the interface is studied using the hematite-silica core-shell particles and the silica shells. The measured contact angle values are utilized in the calculations of the detachment and surface energies of the hematite particles adsorbed at the interface.

  19. Designing the Instructional Interface.

    ERIC Educational Resources Information Center

    Lohr, L. L.

    2000-01-01

    Designing the instructional interface is a challenging endeavor requiring knowledge and skills in instructional and visual design, psychology, human-factors, ergonomic research, computer science, and editorial design. This paper describes the instructional interface, the challenges of its development, and an instructional systems approach to its…

  20. Thread Pool Interface (TPI)

    2008-04-01

    Thread Pool Interface (TpI) provides a simple interface for running functions written in C or C++ in a thread-parallel mode. Application or library codes may need to perform operations thread-parallel on machines with multicore processors. the TPI library provides a simple mechanism for managing thread activation, deactivation, and thread-parallel execution of application-provided subprograms.

  1. The User Interface.

    ERIC Educational Resources Information Center

    Lindeman, Martha J.; And Others

    1989-01-01

    The first of three articles on the design of user interfaces for information retrieval systems discusses the need to examine types of display, prompting, and input as separate entities. The second examines the use of artificial intelligence in creating natural language interfaces, and the third outlines standards for case studies in human computer…

  2. Communication Interface for SAMS

    NASA Technical Reports Server (NTRS)

    Koffman, M.; Hartley, F.

    1995-01-01

    An interface is described that supplies communications between the flight instruments and the analog input of an existing conventional recording unit for the Shuttle Space Acceleration Measurement System (SAMS), a data acquisition unit. The architecture and current implementation of an STD bus/LonTalk communication interface are described.

  3. Interface colloidal robotic manipulator

    DOEpatents

    Aronson, Igor; Snezhko, Oleksiy

    2015-08-04

    A magnetic colloidal system confined at the interface between two immiscible liquids and energized by an alternating magnetic field dynamically self-assembles into localized asters and arrays of asters. The colloidal system exhibits locomotion and shape change. By controlling a small external magnetic field applied parallel to the interface, structures can capture, transport, and position target particles.

  4. Interface physics in microporous media : LDRD final report.

    SciTech Connect

    Yaklin, Melissa A.; Knutson, Chad E.; Noble, David R.; Aragon, Alicia R.; Chen, Ken Shuang; Giordano, Nicholas J.; Brooks, Carlton, F.; Pyrak-Nolte, Laura J.; Liu, Yihong

    2008-09-01

    This document contains a summary of the work performed under the LDRD project entitled 'Interface Physics in Microporous Media'. The presence of fluid-fluid interfaces, which can carry non-zero stresses, distinguishes multiphase flows from more readily understood single-phase flows. In this work the physics active at these interfaces has been examined via a combined experimental and computational approach. One of the major difficulties of examining true microporous systems of the type found in filters, membranes, geologic media, etc. is the geometric uncertainty. To help facilitate the examination of transport at the pore-scale without this complication, a significant effort has been made in the area of fabrication of both two-dimensional and three-dimensional micromodels. Using these micromodels, multiphase flow experiments have been performed for liquid-liquid and liquid-gas systems. Laser scanning confocal microscopy has been utilized to provide high resolution, three-dimensional reconstructions as well as time resolved, two-dimensional reconstructions. Computational work has focused on extending lattice Boltzmann (LB) and finite element methods for probing the interface physics at the pore scale. A new LB technique has been developed that provides over 100x speed up for steady flows in complex geometries. A new LB model has been developed that allows for arbitrary density ratios, which has been a significant obstacle in applying LB to air-water flows. A new reduced order model has been developed and implemented in finite element code for examining non-equilibrium wetting in microchannel systems. These advances will enhance Sandia's ability to quantitatively probe the rich interfacial physics present in microporous systems.

  5. Two-Dimensional Crystals of Icosahedral Viruses at Liquid interfaces

    NASA Astrophysics Data System (ADS)

    Fukuto, Masafumi; Yang, Lin; Checco, Antonio; Kuzmenko, Ivan; Nguyen, Quyen; Mank, Nick; Wang, Qian

    2012-02-01

    Two-dimensional (2D) assembly of turnip yellow mosaic virus (TYMV) on cationic lipid monolayers is investigated at the air-water interface. TYMV, an icosahedral virus with a diameter of 28 nm, exhibits well-defined roughness, charge distribution, and hydrophilic/hydrophobic patches on its surface. The electrostatic attraction to the lipid-coated aqueous interface provides means to impose a specific virus orientation and hence reduce the number of possible inter-particle interactions. The 2D geometry is particularly advantageous in dissecting the role of anisotropy in aqueous-media assembly, which involves various types of similarly weak interactions. We show that the assembly approach used not only facilitates crystallization but also provides insights on how complex anisotropic interactions can be exploited to generate long-range order. Specifically, we report an in situ x-ray scattering observation of novel 2D crystal forms of TYMV that reflect the virus' icosahedral symmetry. The symmetry, shape, and surface heterogeneities of TYMV suggest a mechanism by which these crystals are stabilized by a combination of hydrophobic, electrostatic, and steric interactions.

  6. SPUR coprocessor interface description

    SciTech Connect

    Hansen, P.M.; Kong, S.I.

    1987-01-01

    This report describes the SPUR coprocessor interface. The interface provides enhanced performance potential by allowing parallel operations between the SPUR processor and SPUR coprocessors. A decoupled control and execution architecture allow data transfers to proceed while coprocessor functions are performed. Implicit and explicit synchronization mechanisms provide the programmer with complete control and flexibility. On-chip coprocessor register files and a wide data path between the memory and coprocessor minimize data transfer overhead. An intelligent interface control unit provides parallel decoding of instructions for maximum performance.

  7. Operator interface for vehicles

    SciTech Connect

    Bissontz, Jay E

    2015-03-10

    A control interface for drivetrain braking provided by a regenerative brake and a non-regenerative brake is implemented using a combination of switches and graphic interface elements. The control interface comprises a control system for allocating drivetrain braking effort between the regenerative brake and the non-regenerative brake, a first operator actuated control for enabling operation of the drivetrain braking, and a second operator actuated control for selecting a target braking effort for drivetrain braking. A graphic display displays to an operator the selected target braking effort and can be used to further display actual braking effort achieved by drivetrain braking.

  8. Application of the ultrasonic technique and high-speed filming for the study of the structure of air-water bubbly flows

    SciTech Connect

    Carvalho, R.D.M.; Venturini, O.J.; Tanahashi, E.I.; Neves, F. Jr.; Franca, F.A.

    2009-10-15

    Multiphase flows are very common in industry, oftentimes involving very harsh environments and fluids. Accordingly, there is a need to determine the dispersed phase holdup using noninvasive fast responding techniques; besides, knowledge of the flow structure is essential for the assessment of the transport processes involved. The ultrasonic technique fulfills these requirements and could have the capability to provide the information required. In this paper, the potential of the ultrasonic technique for application to two-phase flows was investigated by checking acoustic attenuation data against experimental data on the void fraction and flow topology of vertical, upward, air-water bubbly flows in the zero to 15% void fraction range. The ultrasonic apparatus consisted of one emitter/receiver transducer and three other receivers at different positions along the pipe circumference; simultaneous high-speed motion pictures of the flow patterns were made at 250 and 1000 fps. The attenuation data for all sensors exhibited a systematic interrelated behavior with void fraction, thereby testifying to the capability of the ultrasonic technique to measure the dispersed phase holdup. From the motion pictures, basic gas phase structures and different flows patterns were identified that corroborated several features of the acoustic attenuation data. Finally, the acoustic wave transit time was also investigated as a function of void fraction. (author)

  9. Spatial trends, sources, and air-water exchange of organochlorine pesticides in the Great Lakes basin using low density polyethylene passive samplers.

    PubMed

    Khairy, Mohammed; Muir, Derek; Teixeira, Camilla; Lohmann, Rainer

    2014-08-19

    Polyethylene passive samplers were deployed during summer and fall of 2011 in the lower Great Lakes to assess the spatial distribution and sources of gaseous and freely dissolved organochlorine pesticides (OCPs) and their air-water exchange. Average gaseous OCP concentrations ranged from nondetect to 133 pg/m(3). Gaseous concentrations of hexachlorobenzene, dieldrin, and chlordanes were significantly greater (Mann-Whitney test, p < 0.05) at Lake Erie than Lake Ontario. A multiple linear regression implied that both cropland and urban areas within 50 and 10 km buffer zones, respectively, were critical parameters to explain the total variability in atmospheric concentrations. Freely dissolved OCP concentrations (nondetect to 114 pg/L) were lower than previously reported. Aqueous half-lives generally ranged from 1.7 to 6.7 years. Nonetheless, concentrations of p,p'-DDE and chlordanes were higher than New York State Ambient Water Quality Standards for the protection of human health from the consumption of fish. Spatial distributions of freely dissolved OCPs in both lakes were influenced by loadings from areas of concern and the water circulation patterns. Flux calculations indicated net deposition of γ-hexachlorocyclohexane, heptachlor-epoxide, and α- and β-endosulfan (-0.02 to -33 ng/m(2)/day) and net volatilization of heptachlor, aldrin, trans-chlordane, and trans-nonachlor (0.0 to 9.0 ng/m(2)/day) in most samples.

  10. Reliability of environmental fate modeling results for POPs based on various methods of determining the air/water partition coefficient (log KAW)

    NASA Astrophysics Data System (ADS)

    Odziomek, K.; Gajewicz, A.; Haranczyk, M.; Puzyn, T.

    2013-07-01

    Air-water partition coefficient (KAW) is one of the key parameters determining environmental behavior of Persistent Organic Pollutants (POPs). Experimentally measured values of KAW are still unavailable for majority of POPs, thus alternative methods of supplying data, including Quantitative Structure-Property Relationships (QSPR) modeling, are often in use. In this paper, applicability of two QSPR methods of predicting KAW were compared with each other in the context of further application of the predicted data in environmental transport and fate studies. According to the first (indirect) method, KAW is calculated from previously predicted values of octanol-water (KOW) and octanol-air (KOA) partition coefficients. In the second (direct) approach, KAW is calculated, based on the estimated value of Henry's law constant (KH) and then adjusted to ensure its consistency with the other two partition coefficients (KOW and KOA). Although the indirect method carries theoretically twice as much error as the direct method, when the predicted values of KAW are then utilized as an input to the environmental fate model The OECD POV and LRTP Screening Tool, ver. 2.2, the indirect method elicits much higher and therefore much more restrictive values of overall persistence (POV) and transfer efficiency (TE) than its equivalent (direct method). High uncertainties related to the application of the direct method result mainly from the necessary adjustment procedure.

  11. Implications of surfactant-induced flow for miscible-displacement estimation of air-water interfacial areas in unsaturated porous media.

    PubMed

    Costanza-Robinson, Molly S; Zheng, Zheng; Henry, Eric J; Estabrook, Benjamin D; Littlefield, Malcolm H

    2012-10-16

    Surfactant miscible-displacement experiments represent a conventional means of estimating air-water interfacial area (A(I)) in unsaturated porous media. However, changes in surface tension during the experiment can potentially induce unsaturated flow, thereby altering interfacial areas and violating several fundamental method assumptions, including that of steady-state flow. In this work, the magnitude of surfactant-induced flow was quantified by monitoring moisture content and perturbations to effluent flow rate during miscible-displacement experiments conducted using a range of surfactant concentrations. For systems initially at 83% moisture saturation (S(W)), decreases of 18-43% S(W) occurred following surfactant introduction, with the magnitude and rate of drainage inversely related to the surface tension of the surfactant solution. Drainage induced by 0.1 mM sodium dodecyl benzene sulfonate, commonly used for A(I) estimation, resulted in effluent flow rate increases of up to 27% above steady-state conditions and is estimated to more than double the interfacial area over the course of the experiment. Depending on the surfactant concentration and the moisture content used to describe the system, A(I) estimates varied more than 3-fold. The magnitude of surfactant-induced flow is considerably larger than previously recognized and casts doubt on the reliability of A(I) estimation by surfactant miscible-displacement.

  12. Time-resolved fast-neutron radiography of air-water two-phase flows in a rectangular channel by an improved detection system

    SciTech Connect

    Zboray, Robert; Dangendorf, Volker; Bromberger, Benjamin; Tittelmeier, Kai; Mor, Ilan

    2015-07-15

    In a previous work, we have demonstrated the feasibility of high-frame-rate, fast-neutron radiography of generic air-water two-phase flows in a 1.5 cm thick, rectangular flow channel. The experiments have been carried out at the high-intensity, white-beam facility of the Physikalisch-Technische Bundesanstalt, Germany, using an multi-frame, time-resolved detector developed for fast neutron resonance radiography. The results were however not fully optimal and therefore we have decided to modify the detector and optimize it for the given application, which is described in the present work. Furthermore, we managed to improve the image post-processing methodology and the noise suppression. Using the tailored detector and the improved post-processing, significant increase in the image quality and an order of magnitude lower exposure times, down to 3.33 ms, have been achieved with minimized motion artifacts. Similar to the previous study, different two-phase flow regimes such as bubbly slug and churn flows have been examined. The enhanced imaging quality enables an improved prediction of two-phase flow parameters like the instantaneous volumetric gas fraction, bubble size, and bubble velocities. Instantaneous velocity fields around the gas enclosures can also be more robustly predicted using optical flow methods as previously.

  13. Organochlorine pesticides in seawater and the surrounding atmosphere of the marginal seas of China: spatial distribution, sources and air-water exchange.

    PubMed

    Lin, Tian; Li, Jun; Xu, Yue; Liu, Xiang; Luo, Chunling; Cheng, Hairong; Chen, Yingjun; Zhang, Gan

    2012-10-01

    Shipboard air and surface seawater samples collected over the Yellow Sea, East China Sea and South China Sea were analyzed for organochlorine pesticides (OCPs). In air, γ-hexachlorocyclohexane (HCH), trans-chlordane (TC) and cis-chlordane (CC) had significantly (p<0.001) higher concentrations than α-HCH, o,p'-Dichlorodiphenyltrichloroethane (DDT), p,p'-DDE, p,p'-DDT and α-endosulfan. Generally, α-HCH concentrations in the atmosphere were quite uniform over the Chinese marginal seas. However, the highest concentrations of γ-HCH, TC, CC and DDT compounds were found in the southern parts of the marginal seas, and higher concentrations of α-endosulfan were observed in the northern part of the marginal seas. In water, the OCP concentrations varied over a narrow range, with hundreds picogram per liter levels. Air-water exchange gradients suggested net deposition or equilibrium for γ-HCH and o,p'-DDT and net volatilization for α-HCH, CC, TC, p,p'-DDE and p,p'-DDT. Due to the potential source of those compounds from coastal water runoff, the ocean water played an important role of OCP sources for the atmosphere after a long period of OCP prohibition.

  14. TSF Interface Package

    2004-03-01

    A collection of packages of classes for interfacing to sparse and dense matrices, vectors and graphs, and to linear operators. TSF (via TSFCore, TSFCoreUtils and TSFExtended) provides the application programmer interface to any number of solvers, linear algebra libraries and preconditioner packages, providing also a sophisticated technique for combining multiple packages to solve a single problem. TSF provides a collection of abstract base classes that define the interfaces to abstract vector, matrix and linear soeratormore » objects. By using abstract interfaces, users of TSF are not limiting themselves to any one concrete library and can in fact easily combine multiple libraries to solve a single problem.« less

  15. Crewstation display interface standardization

    NASA Astrophysics Data System (ADS)

    Hardy, Gregory J.

    1999-08-01

    Military sensors and crewstation displays are all moving to digital-based technologies, an epochal shift from the previous world of analog interfaces throughout the video chain. It is no longer possible to specify a sensor and display to the same interface specification such as the venerable RS-170 and RS- 343 standards without paying an unacceptable resolution penalty. Consequently a new standard is required to allow sensor and display manufacturers to easily design system interfaces without relying on cumbersome, costly and unique interface control documents. This paper presents one possible hardware and protocol standard based on FibreChannel technology, and solicits inputs into the standards setting process which is now in progress.

  16. Scalable coherent interface

    SciTech Connect

    Alnaes, K.; Kristiansen, E.H. ); Gustavson, D.B. ); James, D.V. )

    1990-01-01

    The Scalable Coherent Interface (IEEE P1596) is establishing an interface standard for very high performance multiprocessors, supporting a cache-coherent-memory model scalable to systems with up to 64K nodes. This Scalable Coherent Interface (SCI) will supply a peak bandwidth per node of 1 GigaByte/second. The SCI standard should facilitate assembly of processor, memory, I/O and bus bridge cards from multiple vendors into massively parallel systems with throughput far above what is possible today. The SCI standard encompasses two levels of interface, a physical level and a logical level. The physical level specifies electrical, mechanical and thermal characteristics of connectors and cards that meet the standard. The logical level describes the address space, data transfer protocols, cache coherence mechanisms, synchronization primitives and error recovery. In this paper we address logical level issues such as packet formats, packet transmission, transaction handshake, flow control, and cache coherence. 11 refs., 10 figs.

  17. Software interface verifier

    NASA Technical Reports Server (NTRS)

    Soderstrom, Tomas J.; Krall, Laura A.; Hope, Sharon A.; Zupke, Brian S.

    1994-01-01

    A Telos study of 40 recent subsystem deliveries into the DSN at JPL found software interface testing to be the single most expensive and error-prone activity, and the study team suggested creating an automated software interface test tool. The resulting Software Interface Verifier (SIV), which was funded by NASA/JPL and created by Telos, employed 92 percent software reuse to quickly create an initial version which incorporated early user feedback. SIV is now successfully used by developers for interface prototyping and unit testing, by test engineers for formal testing, and by end users for non-intrusive data flow tests in the operational environment. Metrics, including cost, are included. Lessons learned include the need for early user training. SIV is ported to many platforms and can be successfully used or tailored by other NASA groups.

  18. Performance Application Programming Interface

    2005-10-31

    PAPI is a programming interface designed to provide the tool designer and application engineer with a consistent interface and methodology for use of the performance counter hardware found in most major microprocessors. PAPI enables software engineers to see, in near real time, the relation between software performance and processor events. This release covers the hardware dependent implementation of PAPI version 3 for the IBM BlueGene/L (BG/L) system.

  19. On the use of evanescent plane waves for low-frequency energy transmission across material interfaces.

    PubMed

    Woods, Daniel C; Bolton, J Stuart; Rhoads, Jeffrey F

    2015-10-01

    The transmission of airborne sound into high-impedance media is of interest in several applications. For example, sonic booms in the atmosphere may impact marine life when incident on the ocean surface, or affect the integrity of existing structures when incident on the ground. Transmission across high impedance-difference interfaces is generally limited by reflection and refraction at the surface, and by the critical angle criterion. However, spatially decaying incident waves, i.e., inhomogeneous or evanescent plane waves, may transmit energy above the critical angle, unlike homogeneous plane waves. The introduction of a decaying component to the incident trace wavenumber creates a nonzero propagating component of the transmitted normal wavenumber, so energy can be transmitted across the interface. A model of evanescent plane waves and their transmission across fluid-fluid and fluid-solid interfaces is developed here. Results are presented for both air-water and air-solid interfaces. The effects of the incident wave parameters (including the frequency, decay rate, and incidence angle) and the interfacial properties are investigated. Conditions for which there is no reflection at the air-solid interface, due to impedance matching between the incident and transmitted waves, are also considered and are found to yield substantial transmission increases over homogeneous incident waves. PMID:26520290

  20. On the use of evanescent plane waves for low-frequency energy transmission across material interfaces.

    PubMed

    Woods, Daniel C; Bolton, J Stuart; Rhoads, Jeffrey F

    2015-10-01

    The transmission of airborne sound into high-impedance media is of interest in several applications. For example, sonic booms in the atmosphere may impact marine life when incident on the ocean surface, or affect the integrity of existing structures when incident on the ground. Transmission across high impedance-difference interfaces is generally limited by reflection and refraction at the surface, and by the critical angle criterion. However, spatially decaying incident waves, i.e., inhomogeneous or evanescent plane waves, may transmit energy above the critical angle, unlike homogeneous plane waves. The introduction of a decaying component to the incident trace wavenumber creates a nonzero propagating component of the transmitted normal wavenumber, so energy can be transmitted across the interface. A model of evanescent plane waves and their transmission across fluid-fluid and fluid-solid interfaces is developed here. Results are presented for both air-water and air-solid interfaces. The effects of the incident wave parameters (including the frequency, decay rate, and incidence angle) and the interfacial properties are investigated. Conditions for which there is no reflection at the air-solid interface, due to impedance matching between the incident and transmitted waves, are also considered and are found to yield substantial transmission increases over homogeneous incident waves.