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Sample records for air-water interface awi

  1. Effect Of Air-Water Interface On Microorganism Transport Under Unsaturated Conditions

    NASA Astrophysics Data System (ADS)

    Torkzaban, S.; Hassanizadeh, S. M.; Schijven, J. F.

    2005-12-01

    Groundwater may become contaminated with pathogenic microorganisms from land application of treated wastewater, septic wells, and effluent from septic tanks, and leaking sewage pipes. The unsaturated zone is of special importance since it often represents the first line of natural defense against groundwater pollution. Moreover, many experimental studies have shown that contaminant removal is more significant under lower saturation levels. Interaction of microbial particles with the air-water interfaces (AWI) has been previously suggested to explain high removal of pathogenic microorganisms during transport through unsaturated soil. The objective of this research was to explore the effect of AWI on virus transport. The transport of bacteriophages MS2 and FiX174 in sand columns was studied under various conditions, such as different pH, and saturation levels. Fitting of a transport model to the breakthrough curves was performed to determine the adsorption parameters. FiX174 with isoelectric point of 6.7 exhibited high affinity to the air-water interface by decreasing pH from 7.5 to 6.2. MS2 with isoelectric point of 3.5 has lower affinity to air-water interfaces than FiX174, but has similar pH- dependence. These results show the importance of electrostatic interactions, instead of hydrophobic, between the AWI and viruses. Adsorption to AWI is strongly pH dependent, increasing as pH decreases. It was found that two-site kinetic model should be used for modeling of virus transport under unsaturated conditions Moreover, by draining the unsaturated column, we found out that the attached viruses to AWI are viable, which is in contrast with the literature where retained viruses to AWI are considered as inactivated.

  2. Measuring interactions between polydimethylsiloxane and serum proteins at the air-water interface.

    PubMed

    Liao, Zhengzheng; Hsieh, Wan-Ting; Baumgart, Tobias; Dmochowski, Ivan J

    2013-07-30

    The interaction between synthetic polymers and proteins at interfaces is relevant to basic science as well as a wide range of applications in biotechnology and medicine. One particularly common and important interface is the air-water interface (AWI). Due to the special energetics and dynamics of molecules at the AWI, the interplay between synthetic polymer and protein can be very different from that in bulk solution. In this paper, we applied the Langmuir-Blodgett technique and fluorescence microscopy to investigate how the compression state of polydimethylsiloxane (PDMS) film at the AWI affects the subsequent adsorption of serum protein [e.g., human serum albumin (HSA) or immunoglobulin G (IgG)] and the interaction between PDMS and protein. Of particular note is our observation of circular PDMS domains with micrometer diameters that form at the AWI in the highly compressed state of the surface film: proteins were shown to adsorb preferentially to the surface of these circular PDMS domains, accompanied by a greater than 4-fold increase in protein found in the interfacial film. The PDMS-only film and the PDMS-IgG composite film were transferred to cover glass, and platinum-carbon replicas of the transferred films were further characterized by scanning electron microscopy and atomic force microscopy. We conclude that the structure of the PDMS film greatly affects the amount and distribution of protein at the interface. PMID:23819833

  3. 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.

  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. Tangential stress beneath wind-driven air water interfaces

    NASA Astrophysics Data System (ADS)

    Banner, Michael L.; Peirson, William L.

    1998-06-01

    The detailed structure of the aqueous surface sublayer flow immediately adjacent to the wind-driven air water interface is investigated in a laboratory wind-wave flume using particle image velocimetry (PIV) techniques. The goal is to investigate quantitatively the character of the flow in this crucial, very thin region which is often disrupted by microscale breaking events. In this study, we also examine critically the conclusions of Okuda, Kawai & Toba (1977), who argued that for very short, strongly forced wind-wave conditions, shear stress is the dominant mechanism for transmitting the atmospheric wind stress into the water motion waves and surface drift currents. In strong contrast, other authors have more recently observed very substantial normal stress contributions on the air side. The availability of PIV and associated image technology now permits a timely re-examination of the results of Okuda et al., which have been influential in shaping present perceptions of the physics of this dynamically important region. The PIV technique used in the present study overcomes many of the inherent shortcomings of the hydrogen bubble measurements, and allows reliable determination of the fluid velocity and shear within 200 [mu]m of the instantaneous wind-driven air water interface.

  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. Microrheology Using Optical Tweezers at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Boatwright, Thomas; Levine, Alex; Dennin, Michael

    2010-11-01

    Microrheological techniques have been used successfully to determine mechanical properties of materials important in cellular structure. Also critical to cellular mechanical functions are biological membranes. Many aspects of biological membranes can be modeled using Langmuir monolayers, which are single layers surfactants at the air-water interface. The macroscopic mechanical properties of Langmuir monolayers have been extensively characterized. In contrast to macroscopic measurements, we report on experimental methods for studying the rheological properties of Langmuir monolayers on the micron scale. A water immersion optical tweezers system is used to trap ˜1 micron diameter beads in a monolayer. The passive motion of the trapped beads is recorded at high frequency and the complex shear modulus is calculated. Preliminary microrheological data of a fatty acid monolayer showing dependence on surface pressure will be presented. Experimental obstacles will also be discussed.

  8. [Virus adsorption from batch experiments as influenced by air-water interface].

    PubMed

    Zhang, Hui; Zhao, Bing-zi; Zhang, Jia-bao; Zhang, Cong-zhi; Wang, Qiu-ying; Chen, Ji

    2007-12-01

    The presence of air-water interface in batch sorption experiments may result in inaccurate estimation of virus adsorption onto various soils. A batch sorption experiment was conducted to compare the adsorption results of MS2 in different soils under presence/absence of air-water interface. Soils with sterilization/nonterilization treatment were used. Virus recovery efficiency in a blank experiment (no soil) was also evaluated as affected by different amount of air-water interface. The presence of air-water interface altered the results of virus adsorption in different soils with different extent, with Sandy fluvo-aquic soil being the most considerably affected, followed by Red loam soil, and the least being Red clay soil, probably because of different soil properties associated with virus adsorption/inactivation. Soil sterilization resulted in more significant difference of virus adsorption onto the Sandy fluvo-aquic soil between the presence and absence of air-water interface, while a reduced difference was observed in the Red loam soil. The presence of air-water interface significantly decreased virus recovery efficiency, with the values being decreased with increase in the amount of air-water interface. Soil particles likely prohibit viruses from reaching the air-water interface or alter the forces at the solid-water-air interface so that the results from the blank experiment did not truly represent results from control blank, which probably resulted in adsorption difference between presence and absence of the air-water interface. PMID:18290440

  9. 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

  10. Monolayers at air-water interfaces: from origins-of-life to nanotechnology.

    PubMed

    Ariga, Katsuhiko; Hill, Jonathan P

    2011-08-01

    The air-water interface presents several interesting features, namely a) a molecularly flat environment, b) a boundary region between two phases with different dielectric constants, c) permits or promotes dynamic interactions within the interface region, and d) a point of interaction between hydrophobic compounds and aqueous molecules. Accordingly, Langmuir monolayers at the air-water interface have several unique characteristics and properties, which require investigation. In this review-type personal account, typical examples of molecular recognition and molecular patterning at air-water interfaces are first introduced, followed by descriptions of specific and unusual properties of monolayers on water. In addition, two examples of our own results concerning Langmuir monolayers are explained. We have selected examples from two apparently unrelated research areas, these being the origin of life and future nanotechnology, in order to emphasize the diverse scientific contribution of research on monolayers at the air-water interface. PMID:21739568

  11. Interaction of Charged Colloidal Particles at the Air-Water Interface.

    PubMed

    Girotto, Matheus; Dos Santos, Alexandre P; Levin, Yan

    2016-07-01

    We study, using Monte Carlo simulations, the interaction between charged colloidal particles confined to the air-water interface. The dependence of force on ionic strength and counterion valence is explored. For 1:1 electrolyte, we find that the electrostatic interaction at the interface is very close to the one observed in the bulk. On the other hand, for salts with multivalent counterions, an interface produces an enhanced attraction between like charged colloids. Finally, we explore the effect of induced surface charge at the air-water interface on the interaction between colloidal particles. PMID:26551757

  12. 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

  13. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

    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.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

  15. 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…

  16. 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. PMID:25358083

  17. 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.

  18. 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.

  19. 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

  20. Rheology and microrheology of materials at the air-water interface

    NASA Astrophysics Data System (ADS)

    Walder, Robert Benjamin

    2008-10-01

    The study of materials at the air-water interface is an important area of research in soft condensed matter physics. Films at the air-water interface have been a system of interest to physics, chemistry and biology for the last 20 years. The unique properties of these surface films provide ideal models for 2-d films, surface chemistry and provide a platform for creating 2 dimensional analogue materials to cellular membranes. Measurements of the surface rheology of cross-linked F-actin networks associated with a lipid monolayer at the air-water interface of a Langmuir monolayer have been performed. The rheological measurements are made using a Couette cell. These data demonstrate that the network has a finite elastic modulus that grows as a function of the cross-linking concentration. We also note that under steady-state flow the system behaves as a power law fluid in which the effective viscosity decreases with imposed shear. A Langmuir monolayer trough that is equipped for simultaneous microrheology and standard rheology measurements has been constructed. The central elements are the trough itself with a full range of optical tools accessing the air-water interface from below the trough and a portable knife-edge torsion pendulum that can access the interface from above. The ability to simultaneously measure the mechanical response of Langmuir monolayers on very different length scales is an important step for our understanding of the mechanical response of two-dimensional viscoelastic networks. The optical tweezer microrheometer is used to study the micromechanical properties of Langmuir monolayers. Microrheology measurements are made a variety of surface pressures that correspond to different ordered phases of the monolayer. The complex shear modulus shows an order of magnitude increase for the liquid condensed phase of DPPC compared to the liquid expanded phase.

  1. 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.

  2. Thermodynamic and dynamic characteristics of hydroxypropylmethylcellulose adsorbed films at the air-water interface.

    PubMed

    Pérez, Oscar E; Sánchez, Cecilio Carrera; Rodríguez Patino, Juan M; Pilosof, Ana M R

    2006-01-01

    Surface pressure isotherms and structural and surface dilatational properties of three hydroxypropylmethycelluloses (HPMCs, called E4M, E50LV, and F4M) adsorbed films at the air-water interface were determined. In this work we present evidence that HPMC molecules are able to diffuse and saturate the air-water interface at very low concentrations in the bulk phase. As bulk concentration increased, structural changes at a molecular level occurred at the interface. These changes corresponded to transition from an expanded structure (structure I) to a condensed one (structure II). When the surface concentration of HPMC was high enough, the collapse of the monolayer was observed. The three HPMCs formed very elastic films at the air-water interface, even at low surface pressures. E4M showed features that make it unique. For instance it showed the highest surface activity, mainly at low bulk concentrations (<10(-4) wt %). The differences observed in surface activity may be attributed to differences in the hydroxypropyl molar substitution and molecular weight of HPMC. All three HPMCs formed films of similar viscoelasticity and elastic dilatational modulus, which can be accounted for by their similar degree of methyl substitution. PMID:16398540

  3. Microstructure of Hairy-Rod Polymers at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Chien, B. T.; Riou, S. A.; Su, Z.; Hsu, S. L.

    1997-03-01

    To better understand the role of long flexible side groups on the microstructure of "hairy-rod" polymer thin films, a series of poly(γ-methyl-L-glutamate-co-γ-n-octadecyl-L- glutamate) of varying degree copolymerization has been investigated at the air-water interface by external reflectance infrared spectroscopy. Coupled with a Langmuir trough, the microstructure of the monolayer films was charaterized directly at the air-water interface as a function of varying surface packing density. The conformational order of the n-octadecyl side groups was subsequently shown to vary strongly as a function of n-octadecyl side group content as well as surface packing density. When conformationally disordered, the n-octadecyl side groups could be likened to that of a Rsolvent-likeS matrix for the rigid- rod main chains in the plane of the interface. By controlling the conformational order and therefore the Rsolvent-likeS character of the n-octadecyl side groups, it was possible to control an in-plane orientation of the rigid-rod main chains relative to that of the compression axis of the Langmuir trough. The orientation of the n- octadecyl side groups out of the plane of the air-water interface was also determined.

  4. A self-consistent field study of a hydrocarbon droplet at the air-water interface.

    PubMed

    Hilz, Emilia; Leermakers, Frans A M; Vermeer, Arnoldus W P

    2012-04-14

    A molecularly detailed self-consistent field (SCF) approach is applied to describe a sessile hydrocarbon droplet placed at the air-water interface. Predictions of the contact angle for macroscopic droplets follow from using Neumann's equation, wherein the macroscopic interfacial tensions are computed from one-gradient calculations for flat interfaces. A two-gradient cylindrical coordinate system with mirror-like boundary conditions is used to analyse the three dimensional shape of the nano-scale oil droplet at the air-water interface. These small droplets have a finite value of the Laplace pressure and concomitant line tension. It has been calculated that the oil-water and oil-vapour interfacial tensions are curvature dependent and increase slightly with increasing interfacial curvature. In contrast, the line tension tends to decrease with curvature. In all cases there is only a weak influence of the line tension on the droplet shape. We therefore argue that the nano-scale droplets, which are described in the SCF approach, are representative for macroscopic droplets and that the method can be used to efficiently generate accurate information on the spreading of oil droplets at the air-water interface in molecularly more complex situations. As an example, non-ionic surfactants have been included in the system to illustrate how a molecularly more complex situation will change the wetting properties of the sessile drop. This short forecast is aimed to outline and to stress the potential of the method. PMID:22395192

  5. Effect of Particulate Contaminants on the Development of Biofilms at Air/Water Interfaces.

    PubMed

    Zhang, Zhenhuan; Christopher, Gordon

    2016-03-22

    The development of biofilms at air/water or oil/water interfaces has important ramifications on several applications, but it has received less attention than biofilm formation on solid surfaces. A key difference between the growth of biofilms on solid surfaces versus liquid interfaces is the range of complicated boundary conditions the liquid interface can create that may affect bacteria, as they adsorb onto and grow on the interface. This situation is exacerbated by the existence of complex interfaces in which interfacially adsorbed components can even more greatly affect interfacial boundary conditions. In this work, we present evidence as to how particle-laden interfaces impact biofilm growth at an air/water interface. We find that particles can enhance the rate of growth and final strength of biofilms at liquid interfaces by providing sites of increased adhesive strength for bacteria. The increased adhesion stems from creating localized areas of hydrophobicity that protrude in the water phase and provide sites where bacteria preferentially adhere. This mechanism is found to be primarily controlled by particle composition, with particle size providing a secondary effect. This increased adhesion through interfacial conditions creates biofilms with properties similar to those observed when adhesion is increased through biological means. Because of the generally understood ubiquity of increased bacteria attachment to hydrophobic surfaces, this result has general applicability to pellicle formation for many pellicle-forming bacteria. PMID:26943272

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. Interfacial properties of mixed films of long-chain organics at the air-water interface

    NASA Astrophysics Data System (ADS)

    Gilman, Jessica B.; Tervahattu, Heikki; Vaida, Veronica

    Organic molecules residing at the air-water interface of atmospheric aerosols will have a critical and direct effect on the aerosols' chemical, physical, and optical properties. It is important to study the interfacial properties of such compounds in order to accurately assess these effects. In this study, the compositions of two organic binary films at the air-water interface were monitored as a function of exposure time to the ambient atmosphere. One film was composed of tetracosanoic acid (lignoceric acid, CH 3(CH 2) 22COOH) and nonacosane (C 29H 60), and the second film was composed of octadecanoic acid (stearic acid, CH 3(CH 2) 16COOH) and octadecane (C 18H 38). These films were used as simplified proxies for the organic coating on atmospheric aerosols. The effect of lengthening the hydrocarbon chain on the interfacial longevity of the compounds in the mixed organic film at the air-aqueous interface was determined. The results show that octadecane in a mixed film desorbs from the interface after 72 h while octadecanoic acid remains. For nonacosane, further lengthening of the carbon chain greatly increased its interfacial longevity so that it was comparable with the fatty acids, which remained stable at the interface for at least 144 h. These results are used to explain the preponderance of long-chain fatty acids on the surfaces of collected aerosols and give insight into the degree to which the presence of other long-chain organics may affect the aerosol's chemical and physical properties.

  12. 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

  13. 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

  14. Self-Assembly of Peptides at the Air/Water Interface

    NASA Astrophysics Data System (ADS)

    Sayar, Mehmet

    2013-03-01

    Peptides are commonly used as building blocks for design and development of novel materials with a variety of application areas ranging from drug design to biotechnology. The precise control of molecular architecture and specific nature of the nonbonded interactions among peptides enable aggregates with well defined structural and functional properties. The interaction of peptides with interfaces leads to dramatic changes in their conformational and aggregation behavior. In this talk, I will discuss our research on the interplay of intermolecular forces and influence of interfaces. In the first part the amphiphilic nature of short peptide oligomers and their behavior at the air/water interface will be discussed. The surface driving force and its decomposition will be analyzed. In the second part aggregation of peptides in bulk water and at an interface will be discussed. Different design features which can be tuned to control aggregation behavior will be analyzed.

  15. Proteins at air-water interfaces: a coarse-grained model.

    PubMed

    Cieplak, Marek; Allan, Daniel B; Leheny, Robert L; Reich, Daniel H

    2014-11-01

    We present a coarse-grained model to describe the adsorption and deformation of proteins at an air-water interface. The interface is introduced empirically in the form of a localized field that couples to a hydropathy scale of amino acids. We consider three kinds of proteins: protein G, egg-white lysozyme, and hydrophobin. We characterize the nature of the deformation and the orientation of the proteins induced by their proximity to and association with the interface. We also study protein diffusion in the layer formed at the interface and show that the diffusion slows with increasing concentration in a manner similar to that for a colloidal suspension approaching the glass transition. PMID:25310625

  16. Specific ion adsorption at the air/water interface: The role of hydrophobic solvation

    NASA Astrophysics Data System (ADS)

    Horinek, Dominik; Herz, Alexander; Vrbka, Lubos; Sedlmeier, Felix; Mamatkulov, Shavkat I.; Netz, Roland R.

    2009-09-01

    Classical force fields for molecular simulations of aqueous electrolytes are still controversial. We study alkali and halide ions at the air/water interface using novel non-polarizable force fields that were optimized based on bulk thermodynamics. In qualitative agreement with polarizable force-field simulations, ion repulsion from the interface decreases with increasing ion size. Iodide is even enhanced at the interface, which is rationalized by hydrophobic solvation at the interface, but exhibits a smaller surface propensity than in previous polarizable simulations. Surprisingly, lithium is less repelled than other cations because of its tightly bound hydration shell. A generalized Poisson-Boltzmann approach that includes ionic potentials of mean force from simulation almost quantitatively matches experimental interfacial tension increments for 1 molar sodium halides and alkali chlorides. We conclude that properly optimized non-polarizable force fields are transferable to interfacial environments and hold the potential for unravelling ion-specific effects even in biological situations involving peptidic surfaces.

  17. Protein adsorption at the electrified air-water interface: implications on foam stability.

    PubMed

    Engelhardt, Kathrin; Rumpel, Armin; Walter, Johannes; Dombrowski, Jannika; Kulozik, Ulrich; Braunschweig, Björn; Peukert, Wolfgang

    2012-05-22

    The surface chemistry of ions, water molecules, and proteins as well as their ability to form stable networks in foams can influence and control macroscopic properties such as taste and texture of dairy products considerably. Despite the significant relevance of protein adsorption at liquid interfaces, a molecular level understanding on the arrangement of proteins at interfaces and their interactions has been elusive. Therefore, we have addressed the adsorption of the model protein bovine serum albumin (BSA) at the air-water interface with vibrational sum-frequency generation (SFG) and ellipsometry. SFG provides specific information on the composition and average orientation of molecules at interfaces, while complementary information on the thickness of the adsorbed layer can be obtained with ellipsometry. Adsorption of charged BSA proteins at the water surface leads to an electrified interface, pH dependent charging, and electric field-induced polar ordering of interfacial H(2)O and BSA. Varying the bulk pH of protein solutions changes the intensities of the protein related vibrational bands substantially, while dramatic changes in vibrational bands of interfacial H(2)O are simultaneously observed. These observations have allowed us to determine the isoelectric point of BSA directly at the electrolyte-air interface for the first time. BSA covered air-water interfaces with a pH near the isoelectric point form an amorphous network of possibly agglomerated BSA proteins. Finally, we provide a direct correlation of the molecular structure of BSA interfaces with foam stability and new information on the link between microscopic properties of BSA at water surfaces and macroscopic properties such as the stability of protein foams. PMID:22530646

  18. 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

  19. 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.

  20. 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

  1. 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. PMID:26978461

  2. Effect of humidity on the adsorption kinetics of lung surfactant at air-water interfaces.

    PubMed

    Zuo, Yi Y; Gitiafroz, Roya; Acosta, Edgar; Policova, Zdenka; Cox, Peter N; Hair, Michael L; Neumann, A Wilhelm

    2005-11-01

    The in vitro adsorption kinetics of lung surfactant at air-water interfaces is affected by both the composition of the surfactant preparations and the conditions under which the assessment is conducted. Relevant experimental conditions are surfactant concentration, temperature, subphase pH, electrolyte concentration, humidity, and gas composition of the atmosphere exposed to the interface. The effect of humidity on the adsorption kinetics of a therapeutic lung surfactant preparation, bovine lipid extract surfactant (BLES), was studied by measuring the dynamic surface tension (DST). Axisymmetric drop shape analysis (ADSA) was used in conjunction with three different experimental methodologies, i.e., captive bubble (CB), pendant drop (PD), and constrained sessile drop (CSD), to measure the DST. The experimental results obtained from these three methodologies show that for 100% relative humidity (RH) at 37 degrees C the rate of adsorption of BLES at an air-water interface is substantially slower than for low humidity. It is also found that there is a difference in the rate of surface tension decrease measured from the PD and CB/CSD methods. These experimental results agree well with an adsorption model that considers the combined effects of entropic force, electrostatic interaction, and gravity. These findings have implications for the development and evaluation of new formulations for surfactant replacement therapy. PMID:16262325

  3. Communication: Vibrational sum-frequency spectrum of the air-water interface, revisited.

    PubMed

    Ni, Yicun; Skinner, J L

    2016-07-21

    Before 2015, heterodyne-detected sum-frequency-generation experiments on the air-water interface showed the presence of a positive feature at low frequency in the imaginary part of the susceptibility. However, three very recent experiments indicate that this positive feature is in fact absent. Armed with a better understanding, developed by others, of how to calculate sum-frequency spectra, we recalculate the spectrum and find good agreement with these new experiments. In addition, we provide a revised interpretation of the spectrum. PMID:27448864

  4. 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.

  5. Communication: Vibrational sum-frequency spectrum of the air-water interface, revisited

    NASA Astrophysics Data System (ADS)

    Ni, Yicun; Skinner, J. L.

    2016-07-01

    Before 2015, heterodyne-detected sum-frequency-generation experiments on the air-water interface showed the presence of a positive feature at low frequency in the imaginary part of the susceptibility. However, three very recent experiments indicate that this positive feature is in fact absent. Armed with a better understanding, developed by others, of how to calculate sum-frequency spectra, we recalculate the spectrum and find good agreement with these new experiments. In addition, we provide a revised interpretation of the spectrum.

  6. 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.

  7. 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

  8. Rapid Facial Fabrication of Silica Colloidal Crystal Film at the Air/Water Interface.

    PubMed

    Wang, Xia; Wang, Yun; Chen, Qiming

    2015-12-01

    A rapid and facial strategy has been developed to self-assemble 2D or 3D silica colloidal crystals at the air/water interface. The surface hydrophilicity of monodisperse silica microspheres were prepared by the Stöber method and modified by physical adsorption of a cationic surfactant (CTAB). The surface-modified silica microspheres were dispersed into an organic solvent and readily self-assemble at the air/water interface to form 2D monolayer film. The surface potential (ζ ) of silica microspheres could be changed with different concentration of CTAB aqueous solution. When the surface potential of silica particles was of -36.67 mV, a 2D monolayer film with close-packed and high-ordered structure could be easily obtained and may further be transferred onto a solid substrate layer by layer to develop a 3D multilayer film. UV-visible spectrophotometer was used to analyze the orderliness of colloidal crystal film, the Bragg diffraction positions and silica diameters were in good agreement with those were theoretically calculated. In addition, Atomic Force microscopy (AFM) was used to observe the arrangement of colloidal crystals. PMID:26682401

  9. Langmuir-Blodgett film of hydrophobin protein from Pleurotus ostreatus at the air-water interface.

    PubMed

    Houmadi, S; Ciuchi, F; De Santo, M P; De Stefano, L; Rea, I; Giardina, P; Armenante, A; Lacaze, E; Giocondo, M

    2008-11-18

    We present results concerning the formation of Langmuir-Blodgett (LB) films of a class I hydrophobin from Pleurotus ostreatus at the air-water interface, and their structure as Langmuir-Blodgett (LB) films when deposited on silicon substrates. LB films of the hydrophobin were investigated by atomic force microscopy (AFM). We observed that the compressed film at the air-water interface exhibits a molecular depletion even at low surface pressure. In order to estimate the surface molecular concentration, we fit the experimental isotherm with Volmer's equation describing the equation of state for molecular monolayers. We found that about (1)/ 10 of the molecules contribute to the surface film formation. When transferred on silicon substrates, compact and uniform monomolecular layers about 2.5 nm thick, comparable to a typical molecular size, were observed. The monolayers coexist with protein aggregates, under the typical rodlet form with a uniform thickness of about 5.0 nm. The observed rodlets appear to be a hydrophilic bilayer and can then be responsible for the surface molecular depletion. PMID:18925762

  10. 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

  11. 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

  12. 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.

  13. 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

  14. 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

  15. 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

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

    DOE PAGESBeta

    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

  17. 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

  18. 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.

  19. 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.

  20. "Ene" Reactions of Singlet Oxygen at the Air-Water Interface.

    PubMed

    Malek, Belaid; Fang, William; Abramova, Inna; Walalawela, Niluksha; Ghogare, Ashwini A; Greer, Alexander

    2016-08-01

    Prenylsurfactants [(CH3)2C═CH(CH2)nSO3(-) Na(+) (n = 4, 6, or 8)] were designed to probe the "ene" reaction mechanism of singlet oxygen at the air-water interface. Increasing the number of carbon atoms in the hydrophobic chain caused an increase in the regioselectivity for a secondary rather than tertiary surfactant hydroperoxide, arguing for an orthogonal alkene on water. The use of water, deuterium oxide, and H2O/D2O mixtures helped to distinguish mechanistic alternatives to homogeneous solution conditions that include dewetting of the π bond and an unsymmetrical perepoxide transition state in the hydroperoxide-forming step. The prenylsurfactants and a photoreactor technique allowed a certain degree of interfacial control of the hydroperoxidation reaction on a liquid support, where the oxidant (airborne (1)O2) is delivered as a gas. PMID:27385423

  1. Transition States for Submerged Superhydrophobic Surfaces: Partially-Pinned Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Tafreshi, Hooman; Hemeda, Ahmed; VCU Team

    2015-11-01

    The pressure at which a superhydrophobic surface transitions from the Cassie state to the Wenzel state is often referred to as the critical pressure. Our mathematical simulations have shown that the Cassie-to-Wenzel transition is a gradual process that takes place over a range of pressures as oppose to an event that happens at a certain pressure. During the transition period, the air-water interface may go through a series pinned, partially-pinned, and de-pinned states that depend on the geometry of the surface asperities. This in turn indicates that the drag-reduction effect produced by a submerged superhydrophobic surface can vary with the hydrostatic pressure, and is highly dependent on sharpness of the surface asperities. The study reported here reviews our recent discoveries in simulating the wetted area and drag reduction effect of superhydrophobic surfaces with different microstructures. National Science Foundation CMM 1029924 and CBET 1402655 programs.

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

    PubMed Central

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

    2015-01-01

    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. PMID:25687953

  3. Near-surface turbulence for evaporative convection at an air/water interface

    NASA Astrophysics Data System (ADS)

    Flack, K. A.; Saylor, J. R.; Smith, G. B.

    2001-11-01

    Turbulence measurements are reported for the flow beneath an air/water interface undergoing evaporative convection. Measurements were obtained using a two component laser Doppler velocimeter system. Two hydrodynamic boundary conditions were considered for the free surface: a shear free surface, which is the case when surfactants are absent, and a constant elasticity surface, created by depositing a monolayer of oleyl alcohol. The shear free boundary condition case results in significantly higher levels of near surface turbulence than the constant elasticity case. This difference between the two cases decreases with distance from the free surface. Profiles of the turbulent fluctuations were obtained for the horizontal and vertical velocity components and are compared with the somewhat analogous case of a heated solid wall.

  4. Brewster Angle Microscopy Study of Model Stratum Corneum Lipid Monolayers at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Adams, Ellen; Champagne, Alex; William, Joseph; Allen, Heather

    2012-04-01

    As the first and last barrier in the body, the stratum corneum (SC) is essential to life. Understanding the interactions and organization of lipids within the SC provides insight into essential physiological processes, including water loss prevention and the adsorption of substances from the environment. Langmuir monolayers have long been used to study complex systems, such as biological membranes and marine aerosols, due to their ability to shed light on intermolecular interactions. In this study, lipid mixtures with varying cholesterol and cerebroside ratios were investigated at the air/water interface. Surface tension measurements along with Brewster angle microscopy (BAM) images were used to examine the lipid phase transitions. Results indicate that cholesterol and cerebrosides form miscible monolayers, exhibiting ideal behavior. BAM images of a singular, uniform collapse phase also suggest formation of a miscible monolayer.

  5. 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

  6. 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.

  7. Halide anion dependence of ionic surfactant adsorption in air/water interface

    NASA Astrophysics Data System (ADS)

    Kim, Doseok; Wang, Wenjie; Sung, Woongmo; Ao, Mingqi; Vaknin, David

    2014-03-01

    It was recently proposed that there is surface excess of halide anions at the air/water interface, and more surface excess of I- than Br- or Cl-, which cannot be explained by Debye-Huckel theory. In case of charged surfaces such as Gibbs monolayer consisting of cationic surfactant molecules, surface excess of anions can also be expected. In this study, by using surface-sensitive grazing angle X-ray fluorescence in conjunction with surface tension measurement, we investigated adsorption behavior of [C12mim]Cl, [C12mim]Br, [C12mim]I aqueous solutions, in which the surface is first covered by [C12mim]+ cations at low concentrations, and the adsorption of the halide anions to this charged interface would follow with the increase in the concentration of solutes. From the surface tension measurements, it was observed that critical micelle concentration of [C12mim]I solution was 4.6 mM, much smaller than that of [C12mim]Cl (16.7 mM) indicating surface activity of surfactant increases with size of halide anions. From X-ray fluorescence, surface excess of halide anion was measured quantitatively from the interface of these solutions. By putting NaCl and NaI in [C12mim]I and [C12mim]Cl solutions, respectively, competition between Cl- and I- adsorption was investigated, to find that I- has stronger adsorption on the charged surface than Cl-.

  8. 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. PMID:25989368

  9. Characterization of predominantly hydrophobic poly(styrene)-poly(ethylene oxide) copolymers at air/water and cyclohexane/water interfaces

    SciTech Connect

    Gragson, D.E.; Jensen, J.M.; Baker, S.M.

    1999-09-14

    Interfacial tension measurements are employed to explore the spreading behavior of predominantly hydrophobic poly(styrene)--poly(ethylene oxide), PS-PEO, diblock copolymers at air/water and cyclohexane/water interfaces. Two copolymers with 7%- and 15.5%-PEO are examined in this study. The former is expected to have a PS block limiting area in air roughly equal to the limiting PEO pancake area, whereas the latter is expected to have a limiting PS block area in air approximately 3 times smaller than the limiting PEO pancake area. At the air/water interface, the 7%-PEO copolymer does not spread well, which is attributed to interference from the hydrophobic PS block. In contrast, the 7%-PEO copolymer spreads well at the cyclohexane/water interface, producing an isotherm with a terminating mean molecular area 3 times smaller than that obtained at the air/water interface. The 15.5%-PEO copolymer spreads well at both the air/water ad cyclohexane/water interfaces due to less interference from the smaller hydrophobic PS block. These observations are compared to compression isotherms, and the results are discussed in terms of the solvating nature of the adjacent cyclohexane phase for the PS block.

  10. 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.

  11. 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. PMID:26607026

  12. epi-Fluorescence imaging at the air-water interface of fibrillization of bovine serum albumin and human insulin.

    PubMed

    Sessions, Kristen; Sacks, Stuart; Li, Shanghao; Leblanc, Roger M

    2014-08-18

    Protein fibrillization is associated with many devastating neurodegenerative diseases. This process has been studied using spectroscopic and microscopic methods. In this study, epi-fluorescence at the air-water interface was developed as an innovative technique for observing fibrillization of bovine serum albumin and human insulin. PMID:24976597

  13. 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

  14. 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.

  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. PMID:27139819

  16. 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

  17. Compression-Induced Fusion of Glassy Core Polymer Micelles at the Air-Water Interface

    NASA Astrophysics Data System (ADS)

    Kim, Hyun Chang; Won, You-Yeon

    The surface mechanical and morphological properties of glassy core polymer micelles at the air-water interface were investigated. Asymmetric PS-PEG and PtBMA-PEG block copolymers with PEG weight fractions larger than 0.5 were formulated in the form of aqueous micelles and spread onto water. Compressed films of PS-PEG and PtBMA-PEG micelles reach high dynamic surface pressures. On the detailed level, however, PS-PEG and PtBMA-PEG micelles exhibit different surface pressure-area profiles. The PtBMA-PEG isotherm shows a transition to a plateau around a surface pressure of 24 mN/m, which is attributed to the PtBMA block as it forms a continuous film; this interpretation is supported by the fact that the surface pressure at the plateau transition is identical to the value of the spreading coefficient for PtBMA. This presents evidence that the core domains of PtBMA-PEG micelles melt and merge into a film when the micellar monolayer is laterally compressed. Such behavior was not observed with PS-PEG micelles. We suspect that under lateral compression, PtBMA-PEG micelles undergo fusion into a continuous film because PtBMA has the natural tendency to spread on the water surface, whereas PS-PEG micelles does not because the dewetting tendency of PS preventing formation of a uniform layer.

  18. 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

  19. Milk whey proteins and xanthan gum interactions in solution and at the air-water interface: a rheokinetic study.

    PubMed

    Perez, Adrián A; Sánchez, Cecilio Carrera; Patino, Juan M Rodríguez; Rubiolo, Amelia C; Santiago, Liliana G

    2010-11-01

    In this contribution, we present experimental information about the effect of xanthan gum (XG) on the adsorption behaviour of two milk whey protein samples (MWP), beta-lactoglobulin (beta-LG) and whey protein concentrate (WPC), at the air-water interface. The MWP concentration studied corresponded to the protein bulk concentration which is able to saturate the air-water interface (1.0 wt%). Temperature, pH and ionic strength of aqueous systems were kept constant at 20 degrees C, pH 7 and 0.05 M, respectively, while the XG bulk concentration varied in the range 0.00-0.25 wt%. Biopolymer interactions in solution were analyzed by extrinsic fluorescence spectroscopy using 1-anilino-8-naphtalene sulphonic acid (ANS) as a protein fluorescence probe. Interfacial biopolymer interactions were evaluated by dynamic tensiometry and surface dilatational rheology. Adsorption behaviour was discussed from a rheokinetic point of view in terms of molecular diffusion, penetration and conformational rearrangement of adsorbed protein residues at the air-water interface. Differences in the interaction magnitude, both in solution and at the interface vicinity, and in the adsorption rheokinetic parameters were observed in MWP/XG mixed systems depending on the protein type (beta-LG or WPC) and biopolymer relative concentration. beta-LG adsorption in XG presence could be promoted by mechanisms based on biopolymer segregative interactions and thermodynamic incompatibility in the interface vicinity, resulting in better surface and viscoelastic properties. The same mechanism could be responsible of WPC interfacial adsorption in the presence of XG. The interfacial functionality of WPC was improved by the synergistic interactions with XG, although WPC chemical complexity might complicate the elucidation of molecular events that govern adsorption dynamics of WPC/XG mixed systems at the air-water interface. PMID:20692133

  20. Dynamic adsorption of weakly interacting polymer/surfactant mixtures at the air/water interface.

    PubMed

    Angus-Smyth, Anna; Campbell, Richard A; Bain, Colin D

    2012-08-28

    The dynamic adsorption of polymer/surfactant mixtures containing poly(ethylene oxide) (PEO) with either tetradecyltrimethylammonium bromide (C(14)TAB) or sodium dodecyl sulfate (SDS) has been studied at the expanding air/water interface created by an overflowing cylinder, which has a surface age of 0.1-1 s. The composition of the adsorption layer is obtained by a new approach that co-models data obtained from ellipsometry and only one isotopic contrast from neutron reflectometry (NR) without the need for any deuterated polymer. The precision and accuracy of the polymer surface excess obtained matches the levels achieved from NR measurements of different isotopic contrasts involving deuterated polymer, and requires much less neutron beamtime. The PEO concentration was fixed at 100 ppm and the electrolyte concentration at 0.1 M while the surfactant concentration was varied over three orders of magnitude. For both systems, at low bulk surfactant concentrations, adsorption of the polymer is diffusion-controlled while surfactant adsorption is under mixed kinetic/diffusion control. Adsorption of PEO is inhibited once the surfactant coverage exceeds 2 μmol m(-2). For PEO/C(14)TAB, polymer adsorption drops abruptly to zero over a narrow range of surfactant concentration. For PEO/SDS, inhibition of polymer adsorption is much more gradual, and a small amount remains adsorbed even at bulk surfactant concentrations above the cmc. The difference in behavior of the two mixtures is ascribed to favorable interactions between the PEO and SDS in the bulk solution and at the surface. PMID:22746543

  1. 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.

  2. Carbon dioxide partial pressure and carbon fluxes of air-water interface in Taihu Lake, China

    NASA Astrophysics Data System (ADS)

    Fan, Chengxin; Hu, Weiping; Ford, Phillip W.; Chen, Yuwei; Qu, Wenchuan; Zhang, Lu

    2005-03-01

    To obtain carbon dioxide (CO2) flux between water-air interface of Taihu lake, monthly water samplers at 14 sites and the local meteorological data of the lake were collected and analyzed in 1998. Carbon dioxide partial pressures (pCO2) at air-water interface in the lake were calculated using alkalinity, pH, ionic strength, active coefficient, and water temperature. The carbon fluxes at different sublakes and areas were estimated by concentration gradient between water and air in consideration of Schmidt numbers of 600 and daily mean windspeed at 10 m above water surface. The results indicated that the mean values of pCO2 in Wuli Lake, Meiliang Bay, hydrophyte area, west littoral zone, riverine mouths, and the open lake areas were 1 807.8±1 071.4 (mean±standard deviation) μatm (1atm=1.013 25×105Pa), 416.3±217.0 μatm, 576.5±758.8 μatm, 304.2±243.5 μatm, 1 933.6±1 144.7 μatm, and 448.5±202.6 μatm, respectively. Maximum and minimum pCO2 values were found in the hypertrophic (4 053.7 μatm) and the eutrophic (3.2 μatm) areas. The riverine mouth areas have the maximum fluxes (82.0±62.8 mmol/m2a). But there was no significant difference between eutrophic and mesotrophic areas in pCO2 and the flux of CO2. The hydrophyte area, however, has the minimum (-0.58±12.9 mmol/m2a). In respect to CO2 equilibrium, input of the rivers will obviously influence inorganic carbon distribution in the riverine estuary. For example, the annual mean CO2 flux in Zhihugang River estuary was 19 times of that in Meiliang Bay, although the former is only a part of the latter. The sites in the body of the lake show a clear seasonal cycle with pCO2 higher than atmospheric equilibrium in winter, and much lower than atmospheric in summer due to CO2 consumption by photosynthesis. The CO2 amount of the net annual evasion that enters the atmosphere is 28.42×104 t/a, of which those from the west littoral zone and the open lake account for 53.8% and 36.7%, respectively.

  3. Surface adsorption behaviour of milk whey protein and pectin mixtures under conditions of air-water interface saturation.

    PubMed

    Perez, Adrián A; Sánchez, Cecilio Carrera; Patino, Juan M Rodríguez; Rubiolo, Amelia C; Santiago, Liliana G

    2011-07-01

    Milk whey proteins (MWP) and pectins (Ps) are biopolymer ingredients commonly used in the manufacture of colloidal food products. Therefore, knowledge of the interfacial characteristics of these biopolymers and their mixtures is very important for the design of food dispersion formulations (foams and/or emulsions). In this paper, we examine the adsorption and surface dilatational behaviour of MWP/Ps systems under conditions in which biopolymers can saturate the air-water interface on their own. Experiments were performed at constant temperature (20 °C), pH 7 and ionic strength 0.05 M. Two MWP samples, β-lactoglobulin (β-LG) and whey protein concentrate (WPC), and two Ps samples, low-methoxyl pectin (LMP) and high-methoxyl pectin (HMP) were evaluated. The contribution of biopolymers (MWP and Ps) to the interfacial properties of mixed systems was evaluated on the basis of their individual surface molecular characteristics. Biopolymer bulk concentration capable of saturating the air-water interface was estimated from surface pressure isotherms. Under conditions of interfacial saturation, dynamic adsorption behaviour (surface pressure and dilatational rheological characteristics) of MWP/Ps systems was discussed from a kinetic point of view, in terms of molecular diffusion, penetration and configurational rearrangement at the air-water interface. The main adsorption mechanism in MWP/LMP mixtures might be the MWP interfacial segregation due to the thermodynamic incompatibility between MWP and LMP (synergistic mechanism); while the interfacial adsorption in MWP/HMP mixtures could be characterized by a competitive mechanism between MWP and HMP at the air-water interface (antagonistic mechanism). The magnitude of these phenomena could be closely related to differences in molecular composition and/or aggregation state of MWP (β-LG and WPC). PMID:21440425

  4. Influence of the tyrosine environment on the second harmonic generation of iturinic antimicrobial lipopeptides at the air-water interface.

    PubMed

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

    2013-12-01

    The second harmonic generation (SHG) response at the air-water interface from the tyrosine-containing natural iturinic cyclo-lipopeptides mycosubtilin, iturin A and bacillomycin D is reported. It is shown that this response is dominated by the single tyrosine residue present in these molecules owing to the large first hyperpolarizability arising from the non-centrosymmetric aromatic ring structure of this amino acid. The SHG response of these iturinic antibiotics is also compared to the response of surfactin, a cyclo-lipopeptide with a similar l,d-amino acid sequence but lacking a tyrosine residue, and PalmATA, a synthetic linear lipopeptide possessing a single tyrosine residue but lacking the amino acid sequence structuring the cycle of the iturinic antibiotics. From the light polarization analysis of the SHG response, it is shown that the tyrosine local environment is critical in defining the SHG response of these peptides at the air-water interface. Our results demonstrate that tyrosine, similar to tryptophan, can be used as an endogenous molecular probe of peptides and proteins for SHG at the air-water interface, paving the way for SHG studies of other tyrosine-containing bioactive molecules. PMID:24149982

  5. 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

  6. 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

  7. Fluorescence light microscopy of pulmonary surfactant at the air-water interface of an air bubble of adjustable size.

    PubMed

    Knebel, D; Sieber, M; Reichelt, R; Galla, H-J; Amrein, M

    2002-07-01

    The structural dynamics of pulmonary surfactant was studied by epifluorescence light microscopy at the air-water interface of a bubble as a model close to nature for an alveolus. Small unilamellar vesicles of dipalmitoylphosphatidylcholine, dipalmitoylphosphatidylglycerol, a small amount of a fluorescent dipalmitoylphosphatidylcholine-analog, and surfactant-associated protein C were injected into the buffer solution. They aggregated to large clusters in the presence of Ca(2+) and adsorbed from these units to the interface. This gave rise to an interfacial film that eventually became fully condensed with dark, polygonal domains in a fluorescent matrix. When now the bubble size was increased or decreased, respectively, the film expanded or contracted. Upon expansion of the bubble, the dark areas became larger to the debit of the bright matrix and reversed upon contraction. We were able to observe single domains during the whole process. The film remained condensed, even when the interface was increased to twice its original size. From comparison with scanning force microscopy directly at the air-water interface, the fluorescent areas proved to be lipid bilayers associated with the (dark) monolayer. In the lung, such multilayer phase acts as a reservoir that guarantees a full molecular coverage of the alveolar interface during the breathing cycle and provides mechanical stability to the film. PMID:12080141

  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. 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

  11. 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. PMID:26427916

  12. 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

  13. Photoswitching the mechanical properties in Langmuir layers of semifluorinated alkyl-azobenzenes at the air-water interface.

    PubMed

    Theodoratou, Antigoni; Jonas, Ulrich; Loppinet, Benoit; Geue, Thomas; Stangenberg, René; Li, Dan; Berger, Rüdiger; Vlassopoulos, Dimitris

    2015-11-21

    Semifluorinated alkyl-azobenzene derivatives (SFAB) can form stable Langmuir layers at the air-water interface. These systems combine the amphiphobic character of semifluorinated alkyl units as structure-directing motifs with photochromic behavior based on the well-known reversible cis-trans isomerization upon irradiation with UV and visible light. Herein, we report our investigations of the structural and dynamic tunability of these SFAB layers at the air-water interface in response to an external light stimulus. The monolayer structures and properties of [4-(heptadecafluorooctyl)phenyl](4-octylphenyl)diazene (F8-azo-H8) and bis(4-octylphenyl)diazene (H8-azo-H8) were studied by neutron reflectivity, surface pressure-area isotherms with compression-expansion cycles, and interfacial rheology. We find that UV irradiation reversibly influences the packing behavior of the azobenzene molecules and interpret this as a transition from organized layer structures with the main axis of the molecule vertically oriented in the trans form to random packing of the cis isomer. Interestingly, this trans-cis isomerization leads to an increase in surface pressure, which is accompanied by a decrease in viscoelastic moduli. These results suggest ways of tailoring the properties of responsive fluid interfaces. PMID:26451399

  14. 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

  15. Thermometric measurements of the molecular sublayer at the air-water interface

    NASA Astrophysics Data System (ADS)

    Ward, B.; Donelan, M. A.

    2006-04-01

    A series of measurements was conducted in the Air-Sea Interaction Saltwater Tank (ASIST) to study the response of the air-water interfacial molecular sublayer under various heat flux and wind speed conditions. In-situ gradients were measured with a platinum-plated tungsten wire microthermometer, which resolved the temperature of the thermally conductive sublayer. Air-sea heat flux was controlled by changing the air-water temperature difference (ΔTAW) and the wind speed, and measurements were made for three ΔTAW regimes over a range of wind speeds. A function was fitted to the measured temperature profiles as a way of extracting the boundary layer thickness in a consistent fashion, from which the λ coefficient after Saunders (1967) was computed. This dataset returned a mean λ coefficient of 2.4 +/- 0.5, which was generally lower than previous studies, and was found to be independent of wind speed in the range of 1 to 9 ms-1.

  16. 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. PMID:25451554

  17. 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.

  18. 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. PMID:22339480

  19. 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.

  20. Adsorption at the air-water interface and emulsification properties of grain legume protein derivatives from pea and broad bean.

    PubMed

    Tsoukala, A; Papalamprou, E; Makri, E; Doxastakis, G; Braudo, E E

    2006-12-01

    Functional properties of native and modified (through induced autolysis) pea (Pisum sativum L.) and broad bean (Vicia faba L.) protein derivatives are studied. In specific, protein solubility and behavior at the air-water interface through surface pressure measurements are investigated. Furthermore the ability of the protein products to act as emulsifying agents and to stabilize emulsions is studied through oil droplet size distribution measurements and by the protein adsorbed at the oil-water interface. The data reveal that the ability of the proteins to act as surfactants and build up a rigid film around the oil droplets, mainly depends on their suitable molecular configuration and structure. Hydrolysis did not promote the functionality of the legume proteins. Broad bean exhibited better functionality than pea, before and after hydrolysis. Some comparisons were also made with lupin (Lupinus albus L.) protein isolate. PMID:17049437

  1. Coadsorption of human milk lactoferrin into the dipalmitoylglycerolphosphatidylcholine phospholipid monolayer spread at the air/water interface.

    PubMed

    Miano, Fausto; Zhao, Xiubo; Lu, Jian R; Penfold, Jeff

    2007-02-15

    The coadsorption of human milk lactoferrin into a spread monolayer of dipalmitoylglycerol phosphatidylcholine (DPPC) at the air/water interface has been studied by neutron reflection. The system is a good model of the preocular tear film outer interface, which was the motivation for the study. The association of the protein with the surface was indicated by an increase of the surface pressure exerted by the DPPC monolayer. The extent of lactoferrin coadsorption was found to decrease with increasing surface pressure in the lipid monolayer, a trend consistent with the observation reported for other proteins, such as lysozyme and beta-lactoglobulin. The neutron reflectivity measurements were subsequently carried out at the three surface pressures of 8, 15, and 35 mN/m to examine the structure and composition of lactoferrin coadsorbed at the interface. Whereas the DPPC monolayer effectively prevented lactoferrin insertion at the high surface pressure, a measurable amount of lactoferrin was found at the air/water interface at the two lower surface pressures. At 15 mN/m it was difficult to identify the distribution of lactoferrin with respect to the DPPC monolayer, due to its relatively low adsorbed amount and much broader distribution. At the lowest surface pressure of 8 mN/m, the lactoferrin coadsorption was found to increase with time over the first few hours. After 5 h the distribution of the lactoferrin layer became similar to, though quantitatively lower than, that adsorbed in the absence of the DPPC monolayer. It is characterized by a top dense sublayer of 15 A with a bottom diffuse sublayer of 60 A, indicating structural unfolding induced by surface adsorption under these conditions. PMID:17114223

  2. Coadsorption of Human Milk Lactoferrin into the Dipalmitoylglycerolphosphatidylcholine Phospholipid Monolayer Spread at the Air/Water Interface

    PubMed Central

    Miano, Fausto; Zhao, Xiubo; Lu, Jian R.; Penfold, Jeff

    2007-01-01

    The coadsorption of human milk lactoferrin into a spread monolayer of dipalmitoylglycerol phosphatidylcholine (DPPC) at the air/water interface has been studied by neutron reflection. The system is a good model of the preocular tear film outer interface, which was the motivation for the study. The association of the protein with the surface was indicated by an increase of the surface pressure exerted by the DPPC monolayer. The extent of lactoferrin coadsorption was found to decrease with increasing surface pressure in the lipid monolayer, a trend consistent with the observation reported for other proteins, such as lysozyme and β-lactoglobulin. The neutron reflectivity measurements were subsequently carried out at the three surface pressures of 8, 15, and 35 mN/m to examine the structure and composition of lactoferrin coadsorbed at the interface. Whereas the DPPC monolayer effectively prevented lactoferrin insertion at the high surface pressure, a measurable amount of lactoferrin was found at the air/water interface at the two lower surface pressures. At 15 mN/m it was difficult to identify the distribution of lactoferrin with respect to the DPPC monolayer, due to its relatively low adsorbed amount and much broader distribution. At the lowest surface pressure of 8 mN/m, the lactoferrin coadsorption was found to increase with time over the first few hours. After 5 h the distribution of the lactoferrin layer became similar to, though quantitatively lower than, that adsorbed in the absence of the DPPC monolayer. It is characterized by a top dense sublayer of 15 Å with a bottom diffuse sublayer of 60 Å, indicating structural unfolding induced by surface adsorption under these conditions. PMID:17114223

  3. 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.

  4. 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.

  5. 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. PMID:26768822

  6. 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.

  7. 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

  8. 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

  9. Studies on 2D hybrid films of half surfactant-covered Au nanoparticles at the air/water interface.

    PubMed

    Pang, Shufeng; Tetsuya, Oikawa; Tomoyuki, Watanabe; Kondo, Takeshi; Kawai, Takeshi

    2005-05-15

    A hybrid monolayer film of Au nanoparticles, half-covered with dioctadecyldimethylammonium chloride (DODAC), was prepared at the air/water interface and characterized using transmission electron microscopy (TEM), a quartz-crystal microbalance, and infrared spectra measurements. TEM images of the hybrid film showed that the distribution of Au nanoparticles depends on the surface density of DODAC and reaction time. IR spectral data provided evidence for a surface-enhanced effect of the Au nanoparticles. The wavenumber of CH(2)-stretch vibrations of DODAC in the infrared external reflection spectra revealed that the DODAC molecules were adsorbed onto the Au nanoparticles in a close-packed crystalline state for any surface density of DODAC, which is different from the usual behavior of Langmuir monolayers. PMID:15837481

  10. Effect of monolayer lipid charges on the structure and orientation of protein VAMP1 at the air-water interface.

    PubMed

    Yassine, Wissam; Milochau, Alexandra; Buchoux, Sebastien; Lang, Jochen; Desbat, Bernard; Oda, Reiko

    2010-05-01

    SNARE proteins are implicated in membrane fusion during neurotransmission and peptide hormone secretion. Relatively little is known about the molecular interactions of their trans- and juxtamembrane domains with lipid membranes. Here, we report the structure and the assembling behavior of one of the SNARE proteins, VAMP1/synaptobrevin1 incorporated in a lipid monolayer at an air-water interface which mimics the membrane environment. Our results show that the protein is extremely sensitive to surface pressure as well as the lipid composition. Monolayers of proteins alone or in the presence of the neutral phospholipid DMPC underwent structural transition from alpha-helix to beta-sheet upon surface compression. In contrast, the anionic phospholipid DMPG inhibited this transition in a concentration-dependent manner. Moreover, the orientation of the proteins was highly sensitive to the charge density of the lipid layers. Thus, the structure of VAMP1 is clearly controlled by protein-lipid interactions. PMID:20085749

  11. Semiconductor Conjugated Polymer-Quantum Dot Nanocomposites at the Air/Water Interface and Their Performance in Thin Film Solar Cells

    NASA Astrophysics Data System (ADS)

    Lin, Zhiqun; Goodman, Matthew; Xu, Jun; Wang, Jun

    2009-03-01

    Organic-inorganic nanocomposites consisting of electroactive conjugated polymer, poly(3-hexylthiophene) (P3HT) intimately tethered on the surface of semiconductor CdSe quantum dot (i.e., P3HT-CdSe nanocomposites) at the air/water interface formed via Langmuir isotherms were explored for the first time. The P3HT-CdSe nanocomposites displayed a high pressure plateau in the Langmuir isotherm, illustrating their complex packing at the air/water interface. Furthermore, photovoltaic devices fabricated from the LB depositions of the P3HT-CdSe nanocomposites exhibited a relatively high short circuit current, ISC, while maintaining a thin film profile. These studies provide insights into the fundamental behaviors of semiconductor organic-inorganic nanocomposites confined at the air/water interface as well as in the active layer of an organic-based photovoltaic device.

  12. 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.

  13. 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

  14. 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

  15. Anomalously large electro-optic Pockels effect at the air-water interface with an electric field applied parallel to the interface

    NASA Astrophysics Data System (ADS)

    Suzuki, Yuto; Osawa, Kengo; Yukita, Shunpei; Kobayashi, Takayoshi; Tokunaga, Eiji

    2016-05-01

    The optical Pockels effect was observed at the air-water interface by electromodulation spectroscopy. When an AC electric field of frequency f was applied parallel to a water surface between Pt electrodes, the field induced a change in the transmitted light intensity synchronized at 1f proportional to the field strength. The 1f signals dominated over 2f signals by one order of magnitude and the signal disappeared when the electrodes were completely immersed under the water surface, strongly suggesting that the observed phenomena were due to the Pockels effect at the air-water interface. The Pockels coefficient was estimated to be | r | = 1.4 × 105 pm/V, which is much larger than that at the solid-water interface. However, this is unusual because the parallel electric field does not induce the break in inversion symmetry required for the appearance of the Pockels effect. The electrowetting effect was experimentally ruled out as a mechanism for the Pockels effect, and this made the existence of a field perpendicular to the surface, although extremely weak, the most likely explanation.

  16. Protein Folding at the Air-Water Interface Studied with X-Ray Reflectivity

    NASA Astrophysics Data System (ADS)

    Gidalevitz, David; Huang, Zhengqing; Rice, Stuart A.

    1999-03-01

    We report the results of x-ray reflectivity measurements of thin films formed by different water-soluble proteins at the air-aqueous solution interface. It is demonstrated that glucose oxidase, alcohol dehydrogenase, and urease molecules denaturate at the air-aqueous solution interface to form 8- to 14- angstrom -thick peptide sheets. X-ray reflectivity data indicate that the spreading of a lipid monolayer at the aqueous solution surface before protein injection does not prevent proteins from unfolding. On the other hand, crosslinking of proteins results in intact enzyme layers at the subphase surface. A model that involves interaction of glucose oxidase molecules with a phospholipid monolayer is proposed. In this model, an observed decrease of the lipid electron density in the protein presence is explained in terms of "holes" in the monolayer film caused by protein molecule adsorption.

  17. Structure of Human Annexin A6 at the Air-Water Interface and in a Membrane-Bound State

    PubMed Central

    Golczak, Marcin; Kirilenko, Aneta; Bandorowicz-Pikula, Joanna; Desbat, Bernard; Pikula, Slawomir

    2004-01-01

    We postulate the existence of a pH-sensitive domain in annexin A6 (AnxA6), on the basis of our observation of pH-dependent conformational and orientation changes of this protein and its N- (AnxA6a) and C-terminal (AnxA6b) halves in the presence of lipids. Brewster angle microscopy shows that AnxA6, AnxA6a, and AnxA6b in the absence of lipids accumulate at the air-water interface and form a stable, homogeneous layer at pH below 6.0. Under these conditions polarization modulation IR absorption spectroscopy reveals significant conformational changes of AnxA6a whereas AnxA6b preserves its α-helical structure. The orientation of protein α-helices is parallel with respect to the interface. In the presence of lipids, polarization modulation IR reflection absorption spectroscopy experiments suggest that AnxA6a incorporates into the lipid/air interface, whereas AnxA6b is adsorbed under the lipid monolayer. In this case AnxA6a regains its α-helical structures. At a higher pressure of the lipid monolayer the average orientation of the α-helices of AnxA6a changes from flat to tilted by 45° with respect to normal to the membrane interface. For AnxA6b no such changes are detected, even at a high pressure of the lipid monolayer—suggesting that the putative pH-sensitive domain of AnxA6 is localized in the N-terminal half of the protein. PMID:15298924

  18. 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

  19. 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. PMID:26524255

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. pH effects on the molecular structure of β-lactoglobulin modified air-water interfaces and its impact on foam rheology.

    PubMed

    Engelhardt, Kathrin; Lexis, Meike; Gochev, Georgi; Konnerth, Christoph; Miller, Reinhard; Willenbacher, Norbert; Peukert, Wolfgang; Braunschweig, Björn

    2013-09-17

    Macroscopic properties of aqueous β-lactoglobulin (BLG) foams and the molecular properties of BLG modified air-water interfaces as their major structural element were investigated with a unique combination of foam rheology measurements and interfacial sensitive methods such as sum-frequency generation and interfacial dilatational rheology. The molecular structure and protein-protein interactions at the air-water interface can be changed substantially with the solution pH and result in major changes in interfacial dilational and foam rheology. At a pH near the interfacial isoelectric point BLG molecules carry zero net charge and disordered multilayers with the highest interfacial dilatational elasticity are formed at the air-water interface. Increasing or decreasing the pH with respect to the isoelectric point leads to the formation of a BLG monolayer with repulsive electrostatic interactions among the adsorbed molecules which decrease the interfacial dilational elasticity. The latter molecular information does explain the behavior of BLG foams in our rheological studies, where in fact the highest apparent yield stresses and storage moduli are established with foams from electrolyte solutions with a pH close to the isoelectric point of BLG. At this pH the gas bubbles of the foam are stabilized by BLG multilayers with attractive intermolecular interactions at the ubiquitous air-water interfaces, while BLG layers with repulsive interactions decrease the apparent yield stress and storage moduli as stabilization of gas bubbles with a monolayer of BLG is less effective. PMID:23961700

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

    PubMed

    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. PMID:27276960

  6. Stabilization of alkylated azacrown ether by fatty acid at the air-water interface.

    PubMed

    Zarbakhsh, Ali; Campana, Mario; Webster, John R P; Wojciechowski, Kamil

    2010-12-01

    The adsorbed amount of partially deuterated dihexadecyl-diaza-18-crown-6 ether (d-ACE16) in the presence of different chain length fatty acids as a function of surface pressure was determined by neutron reflectometry technique. The highest adsorbed amount of the azacrown ether was observed for the mixture of ACE16 with hexadecanoic (palmitic) acid, pointing to the importance of chain length matching between the two species for optimum stabilization of the mixed monolayer. The contrast variation technique was used to estimate the contribution to the total adsorbed amount from stearic acid and ACE16. It was found that the mixed Langmuir monolayer is stable against dissolution up to a surface pressure of 20 mN m(-1). Above this pressure, however, the spread and adsorbed amounts start to deviate, indicative of partial dissolution into the aqueous subphase. The consequences of this behavior for the transport of metal ions through the interfaces of permeation liquid membranes (PLMs) are discussed. PMID:21049946

  7. 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.

  8. Organization of T-shaped facial amphiphiles at the air/water interface studied by infrared reflection absorption spectroscopy.

    PubMed

    Schwieger, Christian; Chen, Bin; Tschierske, Carsten; Kressler, Jörg; Blume, Alfred

    2012-10-11

    We studied the behavior of monolayers at the air/water interface of T-shaped facial amphiphiles which show liquid-crystalline mesophases in the bulk. The compounds are composed of a rigid p-terphenyl core (TP) with two terminal hydrophobic ether linked alkyl chains of equal length and one facial hydrophilic tri(ethylene oxide) chain with a carboxylic acid end group. Due to their amphiphilic nature they form stable Langmuir films at the air/water interface. Depending on the alkyl chain length they show markedly different compression isotherms. We used infrared reflection absorption spectroscopy (IRRAS) to study the changes in molecular organization of the TP films upon compression. We could retrieve information on layer thickness, alkyl chain crystallization, and the orientation of the TP cores within the films. Films of TPs with long (16 carbon atoms: TP 16/3) and short (10 carbon atoms: TP 10/3) alkyl chains were compared. Compression of TP 16/3 leads to crystallization of the terminal alkyl chains, whereas the alkyl chains of TP 10/3 stay fluid over the complete compression range. TP 10/3 shows an extended plateau in the compression isotherm which is due to a layering transition. The mechanism of this layering transition is discussed. Special attention was paid to the question of whether a so-called roll-over collapse occurs during compression. From the beginning to the end of the plateau, the layer thickness is increased from 15 to 38 Å and the orientation of the TP cores changes from parallel to the water surface to isotropic. We conclude that the plateau in the compression isotherm reflects the transition of a TP monolayer to a TP multilayer. The monolayer consists of a sublayer of well-organized TP cores underneath a sublayer of fluid alkyl chains whereas the multilayer consists of a well oriented bottom layer and a disordered top layer. Our findings do not support the model of a roll-over collapse. This study demonstrates how the IRRA band intensity of OH

  9. Hierarchical assembly of an achiral pi-conjugated molecule into a chiral nanotube through the air/water interface.

    PubMed

    Yao, Pingping; Wang, Haifeng; Chen, Penglei; Zhan, Xiaowei; Kuang, Xun; Zhu, Daoben; Liu, Minghua

    2009-06-16

    An achiral pi-conjugated fluorinated fused pyrazine derivative has been spread at the air/water interface, and its assembling property is investigated. It has been found that the compound, although without any long alkyl chain, could be spread as a floating film on water surface, the surface pressure of which can be compressed up to ca. 70 mN/m. An inflection point has been observed in the isotherm of the floating film on water surface. The atomic force microscope (AFM), scanning electron microscope (SEM) as well as the transmission electron microscope (TEM) observations revealed that the floating film first formed a multilayer structure and then was compressed into nanotubes after the inflection region as a result of the rolling of the ultrathin film. Interestingly, the rolled nanotubes show circular dichroism although the molecule itself is an achiral species, suggesting the chiral nanotube is predominantly produced on the water surface. The investigation provides an effective way to fabricate supramolecular-based organic chiral nanotubes through an interfacial supramolecular assembly process. PMID:19459675

  10. 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

  11. FTIR external reflectance studies of lipid monolayers at the air-water interface: Applications to pulmonary surfactant

    NASA Astrophysics Data System (ADS)

    Wilkin, Jennifer M.; Dluhy, Richard A.

    1998-06-01

    FTIR external reflectance spectra of monomolecular films of natural products and model mixtures relevant to pulmonary surfactant physiology were collected concurrently with surface measurements directly at the air-water interface. Films studied were calf lung surfactant extract (CLSE) and its phospholipid fraction (PPL) along with 2:1 DPPC-d62:DPPG and 2:1 DPPC-d62:DOPG containing 0, 1 or 2 wt % of the hydrophobic surfactant proteins SP-B and SP-C (SP-B+C). The CH2 antisymmetric and symmetric stretching bands (~2920 and 2852 cm-1) along with the analogous CD2 stretching bands (~2194 and 2089 cm-1) were analyzed, and band heights, integrated intensities and peak frequency positions were plotted as a function of measured surface pressure. Data suggest that 2:1 DPPC-d62:DPPG+2 wt % SP-B+C is the most ordered and stable of the films and can be compressed to the highest sustainable surface pressure. Data from the model mixtures indicate that the surfactant protein interacts differently with each of the lipid components. Plots of the CH/CD intensity ratios versus surface pressure show an increase in this ratio upon the addition of SP-B+C as the protein apparently orders the CH component (DPPG or DOPG) and slightly disorders the CD component (DPPC-d62).

  12. Superposition-additive approach: thermodynamic parameters of clusterization of monosubstituted alkanes at the air/water interface.

    PubMed

    Vysotsky, Yu B; Belyaeva, E A; Fomina, E S; Fainerman, V B; Aksenenko, E V; Vollhardt, D; Miller, R

    2011-12-21

    The applicability of the superposition-additive approach for the calculation of the thermodynamic parameters of formation and atomization of conjugate systems, their dipole electric polarisabilities, molecular diamagnetic susceptibilities, π-electron circular currents, as well as for the estimation of the thermodynamic parameters of substituted alkanes, was demonstrated earlier. Now the applicability of the superposition-additive approach for the description of clusterization of fatty alcohols, thioalcohols, amines, carboxylic acids at the air/water interface is studied. Two superposition-additive schemes are used that ensure the maximum superimposition of the graphs of the considered molecular structures including the intermolecular CH-HC interactions within the clusters. The thermodynamic parameters of clusterization are calculated for dimers, trimers and tetramers. The calculations are based on the values of enthalpy, entropy and Gibbs' energy of clusterization calculated earlier using the semiempirical quantum chemical PM3 method. It is shown that the proposed approach is capable of the reproduction with sufficiently enough accuracy of the values calculated previously. PMID:22042000

  13. Influence of temperature on microdomain organization of mixed cationic-zwitterionic lipidic monolayers at the air-water interface.

    PubMed

    Bordi, F; Cametti, C; Di Venanzio, C; Sennato, S; Zuzzi, S

    2008-02-15

    The thermodynamic behavior of mixed DOTAP-DPPC monolayers at the air-water interface has been investigated in the temperature range from 15 to 45 degrees C, covering the temperature interval where the thermotropic phase transition of DPPC, from solid-like to liquid-like, takes place. Based on the regular solution theory, the miscibility of the two lipids in the mixed monolayer was evaluated in terms of the excess Gibbs free energy of mixing DeltaG(ex), activity coefficients f(1) and f(2) and interaction parameter omega between the two lipids. The mixed DOTAP-DPPC film was found to have positive deviations from ideality at low DOTAP mole fractions, indicating a phase-separated binary mixture. This effect depends on the temperature and is largely conditioned by the structural chain conformation of the DPPC lipid monolayer. The thermodynamic parameters associated to the stability and the miscibility of these two lipids in a monolayer structure have been discussed in the light of the phase diagram of the DOTAP-DPPC aqueous mixtures obtained from differential scanning calorimetry measurements. The correlation between the temperature behavior of DOTAP-DPPC monolayers and their bulk aqueous mixtures has been briefly discussed. PMID:17936597

  14. 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.

  15. Investigating Langmuir films at the air-water interface using a planar array infrared reflection-absorption spectrograph

    NASA Astrophysics Data System (ADS)

    Kim, Young Shin

    In this work, a new planar array infrared reflection-absorption spectrograph (PA-IRRAS) was developed to investigate a broad range of Langmuir films at the air-water interface. This instrument is capable of recording sample and reference spectra simultaneously with an optical setup that is the same as that of a single-beam instrument but splits the incident infrared beam into two sections on a plane mirror (H) or a water trough. With this design, the instrument could accommodate large infrared accessories, such as a water trough. In addition, water bands were subtracted to obtain a high quality spectrum for a poly(lactic acid) (PLA) Langmuir film on the water subphase with a resolution of about 8 cm-1 in 10.8 sec. With this instrument, two types of monolayer systems were studied; polymeric and lipid Langmuir films at the air-water interface. For the polymeric monolayer system, PA-IRRAS was used as a probe to follow the real-time conformational changes associated with intermolecular interactions of the polymer chains during the compression of the monolayers. It was found that the mixture of poly(D-lactic acid) (PDLA) and poly(L-lactic acid) (PLLA) (D/L) formed a stereocomplex when the mixed solution developed the two-dimensional monolayer at the air-water interface. The stereocomplexation occurred before film compression, indicating that there is no direct correlation between film compression and stereocomplexation. For the lipid monolayer system, PA-IRRAS was also used as a probe to investigate the origin of the disruption of a lipid monolayer upon protein adsorption at the air-water interface. Analysis of the time-resolved PA-IRRAS spectra revealed that Cu(II) ion-chelated DSIDA lipid monolayer (Cu 2+-DSIDA) was readily disrupted by myoglobin adsorption as demonstrated by a blue shift of 1.7 cm-1 and a lower intensity in the vas(CH2) stretch mode of the lipid monolayer over a period of five hours. To find the origin of the disruption of the lipid monolayer, a

  16. Calcium phosphate growth beneath a polycationic monolayer at the air-water interface: effects of oscillating surface pressure on mineralization.

    PubMed

    Junginger, Mathias; Bleek, Katrin; Kita-Tokarczyk, Katarzyna; Reiche, Jürgen; Shkilnyy, Andriy; Schacher, Felix; Müller, Axel H E; Taubert, Andreas

    2010-11-01

    The self-assembly of the amphiphilic block copolymer poly(butadiene)-block-poly[2-(dimethylamino)ethyl methacrylate] at the air-water interface and the mineralization of the monolayers with calcium phosphate was investigated at different pH values. As expected for polyelectrolytes, the subphase pH strongly affects the monolayer properties. The focus of the current study, however, is on the effect of an oscillating (instead of a static) polymer monolayer on calcium phosphate mineralization. Monitoring of the surface pressure vs. mineralization time shows that the monolayer is quite stable if the mineralization is performed at pH 8. In contrast, the monolayer at pH 5 shows a measurable decrease of the surface pressure already after ca. 2 h of mineralization. Transmission electron microscopy reveals that mineralization at low pH under constant oscillation leads to small particles, which are arranged in circular features and larger entities with holes of ca. 200 nm. The larger features with the holes disappear as the mineralization is continued in favor of the smaller particles. These grow with time and form necklace-like architectures of spherical particles with a uniform diameter. In contrast, mineralization at pH 8 leads to very uniform particle morphologies already after 2 h. The mineralization products consist of a circular feature with a dark dot in the center. The increasing contrast of the precipitates in the electron micrographs with mineralization time indicates an increasing degree of mineralization vs. reaction time. The study therefore shows that mechanical effects on mineralization at interfaces are quite complex. PMID:20835481

  17. Calcium phosphate growth beneath a polycationic monolayer at the air-water interface: effects of oscillating surface pressure on mineralization

    NASA Astrophysics Data System (ADS)

    Junginger, Mathias; Bleek, Katrin; Kita-Tokarczyk, Katarzyna; Reiche, Jürgen; Shkilnyy, Andriy; Schacher, Felix; Müller, Axel H. E.; Taubert, Andreas

    2010-11-01

    The self-assembly of the amphiphilic block copolymer poly(butadiene)-block-poly[2-(dimethylamino)ethyl methacrylate] at the air-water interface and the mineralization of the monolayers with calcium phosphate was investigated at different pH values. As expected for polyelectrolytes, the subphase pH strongly affects the monolayer properties. The focus of the current study, however, is on the effect of an oscillating (instead of a static) polymer monolayer on calcium phosphate mineralization. Monitoring of the surface pressure vs. mineralization time shows that the monolayer is quite stable if the mineralization is performed at pH 8. In contrast, the monolayer at pH 5 shows a measurable decrease of the surface pressure already after ca. 2 h of mineralization. Transmission electron microscopy reveals that mineralization at low pH under constant oscillation leads to small particles, which are arranged in circular features and larger entities with holes of ca. 200 nm. The larger features with the holes disappear as the mineralization is continued in favor of the smaller particles. These grow with time and form necklace-like architectures of spherical particles with a uniform diameter. In contrast, mineralization at pH 8 leads to very uniform particle morphologies already after 2 h. The mineralization products consist of a circular feature with a dark dot in the center. The increasing contrast of the precipitates in the electron micrographs with mineralization time indicates an increasing degree of mineralization vs. reaction time. The study therefore shows that mechanical effects on mineralization at interfaces are quite complex.

  18. 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

  19. 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

  20. Enhanced stabilization of aerosol-OT surfactant monolayer upon interaction with small amounts of bovine serum albumin at the air-water interface.

    PubMed

    Caetano, Wilker; Ferreira, Marystela; Oliveira, Osvaldo N; Itri, Rosangela

    2004-10-10

    An investigation is made of the influence from small amounts of the protein bovine serum albumin (BSA) on the lateral organization of low molecular weight surfactant sodium bis-2-ethylhexyl sulfosuccinate (AOT) at the air-water interface. Surface pressure (pi - A), surface potential (deltaV - A) and Brewster angle microscopy (BAM) experiments were carried out, with particular emphasis on the monolayer stability under successive compression-expansion cycles. AOT monolayer is not stable at the air-water interface, which means that the majority of AOT molecules go into the aqueous subphase as monomers and/or normal micelles. When a waiting time elapses between spreading and compression, the surfactant monolayer tends to reorganize partially at the air-water interface, with a monolayer expansion being observed for waiting times as large as 12 h. The incorporation of very small amount of BSA (10(-9)M) at the interface, also inferred from BAM, increases the monolayer stability as revealed by pi - A and deltaV - A results. For a waiting time of circa 3 h, the mixed monolayer reaches its maximum stability. This must be related to protein (and/or protein-surfactant complexes) adsorbed onto the AOT monolayer, thus altering the BSA conformation to accommodate its hydrophobic/hydrophilic residues. Furthermore, the effects from such small amounts of BSA in the monolayer formation and stabilization mean that the AOT monolayer responds cooperatively to BSA. PMID:15465300

  1. 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

  2. Unusual Adsorption at the Air-Water Interface of a Zwitterionic Carboxybetaine with a Large Charge Separation.

    PubMed

    Ma, Kun; Li, Pei Xun; Dong, Chu Chuan; Thomas, Robert K; Penfold, Jeffrey

    2016-04-12

    The structures of layers of three different dodecylcarboxybetaine surfactants adsorbed at the air-water interface have been determined by neutron reflection. The zwitterionic compounds differed in the length of the spacer separating the quaternary ammonium and carboxylate groups, which was (CH2)1, (CH2)4, or (CH2)8. The limiting area per molecule was found to be 45, 52, or 84 Å(2), respectively, and compared reasonably with results from surface tension showing that the Gibbs prefactor is 1 in each case. Isotopic labeling was used to distinguish between the position of the alkyl and spacer groups in the layer. The spacer was found to be well-immersed in water for the (CH2)1 and (CH2)4 spacers but significantly above water for the (CH2)8 spacer. The distribution of the (CH2)8 spacer along the surface normal was found to be similar to that of the dodecyl group; i.e., it projects out of the water, contrary to an earlier hypothesis that it forms a loop. Comparison of the overlap of water with dodecyl and spacer groups also indicates that the (CH2)8 spacer is well out of the water. This in turn suggests that the anionic carboxylic acid group, which is dissociated in solution, is not ionized in the adsorbed layer. A further observation is that the dodecylcarboxybetaine with the (CH2)8 spacer reaches surface saturation at one-tenth of the critical micelle concentration. This is highly unusual and is attributed to the long spacer destabilizing the micelle relative to the surface layer. PMID:27010322

  3. 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. PMID:24762096

  4. 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

  5. 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

  6. 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

  7. Interaction of poly(ethylene-glycols) with air-water interfaces and lipid monolayers: investigations on surface pressure and surface potential.

    PubMed Central

    Winterhalter, M; Bürner, H; Marzinka, S; Benz, R; Kasianowicz, J J

    1995-01-01

    We have characterized the surface activity of different-sized poly(ethylene-glycols) (PEG; M(r) 200-100,000 Da) in the presence or absence of lipid monolayers and over a wide range of bulk PEG concentrations (10(-8)-10% w/v). Measurements of the surface potential and surface pressure demonstrate that PEGs interact with the air-water and lipid-water interfaces. Without lipid, PEG added either to the subphase or to the air-water interface forms relatively stable monolayers. Except for very low molecular weight polymers (PEGs < 1000 Da), low concentrations of PEG in the subphase (between 10(-5) and 10(-4)% w/v) increase the surface potential from zero (with respect to the potential of a pure air-water interface) to a plateau value of approximately 440 mV. At much higher polymer concentrations, > 10(-1)% (w/v), depending on the molecular weight of the PEG and corresponding to the concentration at which the polymers in solution are likely to overlap, the surface potential decreases. High concentrations of PEG in the subphase cause a similar decrease in the surface potential of densely packed lipid monolayers spread from either diphytanoyl phosphatidylcholine (DPhPC), dipalmitoyl phosphatidylcholine (DPPC), or dioleoyl phosphatidylserine (DOPS). Adding PEG as a monolayer at the air-water interface also affects the surface activity of DPhPC or DPPC monolayers. At low lipid concentration, the surface pressure and potential are determined by the polymer. For intermediate lipid concentrations, the surface pressure-area and surface potential-area isotherms show that the effects due to lipid and PEG are not always additive and that the polymer's effect is distinct for the two lipids. When PEG-lipid-mixed monolayers are compressed to surface pressures greater than the collapse pressure for a PEG monolayer, the surface pressure-area and surface potential-area isotherms approach that of the lipid alone, suggesting that for this experimental condition PEG is expelled from the

  8. External reflection FTIR of peptide monolayer films in situ at the air/water interface: experimental design, spectra-structure correlations, and effects of hydrogen-deuterium exchange.

    PubMed Central

    Flach, C R; Brauner, J W; Taylor, J W; Baldwin, R C; Mendelsohn, R

    1994-01-01

    A Fourier transform infrared spectrometer has been interfaced with a surface balance and a new external reflection infrared sampling accessory, which permits the acquisition of spectra from protein monolayers in situ at the air/water interface. The accessory, a sample shuttle that permits the collection of spectra in alternating fashion from sample and background troughs, reduces interference from water vapor rotation-vibration bands in the amide I and amide II regions of protein spectra (1520-1690 cm-1) by nearly an order of magnitude. Residual interference from water vapor absorbance ranges from 50 to 200 microabsorbance units. The performance of the device is demonstrated through spectra of synthetic peptides designed to adopt alpha-helical, antiparallel beta-sheet, mixed beta-sheet/beta-turn, and unordered conformations at the air/water interface. The extent of exchange on the surface can be monitored from the relative intensities of the amide II and amide I modes. Hydrogen-deuterium exchange may lower the amide I frequency by as much as 11-12 cm-1 for helical secondary structures. This shifts the vibrational mode into a region normally associated with unordered structures and leads to uncertainties in the application of algorithms commonly used for determination of secondary structure from amide I contours of proteins in D2O solution. PMID:7919013

  9. 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.

  10. 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.

  11. 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

  12. 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

  13. 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. PMID:26982820

  14. How does spacer length of imidazolium gemini surfactants control the fabrication of 2D-Langmuir films of silver-nanoparticles at the air-water interface?

    PubMed

    Datta, Sougata; Biswas, Joydeep; Bhattacharya, Santanu

    2014-09-15

    A series of gemini surfactants based on cationic imidazolium ring as polar headgroup, abbreviated as [Im-n-Im], 2Br(-) (n=2, 5, 6 and 12), was synthesized. Their ability to stabilize silver nanoparticles in aqueous media was investigated. The resulting suspensions were characterized by UV-Vis spectroscopy and transmission electron microscopy (TEM). They exhibit specific morphologies by adopting different supramolecular assemblies in aqueous media depending on the internal packing arrangements and on the number of spacer methylene units [-(CH2)n-]. Individual colloids were extracted from the aqueous to chloroform layer and spread at the air/water interface to allow the formation of well-defined Langmuir films. By analysis of the surface pressure-area isotherms, the details about the packing behavior and orientation of the imidazolium gemini surfactant capped silver nanoparticles were obtained. Morphological features of the dynamic process of monolayer compression at the air-water interface were elucidated using Brewster angle microscopy (BAM). These monolayers were further transferred on mica sheets by the Langmuir-Blodgett technique at their associated collapse pressure and the morphology of these monolayers was investigated by atomic force microscopy (AFM). The number of spacer methylene units [-(CH2)n-] of the gemini surfactants exerted critical influence in modulating the characteristics of the resulting Langmuir films. PMID:24998058

  15. Ellipsometric study of molecular orientations of Thermomyces lanuginosus lipase at the air-water interface by simultaneous determination of refractive index and thickness.

    PubMed

    Muth, Marco; Schmid, Reiner P; Schnitzlein, Klaus

    2016-04-01

    Ellipsometric studies of very thin organic films suffer from the low refractive index contrast between layer and bulk substrate. We demonstrate that null ellipsometry can not only provide detailed information about the adsorption kinetics and surface excess values, but in addition on layer thicknesses with submonolayer resolution of a lipase from Thermomyces lanuginosus at the air-water interface. While measuring very close to the Brewster angle, refractive indices and layer-thicknesses can both be determined with a precision that is sufficiently high to make conclusions on the density and orientation of the molecules at the interface. The orientation was found to be concentration- and pH value-dependent. At the isoelectric point, the lipase was almost vertically oriented with respect to the surface, while for pure distilled water and low lipase concentration a rather horizontal alignment was found. Further experiments, varying the size of the interfacial area in a Langmuir trough, confirm the different layer structures. PMID:26735895

  16. 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

  17. 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. PMID:25697294

  18. 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.

  19. Savinase action on bovine serum albumin (BSA) monolayers demonstrated with measurements at the air-water interface and liquid Atomic Force Microscopy (AFM) imaging.

    PubMed

    Balashev, Konstantin; Callisen, Thomas H; Svendsen, Allan; Bjørnholm, Thomas

    2011-12-01

    We studied the enzymatic action of Savinase on bovine serum albumin (BSA) organized in a monolayer spread at the air/water interface or adsorbed at the mica surface. We carried out two types of experiments. In the first one we followed the degradation of the protein monolayer by measuring the surface pressure and surface area decrease versus time. In the second approach we applied AFM imaging of the supported BSA monolayers adsorbed on mica solid supports and extracted information for the enzyme action by analyzing the obtained images of the surface topography in the course of enzyme action. In both cases we obtained an estimate for the turnover number (TON) of the enzyme reaction. PMID:21868205

  20. Solution self-assembly and adsorption at the air-water interface of the monorhamnose and dirhamnose rhamnolipids and their mixtures.

    PubMed

    Chen, M L; Penfold, J; Thomas, R K; Smyth, T J P; Perfumo, A; Marchant, R; Banat, I M; Stevenson, P; Parry, A; Tucker, I; Grillo, I

    2010-12-01

    The self-assembly in solution and adsorption at the air-water interface, measured by small-angle neutron scattering, SANS, and neutron reflectivity, NR, of the monorhamnose and dirhamnose rhamnolipids (R1, R2) and their mixtures, are discussed. The production of the deuterium-labeled rhamnolipids (required for the NR studies) from a Pseudomonas aeruginosa culture and their separation into the pure R1 and R2 components is described. At the air-water interface, R1 and R2 exhibit Langmuir-like adsorption isotherms, with saturated area/molecule values of about 60 and 75 Å(2), respectively. In R1/R2 mixtures, there is a strong partitioning of R1 to the surface and R2 competes less favorably because of the steric or packing constraints of the larger R2 dirhamnose headgroup. In dilute solution (<20 mM), R1 and R2 form small globular micelles, L(1), with aggregation numbers of about 50 and 30, respectively. At higher solution concentrations, R1 has a predominantly planar structure, L(α) (unilamellar, ULV, or bilamellar, BLV, vesicles) whereas R2 remains globular, with an aggregation number that increases with increasing surfactant concentration. For R1/R2 mixtures, solutions rich in R2 are predominantly micellar whereas solutions rich in R1 have a more planar structure. At an intermediate composition (60 to 80 mol % R1), there are mixed L(α)/L(1) and L(1)/L(α) regions. However, the higher preferred curvature associated with R2 tends to dominate the mixed R1/R2 microstructure and its associated phase behavior. PMID:21028852

  1. Visualization of an adsorption model for surfactant transport from micelle solutions to a clean air/water interface using fluorescence microscopy.

    PubMed

    Song, Qing; Yuan, Mingjun

    2011-05-01

    This work pertains to visualizing a transport model for adsorption of surfactants from micelle solutions onto a clean air/water interface. Under the condition of surfactant adsorption from very dilute solutions, the time scale for diffusion of a surfactant monomer is much slower than the time scale for kinetic breakdown of the aggregates. A theoretical model predicts two regimes for the adsorption dynamics. We visualize these two regimes under the mechanism of solubilization using fluorescence microscopy, in which an insoluble fluorescent probe, NBD-HAD (4-(hexadecylamino)-7-nitrobenz-2-oxa-1,3-diazole), is used to illuminate the micelles. The dye fluoresces in the microenvironment of micelles but is quenched in the aqueous solution on laser excitation. The region containing micelles is illuminated, but the region which does not contain micelles appears dark. For surfactant solution of C(14)E(6) at concentration just above the critical micelle concentration (C(CMC)), C(CMC)=4.4 mg/L, a dark region between the bright image of the air/water interface and the micelle-containing zone is observed. This dark region becomes smaller with time and finally disappears once equilibrium is reached. For a surfactant solution of C(14)E(6) at the concentration of 4.74C(CMC), which is higher than a critical total surfactant concentration (C(T)(c)) of 4.25C(CMC), we observe bright images through surfactant solutions during the adsorption process. Fluorescence images validate the theoretical model. PMID:21349535

  2. 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

  3. 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.

  4. Quantum chemical approach in the description of the amphiphile clusterization at the air/liquid and liquid/liquid interfaces with phase nature accounting. I. Aliphatic normal alcohols at the air/water interface.

    PubMed

    Vysotsky, Yuri B; Belyaeva, Elena A; Kartashynska, Elena S; Fainerman, Valentine B; Smirnova, Natalia A

    2015-02-19

    A new model based on the quantum chemical approach is proposed to describe structural and thermodynamic parameters of clusterization for substituted alkanes at the air/liquid and liquid/liquid interfaces. The new model by the authors, unlike the previous one, proposes an explicit account of the liquid phase (phases) influence on the parameters of monomers, clusters and monolayers of substituted alkanes at the regarded interface. The calculations were carried out in the frameworks of the quantum chemical semiempirical PM3 method (Mopac 2012), using the COSMO procedure. The new model was tested in the calculations of the clusterization parameters of fatty alcohols under the standard conditions at the air/water interface. The enthalpy, Gibbs' energy and absolute entropy of formation for alcohol monomers alongside with clusterization parameters for the cluster series including the monolayer at air/water interface were calculated. In our calculations the sinkage of monomers, molecules in clusters and monolayers was varied from 1 up to 5 methylene groups. Thermodynamic parameters calculated using the proposed model for the alcohol monolayers are in a good agreement with the corresponding experimental data. However, the proposed model cannot define the most energetically preferable immersion of the monolayer molecules in the water phase. PMID:25640463

  5. 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. PMID:22051345

  6. 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

  7. 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

  8. 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.

  9. 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. PMID:25644035

  10. Conformational analyses of bacillomycin D, a natural antimicrobial lipopeptide, alone or in interaction with lipid monolayers at the air-water interface.

    PubMed

    Nasir, Mehmet Nail; Besson, Françoise

    2012-12-01

    Bacillomycin D is a natural antimicrobial lipopeptide belonging to the iturin family. It is produced by Bacillus subtilis strains. Bacillomycin D is characterized by its strong antifungal and hemolytic properties, due to its interaction with the plasma membrane of sensitive cells. Until now, only few limited analyses were conducted to understand the biological activities of bacillomycin D at the molecular level. Our purpose was to analyze the conformation of bacillomycin D using IR spectroscopy and to model its interactions with cytoplasmic membranes using Langmuir interfacial monolayers. Our findings indicate that bacillomycin D contains turns and allow to model its three-dimensional structure. Bacillomycin D formed a monolayer film at the air-water interface and kept its turn conformation, as shown by polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS). To identify the membrane lipid target of bacillomycin D, its interactions with pure lipid monolayers were analyzed and an original behavior of the lipopeptide toward cholesterol-containing monolayers was shown. This original behavior was lost when bacillomycin D was interacting with pure cholesteryl acetate monolayers, suggesting the involvement of the alcohol group of cholesterol in the lipopeptide-cholesterol interaction. PMID:22967349

  11. Miscibility of dl-α-tocopherol β-glucoside in DPPC monolayer at air/water and air/solid interfaces.

    PubMed

    Neunert, G; Makowiecki, J; Piosik, E; Hertmanowski, R; Polewski, K; Martynski, T

    2016-10-01

    The role of newly synthesized tocopherol glycosidic derivative in modifying molecular organization and phase transitions of phospholipid monolayer at the air/water interface has been investigated. Two-component Langmuir films of dl-α-tocopheryl β-D-glucopyranoside (BG) mixed with dipalmitoyl phosphatidylcholine (DPPC) in the whole range of mole fractions were formed at the water surface. An analysis of surface pressure versus mean molecular area (π-A) isotherms and Brewster angle microscope images showed that the presence of BG molecules changes the structure and packing of the DPPC monolayer in a BG concentration dependent manner. BG molecules incorporated into DPPC monolayer inhibit its liquid expanded to liquid condensed phase transition proportionally to the BG concentration. The monolayers were also transferred onto solid substrates and visualized using an atomic force microscope. The results obtained indicate almost complete miscibility of BG and DPPC in the monolayers at surface pressures present in the biological cell membrane (30-35·10(-3) N·m(-1)) for a BG mole fraction as high as 0.3. This makes the monolayer less packed and more disordered, leading to an increased permeability. The results support our previous molecular dynamics simulation data. PMID:27287132

  12. 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

  13. 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

  14. 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

  15. Interaction of the cationic peptide bactenecin with phospholipid monolayers at the air-water interface: i interaction with 1,2-dipalmitoyl-sn-glycero-3-phosphatidilcholine.

    PubMed

    López-Oyama, A B; Flores-Vázquez, A L; Burboa, M G; Gutiérrez-Millán, L E; Ruiz-García, J; Valdez, M A

    2009-07-23

    In this work we have investigated the influence of NaCl on the adsorption of the antimicrobial cationic peptide bactenecin in the monolayer of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) at the air-water interface, as a function of NaCl concentrations in the subphase. We show that the effect of the salt concentration on DPPC monolayers is a monotonic decrease of the liquid-condensed-liquid-expanded (LC-LE) coexistence region. By contrast, the effect of the bactenecin adsorption at the DPPC monolayer not only removed the LC-LE coexistence region plateau, but also shifted the DPPC isotherms to higher pressures and increased the compressibility of the DPPC/bactenecin monolayers with respect to the pure DPPC monolayer around the LC phase. Analysis of the domain structure, obtained by Brewster angle and atomic force microscopes, indicates that the salt concentration in the subphase builds an electrostatic barrier, increasing the rigidity of DPPC monolayers and limiting the bactenecin adsorption at the LC-LE phase coexistence. PMID:19569630

  16. Morphology and thermochromic phase transition of merocyanine J-aggregate monolayers at the air-water and solid-water interfaces

    NASA Astrophysics Data System (ADS)

    Kato, Noritaka; Saito, Kentaro; Serata, Toshinori; Aida, Hiroaki; Uesu, Yoshiaki

    2001-07-01

    Thermal changes of the merocyanine dye (MD) monolayer at the air-water interface were investigated under various subphase conditions in order to elucidate the formation mechanism and to control morphological and chromatic properties of two-dimensional MD J-aggregate crystallites (JC) formed in the monolayer. The dissociation temperature (Td) of the JC to the monomer MD was measured for different counterions of MD molecules in the subphase. The JC size was found to be dependent on the subphase temperature; it becomes larger when the JC is formed at a temperature closer to Td. This phenomenon is qualitatively reproduced by the numerical simulation of the Cahn-Hilliard equation. In the case of the MD monolayer on the subphase which contains two kinds of counterions, it exhibits a reversible thermochromic transition between two different JC states. The chromatic change is discrete, and is attributed to the structural phase transition of the JC induced by the mutual recombination of two kinds of counterions to MD molecules. The structural difference between the high and low temperature JC states is examined by the point dipole model. The transition temperature and thermal hysteresis width can be varied by the fraction of 2 counterions. In situ observations using a multipurpose nonlinear optical microscope revealed that the transition is of first order and the nucleation and growth process of the low temperature phase in the high temperature matrix was observed. The JC size of the low temperature phase became much larger through the recrystallization process. For future application of this phenomenon, an airtight cell consisting of two monolayers at the solid-water interface and the subphase was developed. In the cell, the same reversible transition occurs, but with a slow relaxation.

  17. 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

  18. Monolayers of the lipid derivatives of isoniazid at the air/water interface and the formation of self-assembled nanostructures in water.

    PubMed

    Jin, Yiguang; Chen, Shufeng; Xin, Rui; Zhou, Yisheng

    2008-07-15

    Isoniazid (INH, isonicotinic acid hydrazide) is one of the most commonly used anti-tubercular drugs. However, resistance of Mycobacterium tuberculosis strains to anti-mycobacterial agents including INH is an increasing problem worldwide. Development of new anti-mycobacterial agents thus has attracted attention. Five lipid derivatives of INH were prepared in this study. They formed monolayers at the air/water interface, and some nanostructures with different morphologies were obtained through molecular self-assembly in water. The derivatives included one fatty acyl derivative containing a 12-C hydrocarbon-long chain (1), three fatty alcohol derivatives with a succinyl as spacer and an 8, 12 or 16-C hydrocarbon-long chain (2, 3 and 4), and one tetrahydro-2H-1,3,5-thiadiazine-2-thione (THTT) derivative containing a 12-C hydrocarbon-long chain (5). The surface pressure-area isotherms depended on the volume and configuration of heads and the length of tails of derivatives. Compound 2 had a relatively large head and a short tail, easily standing uprightly at the interface. Under a certain surface pressure, the linear polar head groups of 3 could be partly squeezed out and insert into subphase because the length of heads were comparable to the one of tails. The very long tails of 4 always maintained above the interface and led to a high collapse pressure. Compound 5 possessed an extended and large head consisting of the THTT and INH groups so that the relatively short tails tilted at the interface and difficultly contact with each other. The THTT rings might be partly squeezed out and enter into air under a certain surface pressure. The self-assembly behaviours of derivatives in water depended on the molecular configuration and agreed with the corresponding monolayer behaviours. The flexible and medium-long tails (1 and 3) led to the derivatives to form nanoscale vesicles, though the short or very long tails did not (2 and 4). Interestingly, intermolecular hydrogen

  19. Self-Assembled Large-Scale Monolayer of Au Nanoparticles at the Air/Water Interface Used as a SERS Substrate.

    PubMed

    Guo, Qinghua; Xu, Minmin; Yuan, Yaxian; Gu, Renao; Yao, Jianlin

    2016-05-10

    Self-assembly of metal nanoparticles has attracted considerable attention because of its unique applications in technologies such as plasmonics, surface-enhanced optics, sensors, and catalysts. However, fabrication of ordered nanoparticle structures remains a significant challenge. Thus, developing an efficient approach for the assembly of large-scale Au nanoparticles films for theoretical studies and for various applications is highly desired. In this paper, a facial approach for fabricating a monolayer film of Au nanoparticles was developed successfully. Using the surfactant polyvinylpyrrolidone (PVP), a large-scale monolayer film of well-ordered, uniform-sized Au nanoparticles was fabricated at the air/water interface. The film exhibited a two-dimensional (2D) hexagonal close-packed (HCP) structure having interparticle gaps smaller than 2 nm. These gaps generated numerous uniform "hot spots" for surface-enhanced Raman scattering (SERS) activity. The as-prepared monolayer film could be transferred to a solid substrate for use as a suitable SERS substrate with high activity, high uniformity, and high stability. The low spot-to-spot and substrate-to-substrate variations of intensity (<10%), the large surface enhancement factor (∼10(6)), and the high stability (∼45 days) make the substrate suitable for SERS measurements. Transfer of the monolayer film onto a glassy carbon electrode produced an Au electrode with clean, well-defined nanostructure suitable for electrochemical SERS measurements. The adsorption process of ionic liquids on the electrode with the monolayer film is similar to that on bulk metal electrodes. The present strategy provides an effective way for self-assembly of Au nanoparticles into well-defined nanostructures that may form optimal reproducible SERS substrates for quantitative analysis. It also provides an electrode with clean, well-defined nanostructure for electrochemical investigations. PMID:27101361

  20. 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

  1. Effect of the fluorination degree of hydrophobic chains on the monolayer behavior of unsaturated diacylphosphatidylcholines bearing partially fluorinated 9-octadecynoyl (stearoloyl) groups at the air-water interface.

    PubMed

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

    2014-11-01

    The effect of the fluorination degree of hydrophobic chains on the monolayer behavior of unsaturated diacylphosphatidylcholines (PCs) was examined by employing a series of PCs bearing partially fluorinated 9-octadecynoyl (stearoloyl) groups (DFnStPCs, n: the number of fluorinated carbon atoms in a stearoloyl group; n=1, 2, 4, 8), including their hydrophobic parts--partially fluorinated stearolic acids (FnStAs)--at the air-water interface. π-A isotherm measurements and Brewster angle microscope observations revealed: (i) all DFnStPCs including FnStAs form monolayers of liquid character at 25 °C; (ii) they form more expanded monolayers than their non-fluorinated counterparts, distearoloyl-PC (DStPC) and stearolic acid, while the monolayer stability increases with n; (iii) compared with DStPC and DF8StPC, DFnStPCs (n=1, 2, 4) in the low-π region tend to show a weakening in their self-aggregation property and an increase in the work required for monolayer compression; (iv) although DF8StPC forms the most expanded monolayer, the behavior of DF8StPC resembles that of DStPC rather than that of DFnStPCs (n=1, 2, 4). The monolayer behavior of DFnStPCs (n=1, 2, 4) is explained by postulating a flatly-lying conformation of hydrophobic chains, in which three polar parts (ester group, triple bond, CF2-CH2 linkage) in chains are immersed in the subphase at large areas. DStPC and DF8StPC lacking a CF2-CH2 linkage, however, do not likely adopt such a conformation. PMID:25264284

  2. 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.

  3. 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. PMID:20151713

  4. 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

  5. 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...

  6. Gas transfer velocities for quantifying methane, oxygen and other gas fluxes through the air-water interface of wetlands with emergent vegetation

    NASA Astrophysics Data System (ADS)

    Poindexter, C.; Variano, E. A.

    2012-12-01

    Empirical models for the gas transfer velocity, k, in the ocean, lakes and rivers are fairly well established, but there are few data to predict k for wetlands. We have conducted experiments in a simulated emergent marsh in the laboratory to explore the relationship between k, wind shear and thermal convection. Now we identify the implications of these results for gas transfer in actual wetlands by (1) quantifying the range of wind conditions in emergent vegetation canopies and the range of thermal convection intensities in wetland water columns, and (2) describing the non-linear interaction of these two stirring forces over their relevant ranges in wetlands. We measured mean wind speeds and wind speed variance within the shearless region of a Schoenoplectus-Typha marsh canopy in the Sacramento-San Joaquin Delta (Northern California, USA). The mean wind speed within this region, , is significantly smaller than wind above the canopy. Based on our laboratory experiments, for calm or even average wind conditions in this emergent marsh k600 is only on the order 0.1 cm hr-1 (for neutrally or stably stratified water columns). We parameterize unstable thermal stratification and the resulting thermal convection using the heat flux through the air-water interface, q. We analyzed a water temperature record for the Schoenoplectus-Typha marsh to obtain a long-term heat flux record. We used these heat flux data along with short-term heat flux data from other wetlands in the literature to identify the range of the gas transfer velocity associated with thermal convection in wetlands. The typical range of heat fluxes through water columns shaded by closed emergent canopies (-200 W m-2 to +200 W m-2) yields k600 values of 0.5 - 2.5 cm hr-1 according to the model we developed in the laboratory. Thus for calm or average wind conditions, the gas transfer velocity associated with thermal convection is significantly larger than the gas transfer velocity associated with wind

  7. 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.

  8. 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.

  9. Spatial Resolution Characterization for AWiFS Multispectral Images

    NASA Technical Reports Server (NTRS)

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

    2007-01-01

    This viewgraph presentation describes the spatial resolution of the AWiFS multispectral images characterized by an estimation of the Modulation Transfer Function (MTF) at Nyquist frequency. The contents include: 1) MTF Analysis; 2) Target Analysis; 3) "Pulse Target"; 4) "Pulse" Method; 5) Target Images; 6) Bridge Profiles; 7) MTF Calculation; 8) MTF Results; and 9) Results Summary.

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. Superposition-additive approach in the description of thermodynamic parameters of formation and clusterization of substituted alkanes at the air/water interface.

    PubMed

    Vysotsky, Yu B; Belyaeva, E A; Fomina, E S; Vasylyev, A O; Vollhardt, D; Fainerman, V B; Aksenenko, E V; Miller, R

    2012-12-01

    The superposition-additive approach developed previously was shown to be applicable for the calculations of the thermodynamic parameters of formation and atomization of conjugate systems, their dipole polarizability, molecular diamagnetic susceptibility, π-electronic ring currents, etc. In the present work, the applicability of this approach for the calculation of the thermodynamic parameters of formation and clusterization at the water/air interface of alkanes, fatty alcohols, thioalcohols, amines, nitriles, fatty acids (C(n)H(2n+1)X, X is the functional group) and cis-unsaturated carboxylic acids (C(n)H(2n-1)COOH) is studied. Using the proposed approach the thermodynamic quantities determined agree well with the available data, either calculated using the semiempirical (PM3) quantum chemical method, or obtained in experiments. In particular, for enthalpy and Gibbs' energy of the formation of substituted alkane monomers from the elementary substances, and their absolute entropy, the standard deviations of the values calculated according to the superposition-additive scheme with the mutual superimposition domain C(n-2)H(2n-4) (n is the number of carbon atoms in the alkyl chain) from the results of PM3 calculations for alkanes, alcohols, thioalcohols, amines, fatty acids, nitriles and cis-unsaturated carboxylic acids are respectively: 0.05, 0.004, 2.87, 0.02, 0.01, 0.77, and 0.01 kJ/mol for enthalpy; 2.32, 5.26, 4.49, 0.53, 1.22, 1.02, 5.30 J/(molK) for absolute entropy; 0.69, 1.56, 3.82, 0.15, 0.37, 0.69, 1.58 kJ/mol for Gibbs' energy, whereas the deviations from the experimental data are: 0.52, 5.75, 1.40, 1.00, 4.86 kJ/mol; 0.52, 0.63, 1.40, 6.11, 2.21 J/(molK); 2.52, 5.76, 1.58, 1.78, 4.86 kJ/mol, respectively (for nitriles and cis-unsaturated carboxylic acids experimental data are not available). The proposed approach provides also quite accurate estimates of enthalpy, entropy and Gibbs' energy of boiling and melting, critical temperatures and standard heat

  15. The formation of surface multilayers at the air-water interface from sodium polyethylene glycol monoalkyl ether sulfate/AlCl(3) solutions: the role of the size of the polyethylene oxide group.

    PubMed

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

    2013-09-17

    Neutron reflectivity, NR, and surface tension, ST, have been used to study the surface adsorption properties at the air-water interface of the anionic surfactant sodium polyethylene glycol monododecyl ether sulfate (sodium lauryl ether sulfate, SLES) in the presence of Al(3+) multivalent counterions, by the addition of AlCl3. In the absence of AlCl3 and at low AlCl3 concentrations monolayer adsorption is observed. With increasing AlCl3 concentration, surface multilayer formation is observed, driven by SLES/Al(3+) complex formation. The onset of multilayer formation occurs initially as a single bilayer or a multilayer structure with a limited number of bilayers, N, ≤3, and ultimately at higher AlCl3 concentrations N is large, >20. The evolution in the surface structure is determined by the surfactant and AlCl3 concentrations, and the size of the polyethylene oxide group in the different SLES surfactants studied. From the NR data, approximate surface phase diagrams are constructed, and the evolution of the surface structure with surfactant and electrolyte concentration is shown to be dependent on the size of the polyethylene oxide group. As the polyethylene oxide group increases in size the multilayer formation requires increasingly higher surfactant and AlCl3 concentrations to promote the formation. This is attributed to the increased steric hindrance of the polyethylene oxide group disrupting SLES/Al(3+) complex formation. PMID:23968161

  16. 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.

  17. 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

  18. 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.

  19. 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.

  20. Operational tsunami modelling with TsunAWI - recent developments and applications

    NASA Astrophysics Data System (ADS)

    Rakowsky, N.; Androsov, A.; Fuchs, A.; Harig, S.; Immerz, A.; Danilov, S.; Hiller, W.; Schröter, J.

    2013-06-01

    In this article, the tsunami model TsunAWI (Alfred Wegener Institute) and its application for hindcasts, inundation studies, and the operation of the tsunami scenario repository for the Indonesian tsunami early warning system are presented. TsunAWI was developed in the framework of the German-Indonesian Tsunami Early Warning System (GITEWS) and simulates all stages of a tsunami from the origin and the propagation in the ocean to the arrival at the coast and the inundation on land. It solves the non-linear shallow water equations on an unstructured finite element grid that allows to change the resolution seamlessly between a coarse grid in the deep ocean and a fine representation of coastal structures. During the GITEWS project and the following maintenance phase, TsunAWI and a framework of pre- and postprocessing routines was developed step by step to provide fast computation of enhanced model physics and to deliver high quality results.

  1. 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

  2. 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.

  3. Data inversion immune to cycle-skipping using AWI

    NASA Astrophysics Data System (ADS)

    Guasch, L.; Warner, M.; Umpleby, A.; Yao, G.; Morgan, J. V.

    2014-12-01

    . This new technique, called Adaptive Waveform Inversion (AWI) appears always superior to conventional FWI.

  4. Estimating gross primary production in Iowa from Advanced Wide Field Sensor (AWiFS) data

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Dr. E. Raymond Hunt, Jr., USDA/ARS, will be presenting recent research on the use of AWiFS shortwave infrared band (Band 5: 1.50 to 1.70 µm wavelength) for the prediction of vegetation water content. Data from many different land cover types show there is a relationship between the normalized diffe...

  5. Estimating crop production in Iowa from Advanced Wide Field Sensor (AWiFS) data

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Indian National Remote Sensing Agency ResourceSat-1 Advanced Wide Field Sensor (AWiFS) data for the USA is being provided online by the USDA Foreign Agricultural Service (FAS) and Arctic Slope Regional Corporation – Management Services (ASRC-MS). Because of the frequent revisit time and pixel sizes...

  6. Development of a scheme for atmospheric correction of Resourcesat-2 AWiFS data

    NASA Astrophysics Data System (ADS)

    Pandya, M. R.; Pathak, V. N.; Shah, D. B.; Trivedi, H. J.; Chipade, R. A.; Singh, R. P.; Kirankumar, A. S.

    2015-08-01

    This paper presents a method called SACRS2, a scheme for atmospheric correction of RS2-AWiFS (Resourcesat2-Advanced Wide Field Sensor) data. The SACRS2 is a computationally fast scheme developed from a physics-based detailed radiative transfer model 6SV for correcting large amount of data from the high-repetivity AWiFS sensor. The method is based on deriving a set of equations with coefficients which depend on the spectral bands of the RS2-AWiFS sensor through forward signal simulations by 6SV. Semi-empirical formulations provided in the SMAC method with a few improvements have been used to describe various atmospheric interactions. A total of 112 coefficients for different equations are determined using the best fit equations against the computations of the 6SV. After the specific coefficients for the RS2-AWiFS spectral bands are determined, the major inputs of the scheme are raw digital numbers recorded by RS2-AWiFS sensor, atmospheric columnar water vapour content, ozone content, aerosol optical thickness at 550 nm and viewing-illumination conditions. Results showed a good performance of the SACRS2 with a maximum relative error in the SACRS2 simulations ranged between 1% for a reflectance of 0.5 and 8.6% for reflectance of 0.05 with respect to 6SV computations. Validation of retrieved surface reflectance using the SACRS2 scheme with respect to in-situ measurements at two sites indicated a capability of this scheme to determine the surface reflectance within 10%. This is a first of its kind scheme developed for the atmospheric correction of any Indian Remote Sensing satellite data. A package containing the SACRS2 software is available on the MOSDAC website for the researchers.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Operational tsunami modeling with TsunAWI - Examples for Indonesia and Chile

    NASA Astrophysics Data System (ADS)

    Rakowsky, Natalja; Androsov, Alexey; Harig, Sven; Immerz, Antonia; Fuchs, Annika; Behrens, Jörn; Danilov, Sergey; Hiller, Wolfgang; Schröter, Jens

    2014-05-01

    The numerical simulation code TsunAWI was developed in the framework of the German-Indonesian Tsunami Early Warning System (GITEWS). The numerical simulation of prototypical tsunami scenarios plays a decisive role in the a priory risk assessment for coastal regions and in the early warning process itself. TsunAWI is based on a finite element discretization, employs unstructured grids with high resolution along the coast, and includes inundation. This contribution gives an overview of the model itself and presents two applications. For GITEWS, the existing scenario database covering 528 epicenters / 3450 scenarios from Sumatra to Bali was extended by 187 epicenters / 1100 scenarios in the Eastern Sunda Arc. Furthermore, about 1100 scenarios for the Western Sunda Arc were recomputed on the new model domain covering the whole Indonesian Seas. These computations would not have been feasible in the beginning of the project. The unstructured computational grid contains 7 million nodes and resolves all coastal regions with 150m, some project regions and the surrounding of tide gauges with 50m, and the deep ocean with 12km edge length. While in the Western Sunda Arc, the large islands of Sumatra and Java shield the Northern Indonesian Archipelago, tsunamis in the Eastern Sunda Arc can propagate to the North. The unstructured grid approach allows TsunAWI to easily simulate the complex propagation patterns with the self-interactions and the reflections at the coastal regions of myriads of 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) to provide data for a lightweight decision support system prototype (built by DLR). This work is part of the initiation project "Multi hazard information and early warning system in cooperation with Chile" and aims at sharing our experience from GITEWS with the Chilean partners.

  13. Estuary Turbulence and Air-Water Carbon Dioxide Exchange

    NASA Astrophysics Data System (ADS)

    Orton, Philip Mark

    The mixing of constituents between estuarine bottom and surface waters or between estuarine surface waters and the atmosphere are two topics of growing interest, in part due to the potentially important role of estuaries in global carbon budgets. These two types of mixing are typically driven by turbulence, and a research project was developed to improve the scientific understanding of atmospheric and tidal controls on estuary turbulence and airwater exchange processes. Highlights of method development and field research on the Hudson River estuary include several deployments of bottom mounted current profilers to quantify the turbulent kinetic energy (TKE) budget, and construction and deployment of an instrumented catamaran that makes autonomous measurements of air-water CO2 exchange (FCO2), water TKE dissipation at 50 cm depth (epsilon50), and other physical properties just above and below the air-water interface. On the Hudson, wind correlates strongly with epsilon50, but surface water speed and airwater heat flux also have moderate correlations with epsilon50. In partially mixed estuaries such as the Hudson, as well as salt wedge estuaries, baroclinic pressure forcing typically causes spring ebb tides to have much stronger upper water column shear than flood tides. The Hudson data are used to show that this shear leads to local shear instability and stronger near-surface turbulence on spring ebbs. Also, buoyancy budget terms are compared to demonstrate how water-to-air heat fluxes can influence stratification and indirectly influence epsilon50. Looking more closely at the role of wind forcing, it is demonstrated that inland propagation of the sea breeze on warm sunny days leads to arrival in phase with peak solar forcing at seaward stations, but several hours later at up-estuary stations. Passage of the sea breeze front raises the air-water CO2 flux by 1-2 orders of magnitude, and drives epsilon50 comparable to spring tide levels in the upper meter of the water

  14. The AWI Climate Model: response to increased resolution in dynamically active regions

    NASA Astrophysics Data System (ADS)

    Sidorenko, Dmitry; Semmler, Tido; Rackow, Thomas; Goessling, Helge F.; Danilov, Sergey; Wang, Qiang; Sein, Dmitry; Jung, Thomas

    2016-04-01

    State-of-the-art climate models do still exhibit pronounced deviations from the measured climate. Those deviations are often common between those models. The challenging problems in the Northern hemisphere include warming and salinization of the deep ocean being most pronounced in the northern North Atlantic, reduced deep water formation in the Labrador Sea which is sometimes accomplished by the sporadic ice coverage of the whole Labrador Sea, and an extensive ice presence in the Barents Sea. All these biases are often attributed in literature to the lack of oceanic resolution. The multi-resolution approach used in the ocean component of the AWI climate model (ECHAM6-FESOM) allows to use enhanced horizontal resolution in dynamical active regions while keeping a coarse-resolution setup everywhere else. In this study we develop strategies for improving the climate model biases by means of increasing resolution in the ocean. The current computations have been performed on multi-centennial time scales using refinement in the different parts of the global ocean. Benefits from the local refinement have been analyzed. It is found that already with moderate refinement of the unstructured ocean grid, AWI-CM performs as well as some of the most sophisticated climate models participating in CMIP5.

  15. 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

  16. 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…

  17. 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

  18. 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. PMID:25855227

  19. Development of regional wheat VI-LAI models using Resourcesat-1 AWiFS data

    NASA Astrophysics Data System (ADS)

    Chaurasia, Sasmita; Nigam, R.; Bhattacharya, B. K.; Sridhar, V. N.; Mallick, K.; Vyas, S. P.; Patel, N. K.; Mukherjee, J.; Shekhar, Chander; Kumar, Dhiraj; Singh, K. R. P.; Bairagi, G. D.; Purohit, N. L.; Parihar, J. S.

    2011-12-01

    The time of forcing of spatial LAI to crop models at single or multiple stages is important to simulate crop biomass and yield in varying agro-climatic conditions and scales. The high temporal resolution (5-day) by Advanced Wide Field Sensor (AWiFS) on-board Resourcesat-1 Satellite IRS-P6 with 56 m spatial resolution and large swath (740 km) has substantially increased the availability of regional clear sky optical remote sensing data. The present study aimed at developing empirical vegetation index VI-LAI models for wheat using AWiFS optical data in four bands and in-situ measurements sampled over five different agro-climatic regions (ACRs) during 2005-2006 followed by validation during 2006-2007. While nonlinear relations exist for all the three normalized indices such as normalized difference vegetation index (NDVI), normalized difference water index (NDWI) and Green NDVI, linear relation was the best fit for ratio vegetation index (RVI). Both NDVI and RVI models generally showed better correlation ranges (0.65-0.84 for NDVI and 0.37-0.76 for RVI) than other indices. The common NDVI-LAI model was found to produce lower root mean square errors (RMSE) between 0.5 and 1.1 from pooled model than those between 0.5 and 1.32 from regional models. The rate of substantial increase in errors from NDVI-LAI model (RMSE of modeled LAI: 0.85 to 1.28) as compared to RVI-LAI model (RMSE of modeled LAI: 1.12 to 1.17) at LAI greater than 3, than below 3 revealed the early saturation of NDVI than RVI. It is therefore recommended that LAI estimates can be used to force crop simulation model upto early vegetative stage based on NDVI and maximum vegetative to reproductive stages based on RVI.

  20. Air-Water Gas Exchange in Wetland Water Columns Due To Wind and Thermal Convection

    NASA Astrophysics Data System (ADS)

    Poindexter, C.; Variano, E. A.

    2011-12-01

    The goal of this work is to provide a parameterization of the air-water gas transfer rate in wetlands, and do so in terms of easily measured environmental variables. This parameterization is intended to support biogeochemical modeling in wetlands by providing an interfacial flux of key importance. Our approach uses laboratory experiments describe the oxygen transfer across an air-water interface in a model wetland. The oxygen transfer is sensitive to the externally imposed wind, vegetation characteristics, and vertical thermal convection. We vary these systematically, determining the gas transfer (or "piston") velocity that describes interfacial gas flux. We measure velocity vector fields near the air-water interface using particle image velocimetry, and use these measurements to help explain the mechanisms behind the measured trends in oxygen transfer. The explanatory power of these measurements includes the relationship between plant geometry and surface divergence. We explore the potential impact of our results on wetland modeling and management, for issues such as carbon sequestration and methane emission.

  1. 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

  2. Monitoring the long term stability of the IRS-P6 AWiFS sensor using the Sonoran and RVPN sites

    NASA Astrophysics Data System (ADS)

    Chander, Gyanesh; Sampath, Aparajithan; Angal, Amit; Choi, Taeyoung; Xiong, Xiaoxiong

    2010-10-01

    This paper focuses on radiometric and geometric assessment of the Indian Remote Sensing (IRS-P6) Advanced Wide Field Sensor (AWiFS) sensor using the Sonoran desert and Railroad Valley Playa, Nevada (RVPN) ground sites. Imageto- Image (I2I) accuracy and relative band-to-band (B2B) accuracy were measured. I2I accuracy of the AWiFS imagery was assessed by measuring the imagery against Landsat Global Land Survey (GLS) 2000. The AWiFS images were typically registered to within one pixel to the GLS 2000 mosaic images. The B2B process used the same concepts as the I2I, except instead of a reference image and a search image; the individual bands of a multispectral image are tested against each other. The B2B results showed that all the AWiFS multispectral bands are registered to sub-pixel accuracy. Using the limited amount of scenes available over these ground sites, the reflective bands of AWiFS sensor indicate a long-term drift in the top-of-atmosphere (TOA) reflectance. Because of the limited availability of AWiFS scenes over these ground sites, a comprehensive evaluation of the radiometric stability using these sites is not possible. In order to overcome this limitation, a cross-comparison between AWiFS and Landsat 7 (L7) Enhanced Thematic Mapper Plus (ETM+) was performed using image statistics based on large common areas observed by the sensors within 30 minutes. Regression curves and coefficients of determination for the 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.

  3. 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. PMID:26633595

  4. In-season time series analysis of Resourcesat-1 AWiFS data for estimating irrigation water requirement

    NASA Astrophysics Data System (ADS)

    Raju, P. V.; Sesha Sai, M. V. R.; Roy, P. S.

    2008-06-01

    AWiFS sensor on board IRS-P6 (Resourcesat-1), with its unique features—wide swath and 5-day revisit capability provides excellent opportunities to carry out in-season analysis of irrigated agriculture. The study carried out in Hirakud command area, Orissa State indicated that the progression of rice crop acreage could be mapped through analysis of time series AWiFS data set. The spectral emergence pattern of rice crop was found useful to identify the period of rice transplantation and its variability across the command area. This information, integrated with agro-meteorological data, was used to quantify 10-daily canal-wise irrigation water requirement. A comparison with field measured actual irrigation supplies indicated an overall supply adequacy of 88% and showed wide variability at lateral canal level ranging between 18% and 109%. The supply pattern also did not correspond with the chronological variations associated with crop water requirement, supplies were 15% excess during initial part of season (December and January) and were 20.1% deficit during later part of season (February to April). Rescheduling the excess supplies of the initial period could have reduced the deficit to 15% during peak season. The study has demonstrated the usefulness of AWiFS data to generate the irrigation water requirement by mid-season, subsequent to which 38% supplies were yet to be allocated. This would support the irrigation managers to reschedule the irrigation water supplies to achieve better synchronization between requirement and supply leading to improved water use efficiency.

  5. 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

  6. 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.

  7. 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.

  8. Automated Burned Area Delineation Using IRS AWiFS satellite data

    NASA Astrophysics Data System (ADS)

    Singhal, J.; Kiranchand, T. R.; Rajashekar, G.; Jha, C. S.

    2014-12-01

    spectral data from the IRS AWiFS sensor. The method is intended to be used by non-specialist users for diagnostic rapid burnt area mapping.

  9. 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.

  10. 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.

  11. Retrieval of Surface Reflectance using SACRS2: a Scheme for Atmospheric Correction of ResourceSat-2 AWiFS data

    NASA Astrophysics Data System (ADS)

    Pandya, M. R.; Pathak, V. N.; Shah, D. B.; Singh, R.. P.

    2014-11-01

    The Indian Remote Sensing (IRS) satellite series has been providing data since 1988 through various Earth observation missions. Before using IRS data for the quantitative analysis and parameter retrieval, it must be corrected for the atmospheric effects because spectral bands of IRS sensors are contaminated by intervening atmosphere. Standard atmospheric correction model tuned for the IRS sensors was not available for deriving surface reflectance. Looking at this gap area, a study was carried out to develop a physicsbased method, called SACRS2- a Scheme for Atmospheric Correction of Resourcesat-2 (RS2) AWiFS data. SACRS2 is a computationally fast scheme developed for correcting large amount of data acquired by RS2-AWiFS sensor using a detailed radiative transfer model 6SV. The method is based on deriving a set of coefficients which depend on spectral bands of the RS2-AWiFS sensor through thousands of forward signal simulations by 6SV. Once precise coefficients of all the physical processes of atmospheric correction are determined for RS2-AWiFS spectral bands then a complete scheme was developed using these coefficients. Major inputs of the SACRS2 scheme are raw digital numbers recorded by RS2-AWiFS sensor, aerosol optical thickness at 550 nm, columnar water vapour content, ozone content and viewing-geometry. Results showed a good performance of SACRS2 with a maximum relative error in the SACRS2 simulations ranged between approximately 2 to 7 percent with respect to reference 6SV computations. A complete software package containing the SACRS2 model along with user guide and test dataset has been released on the website (www.mosdac.gov.in) for the researchers.

  12. 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...

  13. 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%.

  14. X-ray microtomography determination of air-water interfacial area-water saturation relationships in sandy porous media.

    PubMed

    Costanza-Robinson, Molly S; Harrold, Katherine H; Lieb-Lappen, Ross M

    2008-04-15

    In this work, total smooth air-water interfacial areas were measured for a series of nine natural and model sandy porous media as a function of water saturation using synchrotron X-ray microtomography. Interfacial areas decreased linearly with water satuation, while the estimated maximum interfacial area compared favorably to the media geometric surface areas. Importantly, relative interfacial area (i.e., normalized by geometric surface area) versus water saturation plots for all media collapsed into a single linear cluster (r2 = 0.93), suggesting that geometric surface area is an important, and perhaps sufficient, descriptor of sandy media that governs total smooth interfacial area-water saturation relationships. Measured relationships were used to develop an empirical model for estimating interfacial area-water saturation relationships for sandy porous media. Model-based interfacial area estimates for independent media were generally slightly higher than interfacial areas measured using aqueous-phase interfacial tracer methods, which may indicate that microtomography captures regions of the air-water interface that are not accessible to aqueous-phase interfacial tracers. The empirical model presented here requires only average particle diameter and porosity as input parameters and can be used to readily estimate air-water interfacial area-water saturation relationships for sandy porous media. PMID:18497149

  15. 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.

  16. Interfacial area measurement and transport modeling in air-water two-phase flow

    NASA Astrophysics Data System (ADS)

    Fu, Xinyu

    In two-fluid model, the interfacial area concentration (IAC) is an important parameter that characterizes the interaction of two-phases at the interface. The accuracy of IAC modeling and local measurements largely affects the efficiency of designing and assessing two-phase flow systems. The prediction of the dynamical evolution of IAC is one of the most challenging tasks in research and application. This thesis is focused on developing advanced local measurement techniques to obtain reliable two-phase parameters and implementing efficient theoretical models for IAC source and sink terms in a two-group interfacial area transport equation based on experiments. In this study, an advanced local measurement technique using a four-sensor conductivity probe has been presented for obtaining IAC in air-water flows. It extends the existing conductivity probe method to slug and churn-turbulent flows with a unified probe design and comprehensive signal processing system. Sophisticated algorithm and software have been implemented that is robust in handling most practical conditions with high reliability. Systematic analyses on the issues of probe applications and benchmarks have been performed. The improved four-sensor method has also been applied to flow conditions with significant local recirculation, which was considered the most challenging situation for local measurement in two-phase flow. Using the well-established instrumentation, solid databases for a two-inch air-water loop have been built with sufficient information on the axial development and the radial distribution of the local parameters. Mechanistic models of major fluid particle interaction phenomena involving two bubble groups have been proposed, including the shearing-off of small bubbles from slug/cap bubbles, the wake entrainment of group-1 bubble into group-2 bubble, the wake acceleration and coalescence between group-2 bubbles, and the breakup of group-2 bubbles due to surface instability. Prediction of

  17. 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.

  18. Micrometeorological Measurement of Fetch- and Atmospheric Stability-Dependent Air- Water Exchange of Legacy Semivolatile Organic Contaminants in Lake Superior

    NASA Astrophysics Data System (ADS)

    Perlinger, J. A.; Tobias, D. E.; Rowe, M. D.

    2008-12-01

    Coastal waters including the Laurentian Great Lakes are particularly susceptible to local, regional, and long- range transport and deposition of semivolatile organic contaminants (SOCs) as gases and/or associated with particles. Recently-marketed SOCs can be expected to undergo net deposition in surface waters, whereas legacy SOCs such as polychlorinated biphenyls (PCBs) are likely to be at equilibrium with respect to air-water exchange, or, if atmospheric concentrations decrease through, e.g., policy implementation, to undergo net gas emission. SOC air-water exchange flux is usually estimated using the two-film model. This model describes molecular diffusion through the air and water films adjacent to the air-water interface. Air-water exchange flux is estimated as the product of SOC fugacity, typically based on on-shore gaseous concentration measurements, and a transfer coefficient, the latter which is estimated from SOC properties and environmental conditions. The transfer coefficient formulation commonly applied neglects resistance to exchange in the internal boundary layer under atmospherically stable conditions, and the use of on-shore gaseous concentration neglects fetch-dependent equilibration, both of which will tend to cause overestimation of flux magnitude. Thus, for legacy chemicals or in any highly contaminated surface water, the rate at which the water is cleansed through gas emission tends to be over-predicted using this approach. Micrometeorological measurement of air-water exchange rates of legacy SOCs was carried out on ships during four transect experiments during off-shore flow in Lake Superior using novel multicapillary collection devices and thermal extraction technology to measure parts-per-quadrillion SOC levels. Employing sensible heat in the modified Bowen ratio, fluxes at three over-water stations along the transects were measured, along with up-wind, onshore gaseous concentration and aqueous concentration. The atmosphere was unstable for

  19. 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

  20. 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

  1. 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.

  2. 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)

  3. 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... Violating Facilities” published pursuant to 40 CFR 15.20. By acceptance of a cooperative agreement in...

  4. 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... Violating Facilities” published pursuant to 40 CFR 15.20. By acceptance of a cooperative agreement in...

  5. 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... Violating Facilities” published pursuant to 40 CFR 15.20. By acceptance of a cooperative agreement in...

  6. 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. 1274.926 Section 1274.926 Aeronautics and Space NATIONAL AERONAUTICS AND SPACE ADMINISTRATION COOPERATIVE AGREEMENTS WITH COMMERCIAL FIRMS Other Provisions and Special Conditions § 1274.926 Clean Air-Water Pollution Control Acts. Clean...

  7. 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.

  8. 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.

  9. Equation of state for a coarse-grained DPPC monolayer at the air/water interface

    NASA Astrophysics Data System (ADS)

    Adhangale, Parag S.; Gaver, Donald P., III

    Pulmonary surfactant, a complex mixture of phospholipids and proteins, secreted by the type II epithelial cells in the lungs, is crucial to reducing the effort required for breathing. A lack of adequate amounts of pulmonary surfactant in underdeveloped lungs of premature infants results in infant respiratory distress syndrome (RDS). Surfactant replacement therapy (SRT) is the approved method of mitigating the effects of RDS. The development of new SRT regimens requires a fundamental understanding of the links between surfactant biochemistry and functionality. We use a coarse-grained (CG) model to predict the surface pressure-surface concentration relationship (equation of state) for pure DPPC, which is a major component of endogenous and synthetic pulmonary surfactant mixtures. We show that the model can be efficiently used to predict the equation of state in excellent agreement with experimental results. We also study the structure of the monolayer as a function of the surface tension of the system. We show that a decrease in the applied surface tension results in an increase in order in the head group region and a decrease in order in the tail region of DPPC. This technique may be useful in the prediction of equations of state for surfactant replacements.

  10. Surface potential of methyl isobutyl carbinol adsorption layer at the air/water interface.

    PubMed

    Phan, Chi M; Nakahara, Hiromichi; Shibata, Osamu; Moroi, Yoshikiyo; Le, Thu N; Ang, Ha M

    2012-01-26

    The surface potential (ΔV) and surface tension (γ) of MIBC (methyl isobutyl carbinol) were measured on the subphase of pure water and electrolyte solutions (NaCl at 0.02 and 2 M). In contrast to ionic surfactants, it was found that surface potential gradually increased with MIBC concentration. The ΔV curves were strongly influenced by the presence of NaCl. The available model in literature, in which surface potential is linearly proportional to surface excess, failed to describe the experimental data. Consequently, a new model, employing a partial charge of alcohol adsorption layer, was proposed. The new model predicted the experimental data consistently for MIBC in different NaCl solutions. However, the model required additional information for ionic impurity to predict adsorption in the absence of electrolyte. Such inclusion of impurities is, however, unnecessary for industrial applications. The modeling results successfully quantify the influence of electrolytes on surface potential of MIBC, which is critical for froth stability. PMID:22172075

  11. 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...

  12. 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.

  13. Photochemical Reactions at the Air-Water Interface in the Troposphere (Invited)

    NASA Astrophysics Data System (ADS)

    Hoffmann, M. R.; Kameel, F. R.; Colussi, A. J.

    2013-12-01

    Increasing awareness that isoprene, ISO, is only partially processed in the gas-phase has turned attention to its reactive uptake by fog, cloud and aerosol droplets. As a hydrophobic gas, ISO would preferentially partition to the surface rather than the bulk of aqueous media. Such media also contain dissolved O2 and water-soluble unsaturated organics, and support OH generation rates (from the solar photolysis of H2O2 dissolved therein) that are several orders of magnitude faster than in the gas-phase. Hence, ISO should be converted to heavier products rather than into the C4-C5 volatile compounds produced in the gas-phase. Here we substantiate such scenario by reporting that the λ > 305 nm photolysis of H2O2 in aqueous dilute ISO solutions yields C10H15OH species as primary products, whose formation both requires and is inhibited by O2. A minimum of seven C10H15OH isomers are resolved by reverse-phase high-performance liquid chromatography and detected as MH+ (m/z = 153) and MH+-18 (m/z = 135) signals by electrospray ionization mass spectrometry. Our findings are consistent with the addition of OH to ISO, followed by HO-ISO reactions with ISO (in competition with O2) leading to second generation HO(ISO)2 radicals that terminate as C10H15OH via β-H abstraction by O2. We show that a significant fraction of gas-phase olefins should be converted into less volatile species via this process on airborne wet particles.

  14. Crystal Perfection of Particle Monolayer at the Air-Water Interface.

    PubMed

    Shinotsuka, Kei; Kajita, Yasuhito; Hongo, Koki; Hatta, Yoshihisa

    2015-10-27

    Crystal growth in colloidal particle monolayers fabricated by Langmuir-Blodgett method on 4 in. sapphire wafers was investigated under the condition of two techniques, that is, ultrasonic annealing at 1.2 to 1.5 MHz and barrier-sway process at 0.2 to 0.5 Hz. Significant increases of the ordered area were obtained by the both techniques and more than 60 times growth was confirmed. The remaining crystal defects after the growth were categorized as grain boundary, vacancy, and line defect. Both techniques exhibited different features regarding the component ratio of the defects, and different mechanisms for the reorientation of particles are discussed. The driving force of these re-orientations is thought to be associated with the 2D Ostwald ripening of colloidal crystals. PMID:26434777

  15. 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

  16. Interaction of polyhedral oligomeric silsesquioxane containing epoxycyclohexyl groups with cholesterol at the air/water interface.

    PubMed

    Dopierała, Katarzyna; Maciejewski, Hieronim; Prochaska, Krystyna

    2016-04-01

    Binary mixtures of cholesterol and fully-condensed octakis[{2-(3,4-epoxycyclohexyl) etyl}dimethyl-silyloxy]octasilsesquioxane (OE-POSS) were characterized using Langmuir trough for obtaining surface pressure-area isotherms. The most characteristic feature of the mixed films is the presence of two collapse points on the isotherms. The first one is attributed to the collapse of less stable OE-POSS and it occurs at similar surface pressures for all compositions, while the second one corresponds to cholesterol collapse. Brewster angle microscopy observations confirmed the collapse behavior of the mixed film. Strong condensing effect was observed for the mean molecular areas dependence on cholesterol content in the film. Moreover, formation of microdomains of each component in the matrix of the other one was confirmed by BAM images. For the reasons of molecular structures and interactions a true mixed and homogenous film did not form in the systems considered. Phase separation was observed for all the compositions experimented. The lack of the interactions of OE-POSS with biomembrane components represented by cholesterol is beneficial for applications of OE-POSS in biomedical devices. PMID:26752210

  17. Thermal stability effects on the structure of the velocity field above an air-water interface

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

    Mean velocity and turbulence measurements are described for turbulent flows above laboratory water waves, under various wind and thermal stratification conditions. Experimental results, when presented in the framework of Monin-Obukhov (1954) similarity theory, support local scaling based on evaluation of stratification effects at the same nondimensional distance from the mean water surface. Such scaling allows an extension of application of the above theory to the outer region of the boundary layer. Throughout the fully turbulent region, ratios of mean velocity gradients, eddy viscosities, and turbulence intensities under nonneutral and neutral conditions correlate well with the parameter z/Lambda (Lambda being a local Obukhov length and z the vertical coordinate of the mean air flow) and show good agreement with established field correlations. The influence of stratification on the wind-stress coefficient can be estimated from an empirical relationship in terms of its value under neutral conditions and a bulk Richardson number.

  18. 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.

  19. 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.

  20. 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.

  1. [Nitrate and nitrite levels in daily food rations of children from the rural Puławy regions].

    PubMed

    Bilczuk, L; Gowin, A; Ebertowska, Z; Mach, H

    1991-01-01

    In the region of Puławy where the operation of the Nitrogen-Compound Manufacturing Plant has lead to an increase in nitrogen compound emission to the environment, nitrate and nitrite contents in daily food rations of children were determined. Daily food rations of children aged 8-9 and 12-13 years were collected from individual farms in four villages situated in the vicinity of the Nitrogen Plant, as well as--for control--from individual farms in Janowiec, a village distant from this Plant. Nitrate and nitrite contents were assayed in 300 daily food rations taken in spring and autumn. Nitrate was reduced to nitrite on a cadmium column whereupon it was determined colorimetrically using sulphanilic acid and N-1-napthyl-ethylenediamine. It was found that in the group of younger children as many as 70%, on the average, of the examined food rations displayed nitrate contents exceeding the admissible levels. In the group of the 12-13 years old children, the percentage of daily food rations whose nitrate content exceeded the admissible level was lower, averaging ca. 30% of all rations examined. The percentage of the daily food rations in which the nitrite content was higher than admissible level was closely similar in both groups of children, averaging ca. 30% of all rations examined. Food rations collected in spring, as compared with those taken in autumn, contained significantly greater amount of nitrate. In both periods of studies, nitrate contents were greater in the food rations from the farms situated near the Nitrogen Plant than in the food rations from farms in Janowiec.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:1803441

  2. 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...

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Critical air/water blow-down in safety valves at low qualities.

    PubMed

    Moncalvo, D; Friedel, L

    2011-02-28

    Critical air/water blow-downs in safety valves for qualities from 0.01 to 0.113 and mass flow rates from 1.5 up to 4.3 kg/s have been observed in our test facility. These critical blow-downs are characterized by a large void fraction and by an intense mixing of the phases both in the valve body and in the outlet pipe. A qualitative estimation of the flow pattern in the outlet pipe using the map of Taitel and Dukler suggests that these air/water flows are intermittent flows--presumably slug flows--evolving to annular flows for qualities above 0.1. Intermittent flows are also predicted for critical air/water and air/glycerine flows taken from the literature for the same safety valve at slightly larger relieving pressures. PMID:21227579

  9. 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.

  10. 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...

  11. [Charge generation and separation at liquid interfaces

    SciTech Connect

    Eisenthal, K.B.

    1992-01-01

    The research is divided into 3 parts: (1)Sum Frequency Generation (SFG) and Monolayer Structure. Picosecond lasers are combined by difference frequency mixing in a nonlinear crystal to generate picosecond, tunable IR pulses, which are used to study orientation of C[double bond]N and CD[sub 3] chromosphores (head group and tail) on lipid monolayers CD[sub 3](CH[sub 2])[sub 21]CN at air/water interface. (2)Femtosecond Dynamics. The femtosecond colliding pulse mode locked laser is being modified to carry out pump-second harmonic (SH) probe studies at liquid interfaces. Picosecond SH knowhow of intermolecular energy transfer, excited state isomerization, and rotational motions at interfaces is now being applied to femtosecond scale. Aromatics adsorbed at air/water interface, generated changes in SH probe signal and their decay back to original value. If the laser is tightly focussed at interface, multiphoton absorption processes occur which destroy the sample; this effect will be exploited. (3)Interface Potential and Acid-Base Equilibria. The interface potential is a key to charge transport; using SHG, we plan to measure the pKa of organic acids at interfaces. In these studies at silica/aqueous interface, the water molecules extending from the interface into the bulk (about 50[Angstrom]) were strongly polarized by SiO[sup [minus

  12. Detailed simulations of air-water interaction phenomena in ocean waves

    NASA Astrophysics Data System (ADS)

    Iafrati, A.; Durante, D.

    2012-04-01

    In the present contribution the flow induced in air by ocean waves is investigated. The air-water interaction problem is of obvious interest in the context of wind generated waves. However, the flow induced in the lower atmosphere layer by ocean waves has also important effects on the exchange processes between atmosphere and ocean and in some circumstances it influences weather conditions on large scales. The problem is studied numerically by a two-dimensional Navier-Stokes solver which models the flow in air and water as that of a single incompressible fluid with density and viscosity expressed as a smooth function of the distance from the interface. The free surface is captured as the zero level set of the distance function. The distance from the interface is reinitialized every time step, so that the thickness of the transition region remains constant in time. The method is applied to two problems characterized by quite different length scales and steepnesses. In both cases the limits associated to the numerical approach and possible effects on the results are discussed. The first application is an attempt of investigating the role played by the flow in air on the dissipation rate of swells. The interest for such problem stems from some studies according to which the flow in air has an important effect on the dissipation of the steepest swells (Ardhuin et al, 2009). Motivated by the above findings, numerical simulations are performed in order to investigate the characteristics of the flow induced in air by swell with wavelengths in a range 50 to 300 m. Results are presented in terms of vorticity field in air with quantitative analyses of the vertical flux of horizontal momentum and of the viscous dissipation in the air phase. The thickness of the air layer which is influenced by the passage of the swell is also given. The second study analyzes the flow induced in air by the evolution of modulated wave trains. In this case the fundamental wavelength is 0.6 m

  13. Molecular Design of Branched and Binary Molecules at Ordered Interfaces

    SciTech Connect

    Kirsten Larson Genson

    2005-12-27

    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.

  14. 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.

  15. Coupling of phytoplankton uptake and air-water exchange of persistent organic pollutants

    SciTech Connect

    Dachs, J.; Eisenreich, S.J.; Baker, J.E.; Ko, F.C.; Jeremiason, J.D.

    1999-10-15

    A dynamic model that couples air-water exchange and phytoplankton uptake of persistent organic pollutants has been developed and then applied to PCB data from a small experimental lake. A sensitivity analysis of the model, taking into account the influence of physical environmental conditions such as temperature, wind speed, and mixing depth as well as plankton-related parameters such as biomass and growth rate was carried out for a number of PCBs with different physical-chemical properties. The results indicate that air-water exchange dynamics are influenced not only by physical parameters but also by phytoplankton biomass and growth rate. New phytoplankton production results in substantially longer times to reach equilibrium. Phytoplankton uptake-induced depletion of the dissolved phase concentration maintains air and water phases out of equilibrium. Furthermore, PCBs in phytoplankton also take longer times to reach equilibrium with the dissolved water phase when the latter is supported by diffusive air-water exchange. However, both model analysis and model application to the Experimental Lakes Area of northwestern Ontario (Canada) suggest that the gas phase supports the concentrations of persistent organic pollutants, such as PCBs, in atmospherically driven aquatic environments.

  16. Dust Control with Use of Air-Water Spraying System / Redukcja Zapylenia Powietrza Z Wykorzystaniem Zraszania Powietrzno-Wodnego

    NASA Astrophysics Data System (ADS)

    Prostański, Dariusz

    2012-12-01

    Results from testing the dust control efficiency, when using air-water spraying system in comparison to the typical water spraying system are presented in the paper. The tests were carried out in conditions of longwall mining and at the places of run-of-mine transportation. Also the results of stand tests of different types of nozzles both for air-water and for water spaying systems carried out at KOMAG's laboratory and in real conditions are presented. The benefits resulting from air-water spraying system have been determined.

  17. 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.

  18. 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 (

  19. Cholesterol Promotes Interaction of the Protein CLIC1 with Phospholipid Monolayers at the Air-Water Interface.

    PubMed

    Hossain, Khondker R; Al Khamici, Heba; Holt, Stephen A; Valenzuela, Stella M

    2016-01-01

    CLIC1 is a Chloride Intracellular Ion Channel protein that exists either in a soluble state in the cytoplasm or as a membrane bound protein. Members of the CLIC family are largely soluble proteins that possess the intriguing property of spontaneous insertion into phospholipid bilayers to form integral membrane ion channels. The regulatory role of cholesterol in the ion-channel activity of CLIC1 in tethered lipid bilayers was previously assessed using impedance spectroscopy. Here we extend this investigation by evaluating the influence of cholesterol on the spontaneous membrane insertion of CLIC1 into Langmuir film monolayers prepared using 1-palmitoyl-2-oleoylphosphatidylcholine, 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-ethanolamine and 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-L-serine alone or in combination with cholesterol. The spontaneous membrane insertion of CLIC1 was shown to be dependent on the presence of cholesterol in the membrane. Furthermore, pre-incubation of CLIC1 with cholesterol prior to its addition to the Langmuir film, showed no membrane insertion even in monolayers containing cholesterol, suggesting the formation of a CLIC1-cholesterol pre-complex. Our results therefore suggest that CLIC1 membrane interaction involves CLIC1 binding to cholesterol located in the membrane for its initial docking followed by insertion. Subsequent structural rearrangements of the protein would likely also be required along with oligomerisation to form functional ion channels. PMID:26875987

  20. 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.

  1. Regionalized global budget of the CO2 exchange at the air-water interface in continental shelf seas

    NASA Astrophysics Data System (ADS)

    Laruelle, Goulven G.; Lauerwald, Ronny; Pfeil, Benjamin; Regnier, Pierre

    2014-11-01

    Over the past decade, estimates of the atmospheric CO2 uptake by continental shelf seas were constrained within the 0.18-0.45 Pg C yr-1 range. However, most of those estimates are based on extrapolations from limited data sets of local flux measurements (n < 100). Here we propose to derive the CO2 air-sea exchange of the shelf seas by extracting 3 · 106 direct surface ocean CO2 measurements from the global database SOCAT (Surface Ocean CO2 Atlas), atmospheric CO2 values from GlobalVIEW and calculating gas transfer rates using readily available global temperature, salinity, and wind speed fields. We then aggregate our results using a global segmentation of the shelf in 45 units and 152 subunits to establish a consistent regionalized CO2 exchange budget at the global scale. Within each unit, the data density determines the spatial and temporal resolutions at which the air-sea CO2 fluxes are calculated and range from a 0.5° resolution in the best surveyed regions to a whole unit resolution in areas where data coverage is limited. Our approach also accounts, for the first time, for the partial sea ice cover of polar shelves. Our new regionalized global CO2 sink estimate of 0.19 ± 0.05 Pg C yr-1 falls in the low end of previous estimates. Reported to an ice-free surface area of 22 · 106 km2, this value yields a flux density of 0.7 mol C m-2 yr-1, ~40% more intense than that of the open ocean. Our results also highlight the significant contribution of Arctic shelves to this global CO2 uptake (0.07 Pg C yr-1).

  2. 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

  3. 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.

  4. 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. PMID:19481762

  5. 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

  6. 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.

  7. 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

  8. NOVEL METHODS FOR MEASURING AIR-WATER INTERFACIAL AREA IN UNSATURATED POROUS MEDIA

    PubMed Central

    Brusseau, Mark L.; Ouni, Asma El; Araujo, Juliana B.; Zhong, Hua

    2015-01-01

    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

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. Air-water gas exchange and CO2 flux in a mangrove-dominated estuary

    NASA Astrophysics Data System (ADS)

    Ho, David T.; Ferrón, Sara; Engel, Victor C.; Larsen, Laurel G.; Barr, Jordan G.

    2014-01-01

    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.

  14. An Air-water Interfacial Area Based Variable Tortuosity Model for Unsaturated Sands

    NASA Astrophysics Data System (ADS)

    Khaleel, R.; Saripalli, P.

    2005-12-01

    A new variable tortuosity definition is introduced that is based on the immiscible fluid (air-water) interfacial area. Unsaturated media tortuosity (τa) is defined as the ratio of aaw to aaw,o where aaw is the estimated air-water interfacial area in a real unsaturated medium (i.e., a soil sample), and aaw,o is the same variable for the corresponding, idealized capillary bundle. We establish equivalence between the real and the idealized media by letting the laboratory-measured retention curve calculate the distribution of capillary tubes, thereby resulting in an identical pore-size distribution but a new retention curve for the idealized medium. The air-water interfacial area for both real and idealized media is directly proportional to the area under their respective retention curves. With τ being the saturated tortuosity, we relate the variable tortuosity ratio (ττa) to the Seɛ term in Mualem's (ɛ=0.5) and Burdine's (ɛ=2) pore-size distribution models. Thus, instead of using tortuosity and/or pore connectivity formulations that have empirical exponents of either 0.5 or 2, the new model depends on variable interfacial area for varying saturation and soil texture, as reflected in the measured retention data. We tested the new definition of tortuosity for 22 repacked Hanford sediments that are comprised of mostly coarse and fine sands but some also contain a sizeable fraction (as high as 27%) of fines (silt and clay). Replacing the Se2 term in van Genuchten-Mualem (VGM) model by the new interfacial area based variable tortuosity ratio, and still using saturated conductivity and retention parameters, as used in the conventional approach, we obtain interfacial area based K(θ) predictions that are nearly identical to the conventional VGM model predictions. We also compare the interfacial area based K(θ) predictions with the standard Brooks-Corey-Burdine (BCB) model predictions. Compared to the VGM model predictions, interfacial area based BCB K(θ) predictions

  15. 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.

  16. 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

  17. 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.

  18. Corrosion of copper-based materials in gamma-irradiated air/water vapor systems

    SciTech Connect

    Reed, D.T.

    1992-04-01

    Experiments were performed to investigate the atmospheric corrosion of copper-based materials in an irradiated air/water vapor system. The three materials investigated were oxygen-free copper (CDA-102), 7% aluminum-bronze (CDA-613), and 70-30 cupronickel (CDA-715). To support the corrosion studies, a number of irradiation studies were performed to characterize the gas phase radiation chemistry of the system. Both copper oxide and nitrate phases were identified as corrosion products depending on the dose rate, humidity and temperature. Uniform corrosion rates increased with temperature, humidity, and dose rate. A clear tie between the radiolytic products generated in the gas phase and the corrosion observed was established.

  19. Corrosion of copper-based materials in gamma-irradiated air/water vapor systems

    SciTech Connect

    Reed, D.T.

    1992-01-01

    Experiments were performed to investigate the atmospheric corrosion of copper-based materials in an irradiated air/water vapor system. The three materials investigated were oxygen-free copper (CDA-102), 7% aluminum-bronze (CDA-613), and 70-30 cupronickel (CDA-715). To support the corrosion studies, a number of irradiation studies were performed to characterize the gas phase radiation chemistry of the system. Both copper oxide and nitrate phases were identified as corrosion products depending on the dose rate, humidity and temperature. Uniform corrosion rates increased with temperature, humidity, and dose rate. A clear tie between the radiolytic products generated in the gas phase and the corrosion observed was established.

  20. Measuring Air-Water Interfacial Area via the Interfacial Partitioning Tracer Test Method

    NASA Astrophysics Data System (ADS)

    El Ouni, A.; Zhong, H.; Mainhagu, J.; Araujo, J. B.; Brusseau, M. L.

    2012-12-01

    Interfacial partitioning tracer tests (IPTT) are one method available for measuring air-water interfacial area (Aa-w). Two variations of the aqueous IPTT method are compared. One involves the standard approach comprising tracer injection under steady unsaturated-flow conditions with a uniform water-saturation distribution within the column. The other involves tracer injection under steady saturated-flowconditions in the presence of trapped residual air. Sodium dodecylbezenesulfonate (SDBS) and pentafluorobenzoic acid (PFBA) were used as the partitioning andnonreactive tracers, respectively. A sandy soil with a median grain diameter of 0.234 mm was used as the porous medium. Initial water saturation, Sw,was approximately 80%. Water saturation was monitored gravimetrically during the experiments. The results of the experiments will be assessed and compared to those of prior studies.

  1. Sea breeze forcing of estuary turbulence and air-water CO2 exchange

    NASA Astrophysics Data System (ADS)

    Orton, Philip M.; McGillis, Wade R.; Zappa, Christopher J.

    2010-07-01

    The sea breeze is often a dominant meteorological feature at the coastline, but little is known about its estuarine impacts. Measurements at an anchored catamaran and meteorological stations along the Hudson River and New York Bay estuarine system are used to illustrate some basic characteristics and impacts of the feature. The sea breeze propagates inland, arriving in phase with peak solar forcing at seaward stations, but several hours later at up-estuary stations. Passage of the sea breeze front raises the water-to-air CO2 flux by 1-2 orders of magnitude, and drives turbulence comparable to spring tide levels in the upper meter of the water column, where most primary productivity occurs in this highly turbid system. Modeling and observational studies often use remotely-measured winds to compute air-water fluxes (e.g., momentum, CO2), and this leads to a factor of two flux error on sea breeze days during the study.

  2. 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.

  3. 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.

  4. 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.

  5. Air-water CO2 exchange in five hypereutrophic lakes in Bangalore, India

    NASA Astrophysics Data System (ADS)

    Singh, G.; Ghosh, P.; Bala, G.; Bastviken, D.

    2014-12-01

    Inland water bodies play a significant role in terrestrial carbon cycling, rather than being just conduits for the transport of terrestrial carbon to the oceans. Recent syntheses estimate that freshwaters emit substantial amounts of CO2 (1.4 Pg C yr-1) (Tranvik et al. 2009) and CH4 (0.65 Pg C yr-1) (Bastviken et al. 2011), which are similar in magnitude to the global terrestrial carbon sink (2.5 ± 1.7 Pg C yr-1) (IPCC 2013). However, eutrophic waters, which constitute the majority of the global freshwater supply (ILEC/UNEP 1994, Liu et al. 2012, Carpenter et al. 1998), are vastly underrepresented in these estimates. These waters, due to high primary productivity leading to CO2 undersaturation, can act as sinks rather than sources of CO2, thus reversing the role of lakes in the carbon cycle (Balmer and Downing 2011, Pacheco et al. 2013). We are investigating the air-water CO2 exchange of five hypereutrophic lakes in urban Bangalore using a novel Non-Dispersive Infrared (NDIR)-based CO2 sensor installed in flux chambers that can be used to measure CO2 exchange in lakes in situ. This work is a part of a larger study called Bangalore Carbon Mapping Study that aims to track the spatial flows of carbon in an urban area of a developing country. Preliminary observations reveal that these lakes absorb CO2 during the photosynthetic hours, at an average rate of 3.4 mg C m-2 h-1. The ongoing study will characterize the complete diurnal cycle of CO2 exchange, its variation over different seasons, and its relationships with various limnological and catchment characteristics. The flux estimates thus produced will also be compared with those predicted by the current models for air-water gas exchange based on wind speed.

  6. Air-water exchange fluxes of polycyclic aromatic hydrocarbons in the tropical coast, Taiwan.

    PubMed

    Cheng, Jing-O; Ko, Fung-Chi; Lee, Chon-Lin; Fang, Meng-Der

    2013-03-01

    Air-water exchange fluxes of polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in air and water samples from two sites on the Kenting coast, located at the southern tip of Taiwan, from January to December 2010. There was no significant difference in the total PAH (t-PAH) concentrations in both gas and dissolved phases between these two sites due to the less local input which also coincided to the low levels of t-PAH concentration; the gas and dissolved phases averaged 1.29±0.59 ng m(-3) and 2.17±1.19 ng L(-1) respectively. The direction and magnitude of the daily flux of PAHs were significantly influenced by wind speed and dissolved PAH concentrations. Individual PAH flux ranged from 627 ng m(-2) d(-1) volatilization of phenanthrene during the rainy season with storm-water discharges raising dissolved phase concentration, to 67 ng m(-2) d(-1) absorption of fluoranthene during high wind speed periods. Due to PAH annual fluxes through air-water exchange, Kenting seawater is a source of low molecular weight PAHs and a reservoir of high molecular weight PAHs. Estimated annual volatilization fluxes ranged from 7.3 μg m(-2) yr(-1) for pyrene to 50 μg m(-2) yr(-1) for phenanthrene and the absorption fluxes ranged from -2.6 μg m(-2) yr(-1) for chrysene to -3.5 μg m(-2) yr(-1) for fluoranthene. PMID:23260251

  7. 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.

  8. 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).

  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. 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

  11. Pollution: A Selected Bibliography of U.S. Government Publications on Air, Water, and Land Pollution 1965-1970.

    ERIC Educational Resources Information Center

    Kiraldi, Louis, Comp.; Burk, Janet L., Comp.

    Materials on environmental pollution published by the various offices of the federal government are presented in this select bibliography. Limited in scope to publications on air, water, and land pollution, the document is designed to serve teachers and researchers working in the field of environmental problems who wish reference to public…

  12. Sea Breeze Forcing of Estuary Turbulence and Air-Water Exchanges

    NASA Astrophysics Data System (ADS)

    Orton, P. M.; McGillis, W. R.; Zappa, C. J.

    2010-12-01

    The sea breeze is often a dominant meteorological feature at the coastline, but little is known about its estuarine impacts. It arises on sunny days with weak synoptic weather forcing, due to O(100 km) scale atmospheric pressure differences that develop as a result of the different solar absorption properties of sea and land. Here, measurements at an anchored catamaran and meteorological stations along the Hudson River and New York Bay estuarine system are used to illustrate some basic characteristics and impacts of the feature. The sea breeze propagates inland, arriving in phase with peak solar forcing at seaward stations, but several hours later at up-estuary stations. Passage of the sea breeze front raises the water-to-air CO2 flux by 1-2 orders of magnitude, and drives turbulence comparable to spring tide levels in the upper meter of the water column, where most primary productivity occurs in this highly turbid system. Modeling and observational studies often use remotely-measured winds with quadratic parameterizations to compute air-water fluxes (e.g. momentum, CO2), and this leads to a factor of two flux error on sea breeze days during the study. We conclude with a survey of how common these features are in the Hudson as well as other estuaries.

  13. Seasonal air-water exchange fluxes of polychlorinated biphenyls in the Hudson River Estuary.

    PubMed

    Yan, Shu; Rodenburg, Lisa A; Dachs, Jordi; Eisenreich, Steven J

    2008-03-01

    Polychlorinated biphenyls (PCBs) were measured in the air and water over the Hudson River Estuary during six intensive field campaigns from December 1999 to April 2001. Over-water gas-phase SigmaPCB concentrations averaged 1100 pg/m3 and varied with temperature. Dissolved-phase SigmaPCB concentrations averaged 1100 pg/L and displayed no seasonal trend. Uncertainty analysis of the results suggests that PCBs with 5 or fewer chlorines exhibited net volatilization. The direction of net air/water exchange could not be determined for PCBs with 6 or more chlorines. Instantaneous net fluxes of SigmaPCBs ranged from +0.2 to +630 ng m(-2) d(-1). Annual fluxes of SigmaPCBs were predicted from modeled gas-phase concentrations, measured dissolved-phase concentrations, daily surface water temperatures and wind speeds. The net volatilization flux was +62 microg m(-2) yr(-1), corresponding to an annual loss of +28 kg/yr of SigmaPCBs from the Hudson River Estuary for the year of 2000. PMID:17854962

  14. 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

  15. Calibration of Dissolved Noble Gas Mass Spectrometric Measurements by an Air-Water Equilibration System

    NASA Astrophysics Data System (ADS)

    Hillegonds, Darren; Matsumoto, Takuya; Jaklitsch, Manfred; Han, Liang-Feng; Klaus, Philipp; Wassenaar, Leonard; Aggarwal, Pradeep

    2013-04-01

    Precise measurements by mass spectrometry of dissolved noble gases (He, Ar, Ne, Kr, Xe) in water samples require careful calibration against laboratory standards with known concentrations. Currently, air pipettes are used for day-to-day calibrations, making estimation of overall analytical uncertainties for dissolved noble gas measurements in water difficult. Air equilibrated water (AEW) is often used as a matrix-equivalent laboratory standard for dissolved gases in groundwater, because of the well-known and constant fractions of noble gases in the atmosphere. AEW standards, however, are only useful if the temperature and pressure of the gas-water equilibrium can be controlled and measured precisely (i.e., to better than 0.5%); contamination and partial sample degassing must also be prevented during sampling. Here we present the details of a new custom air-water equilibration system which consists of an insulated 600 liter tank filled with deionized water, held isothermally at a precise target temperature (<0.05 °C) through the use of a heat exchanger. The temperature and total dissolved gas of the water in the tank are monitored continually, as are atmospheric pressure and air temperature in the laboratory. Different noble gas concentration standards can be reliably produced by accurately controlling the water temperature of the equilibration system. Equilibration characteristics and reproducibility of this system for production of copper tubes containing known amounts of noble gases will be presented.

  16. Experimental investigation on liquid film asymmetry in air-water horizontal annular flow

    NASA Astrophysics Data System (ADS)

    Setyawan, Andriyanto; Deendarlianto, Indarto, Neo, Fredrick

    2016-06-01

    The asymmetry of circumferential liquid film thickness distribution in an air-water horizontal annular flow has been experimentally investigated using superficial gas and liquid velocity of 10 - 40 m/s and 0.025 to 0.4 m/s, respectively. In general, the film at the bottom of the pipe will be thicker than that of the side and the top. The asymmetry parameter could be expressed in the ratio of average film thickness to the bottom film thickness or the ratio of the top-to-bottom film thickness. Measurement using compact multiple probe instrument shows that the circumferential film thickness distribution is strongly affected by superficial gas velocity. The higher gas velocity results in the more uniform liquid film circumferential distribution. In comparison to the existing correlations, the asymmetry parameter resulted from the experiment shows a good agreement. It is also shown from the experiment that a less symmetry of film thickness distribution is resulted when the gravity force is dominant. A more symmetry distribution is resulted when the inertial force takes control.

  17. 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., Jr.

    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.

  18. Flow Regimes of Air-Water Counterflow Through Cross Corrugated Parallel Plates

    SciTech Connect

    de Almeida, V.F.

    2000-06-07

    Heretofore unknown flow regimes of air-water counterflow through a pair of transparent vertical parallel cross corrugated plates were observed via high-speed video. Air flows upward driven by pressure gradient and water, downward driven by gravity. The crimp geometry of the corrugations was drawn from typical corrugated sheets used as filling material in modern structured packed towers. Four regimes were featured, namely, rivulet, bicontinuous, flooding fronts, and flooding waves. It is conceivable that the regimes observed might constitute the basis for understanding how gas and liquid phases contend for available space in the interstices of structured packings in packed towers. Flow regime transitions were expressed in terms of liquid load (liquid superficial velocity) and gas flow factor parameters commonly used in pressure drop and capacity curves. We have carefully examined the range of parameters equivalent to the ill-understood high-liquid-flow operation in packed towers. More importantly, our findings should prove valuable in validating improved first-principles modeling of gas-liquid flows in these industrially important devices.

  19. Time-resolved Fast Neutron Radiography of Air-water Two-phase Flows

    NASA Astrophysics Data System (ADS)

    Zboray, Robert; Dangendorf, Volker; Mor, Ilan; Tittelmeier, Kai; Bromberger, Benjamin; Prasser, Horst-Michael

    Neutron imaging, in general, is a useful technique for visualizing low-Z materials (such as water or plastics) obscured by high-Z materials. However, when significant amounts of both materials are present and full-bodied samples have to be examined, cold and thermal neutrons rapidly reach their applicability limit as the samples become opaque. In such cases one can benefit from the high penetrating power of fast neutrons. In this work we demonstrate the feasibility of time-resolved, fast neutron radiography of generic air-water two-phase flows in a 1.5 cm thick flow channel with Aluminum walls and rectangular cross section. The experiments have been carried out at the high-intensity, white-beam facility of the Physikalisch-Technische Bundesanstalt, Germany. Exposure times down to 3.33 ms have been achieved at reasonable image quality and acceptable motion artifacts. Different two-phase flow regimes such as bubbly slug and churn flows have been examined. Two-phase flow parameters like the volumetric gas fraction, bubble size and bubble velocities have been measured.

  20. 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.

  1. 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 ...

  2. [Charge generation and separation at liquid interfaces]. Technical progress report

    SciTech Connect

    Eisenthal, K.B.

    1992-12-01

    The research is divided into 3 parts: (1)Sum Frequency Generation (SFG) and Monolayer Structure. Picosecond lasers are combined by difference frequency mixing in a nonlinear crystal to generate picosecond, tunable IR pulses, which are used to study orientation of C{double_bond}N and CD{sub 3} chromosphores (head group and tail) on lipid monolayers CD{sub 3}(CH{sub 2}){sub 21}CN at air/water interface. (2)Femtosecond Dynamics. The femtosecond colliding pulse mode locked laser is being modified to carry out pump-second harmonic (SH) probe studies at liquid interfaces. Picosecond SH knowhow of intermolecular energy transfer, excited state isomerization, and rotational motions at interfaces is now being applied to femtosecond scale. Aromatics adsorbed at air/water interface, generated changes in SH probe signal and their decay back to original value. If the laser is tightly focussed at interface, multiphoton absorption processes occur which destroy the sample; this effect will be exploited. (3)Interface Potential and Acid-Base Equilibria. The interface potential is a key to charge transport; using SHG, we plan to measure the pKa of organic acids at interfaces. In these studies at silica/aqueous interface, the water molecules extending from the interface into the bulk (about 50{Angstrom}) were strongly polarized by SiO{sup {minus}} charges at the interface. In summary, a new spectroscopic technique is being applied to study of neutral and charged lipid monolayers, interface pKa values, interface potential and orientational structure and vibrational spectroscopy of lipids.

  3. 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.

  4. Fluid (Air/Water) Cushion Transportation Technology for Emplacing Heavy Canisters into Horizontal Disposal Drifts

    SciTech Connect

    Bosgiraud, J.M.; Seidler, W.K.; Londe, L.; Thurner, E.; Pettersson, S.

    2008-07-01

    The disposal of certain types of radioactive waste canisters in a deep repository involves handling and emplacement of very heavy loads. The weight of these particular canisters can be in the order of 20 to 50 metric tons. They generally have to be handled underground in openings that are not much larger than the canisters themselves as it is time consuming and expensive to excavate and backfill large openings in a repository. This therefore calls for the development of special technology that can meet the requirements for safe operation at an industrial scale in restrained operating spaces. Air/water cushion lifting systems are used world wide in the industry for moving heavy loads. However, until now the technology needed for emplacing heavy cylindrical radioactive waste packages in bored drifts (with narrow annular gaps) has not been previously developed or demonstrated. This paper describes the related R and D work carried out by ANDRA (for air cushion technology) and by SKB and Posiva (for water cushion technology) respectively, mainly within the framework of the European Commission (EC) funded Integrated Project called ESDRED (6. European Framework Programme). The background for both the air and the water cushion applications is presented. The specific characteristics of the two different emplacement concepts are also elaborated. Then the various phases of the Test Programmes (including the Prototype phases) are detailed and illustrated for the two lifting media. Conclusions are drawn for each system developed and evaluated. Finally, based on the R and D experience, improvements deemed necessary for an industrial application are listed. The tests performed so far have shown that the emplacement equipment developed is operating efficiently. However further tests are required to verify the availability and the reliability of the equipment over longer periods of time and to identify the modifications that would be needed for an industrial application in a

  5. Microwave plasma source operating with atmospheric pressure air-water mixtures

    SciTech Connect

    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 {yields} NO{sup +}+ 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 NO{sub 2} and nitrous acid HNO{sub 2} have also been detected by mass and Fourier Transform Infrared spectroscopy. The relative population density of O({sup 3}P) 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 O{sub 2}(a{sup 1}{Delta}{sub g}) singlet delta oxygen molecules and OH radicals (1% and 5%, respectively) can be achieved in the discharge zone. In the late afterglow the O{sub 2}(a{sup 1}{Delta}{sub g}) 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.

  6. 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

  7. Tide and Wind Forcing of Estuarine Air-Water Gas Transfer

    NASA Astrophysics Data System (ADS)

    Orton, P. M.; Zappa, C. J.; McGillis, W. R.

    2008-12-01

    Recent studies have demonstrated that while gas transfer is primarily driven by wind, tidal currents can drive gas exchange in estuaries. Studies have also shown that the turbulent kinetic energy (TKE) dissipation just below the sea surface is a good proxy for the gas exchange velocity (k) for a wide range of forcing processes (e.g. wind, currents, rain). However, the connection between tidally-driven turbulence and gas exchange has not been investigated in detail. In this study, an autonomous instrumented surface platform deployment and one-dimensional numerical modeling are used to examine the influence of wind, tidal current shear, and water column bottom boundary layer (BBL) growth on gas transfer in an estuary. An autonomous instrumented surface platform was deployed for one month at a shallow site in the Hudson River estuary, measuring wind velocity, water velocity, TKE dissipation, air-water CO2 gradient and flux, and gas transfer velocity. Currents were 0-0.8 m s-1, winds 0-14 m s-1, depths 4.7-6.2 m, significant wave heights 0-0.8 m, and water pCO2 700-1600 μatm during the study. Surveys spanning the entire estuary from 2002 to the present broaden our understanding of tidal currents, stratification and turbulence to the entire estuary, with over a billion acoustic velocity measurements, millions of turbulence measurements, and 50 CTD surveys up the entire length of the estuary. The estuarine observations show a strong relationship between wind and k, but several recent parameterizations of k as a function of wind speed under-predict k for low-to-moderate winds (1-6 m s- 1). Upper water-column TKE dissipation and k are correlated, consistent with a recent parameterization. Both processes show enhancement when the turbulent BBL nears the sea surface. One-dimensional turbulence modeling is used to expand these results to a broad range of estuaries.

  8. 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.

  9. A study of dilational rheological properties of polymers at interfaces.

    PubMed

    Cao, Xulong; Li, Yang; Jiang, Shengxiang; Sun, Huanquan; Cagna, Alain; Dou, Lixia

    2004-02-15

    Viscoelastic properties of two polymers, partially hydrolyzed polyacrylamide and partially hydrolyzed modified polyacrylamide, widely used in chemical flooding in the petroleum industry, were investigated at three interfaces, water-air, water-dodecane, and water-crude oil, by means of a dilational method provided by I.T. Concept, France, at 85 degrees C. Polymer solutions were prepared in brine with 10,000 mg/l sodium chloride and 2000 mg/l calcium chloride. It has been shown that the viscoelastic modulus increases with the increment of polymer concentration in the range of 0-1500 mg/l at the water-air interface. Each polymer shows different viscoelatic behavior at different interfaces. Generally speaking, values of the viscoelastic modulus (E), the real part (E'), and the imaginary part (E") at the crude oil-water interface for each polymer are lower than at the air-water or water-dodecane interface. The two polymers display different interfacial properties at the same interface. Polymer No. 2 gives more viscous interfaces than polymer No. 1. All the information obtained from this paper will be helpful in understanding the interfacial rheology of ultra-high-molecular-weight polymer solutions. PMID:14697692

  10. 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

  11. Aqueous solubility, Henry's law constants and air/water partition coefficients of n-octane and two halogenated octanes.

    PubMed

    Sarraute, S; Delepine, H; Costa Gomes, M F; Majer, V

    2004-12-01

    New data on the aqueous solubility of n-octane, 1-chlorooctane and 1-bromooctane are reported between 1 degree C and 45 degrees C. Henry's law constants, K(H), and air/water partition coefficients, K(AW), were calculated by associating the measured solubility values to vapor pressures taken from literature. The mole fraction aqueous solubility varies between (1.13-1.60)x10(-7) for n-octane with a minimum at approximately 23 degrees C, (3.99-5.07)x10(-7) for 1-chlorooctane increasing monotonically with temperature and (1.60-3.44)x10(-7) for 1-bromooctane with a minimum near 18 degrees C. The calculated air-water partition coefficients increase with temperature and are two orders of magnitude lower for the halogenated derivatives compared to octane. The precision of the results, taken as the average absolute deviations of the aqueous solubility, the Henry's law constants, or the air/water partition coefficients, from appropriate smoothing equations as a function of temperature is of 3% for n-octane and of 2% and 4% for 1-chlorooctane and 1-bromooctane, respectively. A new apparatus based on the dynamic saturation column method was used for the solubility measurements. Test measurements with n-octane indicated the capability of measuring solubilities between 10(-6) and 10(-10) in mole fraction, with an estimated accuracy better than +/-10%. A thorough thermodynamic analysis of converting measured data to air/water partition coefficients is presented. PMID:15519399

  12. Performance of a combined three-hole conductivity probe for void fraction and velocity measurement in air-water flows

    NASA Astrophysics Data System (ADS)

    Borges, João Eduardo; Pereira, Nuno H. C.; Matos, Jorge; Frizell, Kathleen H.

    2010-01-01

    The development of a three-hole pressure probe with back-flushing combined with a conductivity probe, used for measuring simultaneously the magnitude and direction of the velocity vector in complex air-water flows, is described in this paper. The air-water flows envisaged in the current work are typically those occurring around the rotors of impulse hydraulic turbines (like the Pelton and Cross-Flow turbines), where the flow direction is not known prior to the data acquisition. The calibration of both the conductivity and three-hole pressure components of the combined probe in a rig built for the purpose, where the probe was placed in a position similar to that adopted for the flow measurements, will be reported. After concluding the calibration procedure, the probe was utilized in the outside region of a Cross-Flow turbine rotor. The experimental results obtained in the present study illustrate the satisfactory performance of the combined probe, and are encouraging toward its use for characterizing the velocity field of other complex air-water flows.

  13. Interfacial area transport across vertical elbows in air-water two-phase flow

    NASA Astrophysics Data System (ADS)

    Yadav, Mohan Singh

    The accurate prediction of two-phase flow using the two-fluid model requires closure relations for the interfacial area concentration ( ai), which can be provided by the interfacial area transport equation (IATE). Models have been developed for the IATE in straight pipe geometries. However, to analyze practical systems, it is important that the IATE accounts for flows in pipes with varying orientation that are interconnected via different flow restrictions. In view of this, the current study performs experiments to investigate the geometric effects of 90- degree vertical elbows in air-water two-phase flows and develops a one-group IATE applicable to vertical-upward-to-horizontal two-phase flows. The experimental facility consists of both vertical and horizontal sections constructed from 50.8 mm inner diameter acrylic pipes that are interconnected via 90-degree glass elbows. The elbows have a radius of curvature of Rc/D = 3 and are installed at L/D = 63 and 244.7 from the inlet. Experiments are performed to characterize the elbow-effect on both global and local two-phase flow parameters. A four-sensor conductivity probe is used to acquire detailed measurements of local two-phase flow parameters at thirteen axial locations along the test section in eight flow conditions that are within the bubbly flow regime at inlet. The measurements show that in bubbly flow conditions, the vertical-upward elbow causes a characteristic bimodal-type bubble distribution and the change in this distribution farther downstream of the elbow corresponds to the dissipation of the elbow-effects. In view of developing the IATE for vertical-upward to horizontal two-phase flows, predictive models for the dissipation length of the elbow-effect and closure relations for advection of gas-phase, pressure loss, and covariance of bubble interactions are developed. The new models are evaluated against the current experimental database. Overall, the model predictions agree with the data within +/-7

  14. Growth of gravity-capillary waves in countercurrent air/water turbulence

    NASA Astrophysics Data System (ADS)

    Soldati, Alfredo; Zonta, Francesco; Onorato, Miguel

    2015-11-01

    We use Direct Numerical Simulation (DNS) of the Navier Stokes equations to analyze the dynamics of the interface between air and water when both phases are driven by opposite pressure gradients (countercurrent configuration). The Reynolds number (Reτ), the Weber number (We) and the Froude number (Fr) fully describe the physical problem. We examine the problem of the transient growth of interface waves for different combinations of physical parameters. Keeping Reτ constant and varying We and Fr , we show that, in the initial stages of the wave generation process, the amplitude of the interface elevation η grows in time as η ~t 2 / 5 . Wavenumber spectra, E (kx) , of the surface elevation in the capillary range are in good agreement with the prediction of the Wave Turbulence Theory. Finally, the wave-induced modification of the average wind and current velocity profiles will be addressed. Support from Regione Autonoma Friuli Venezia Giulia under grant PAR FSC 2007/2013 is gratefully acknowledged.

  15. 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

  16. Molecular Interactions in Monolayers οf Azo Dye/Liquid Crystal Mixtures at Interfaces

    NASA Astrophysics Data System (ADS)

    Bauman, D.; Płóciennik, A.; Inglot, K.

    2009-08-01

    Full Text PDF A study of azo dye/liquid crystal mixtures in monolayers formed at an air-water interface (the Langmuir films) and at a solid surface (the Langmuir-Blodgett films) has been performed. Five azo dyes with various molecular structure and the liquid crystal 4-octyl-4' cyanobiphenyl (8CB) have been used. The dyes have been added to the liquid crystal at various molar fractions. Surface pressure and surface potential versus mean molecular area isotherms for the Langmuir films have been recorded and information about intermolecular interactions at the air-water interface has been obtained. On the basis of electronic absorption measurements for the Langmuir and Langmuir-Blodgett films the conclusions about the ability of dyes molecules to form self aggregates at the interfaces have been drawn. The influence of the dye molecular structure and its concentration on aggregates' geometry has been found.

  17. Consistency in the Sum Frequency Generation Intensity and Phase Vibrational Spectra of the Air/Neat Water Interface

    SciTech Connect

    Feng, Ranran; Guo, Yuan; Lu, Rong; Velarde Ruiz Esparza, Luis A.; Wang, Hongfei

    2011-06-16

    Tremendous progresses have been made in quantitative understanding and interpretation of the hydrogen bonding and ordering structure at the air/water interface since the first sum-frequency generation vibrational spectroscopy (SFG-VS) measurement on the neat air/water interface by Q. Du et al. in 1993 (PRL, 70, 2312-2316, 1993.). However, there are still disagreements and controversies on the consistency between the different experiment measurements and the theoretical computational results. One critical problem lies in the inconsistency between the SFG-VS intensity measurements and the recently developed SFG-VS phase spectra measurements of the neat air/water interface, which has inspired various theoretical efforts trying to understand them. In this report, the reliability of the SFG-VS intensity spectra of the neat air/water interface is to be quantitatively examined, and the sources of possible inaccuracies in the SFG-VS phase spectral measurement is to be discussed based on the non-resonant SHG phase measurement results. The conclusion is that the SFG-VS intensity spectra data from different laboratories are now quantitatively converging and in agreement with each other, and the possible inaccuracies and inconsistencies in the SFG-VS phase spectra measurements need to be carefully examined against the properly corrected phase standard.

  18. 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.

  19. 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.

  20. Polycyclic aromatic hydrocarbon (PAH) and oxygenated PAH (OPAH) air-water exchange during the deepwater horizon oil spill.

    PubMed

    Tidwell, Lane G; Allan, Sarah E; O'Connell, Steven G; Hobbie, Kevin A; Smith, Brian W; Anderson, Kim A

    2015-01-01

    Passive sampling devices were used to measure air vapor and water dissolved phase concentrations of 33 polycyclic aromatic hydrocarbons (PAHs) and 22 oxygenated PAHs (OPAHs) at four Gulf of Mexico coastal sites prior to, during, and after shoreline oiling from the Deepwater Horizon oil spill (DWH). Measurements were taken at each site over a 13 month period, and flux across the water-air boundary was determined. This is the first report of vapor phase and flux of both PAHs and OPAHs during the DWH. Vapor phase sum PAH and OPAH concentrations ranged between 1 and 24 ng/m(3) and 0.3 and 27 ng/m(3), respectively. PAH and OPAH concentrations in air exhibited different spatial and temporal trends than in water, and air-water flux of 13 individual PAHs were strongly associated with the DWH incident. The largest PAH volatilizations occurred at the sites in Alabama and Mississippi in the summer, each nominally 10,000 ng/m(2)/day. Acenaphthene was the PAH with the highest observed volatilization rate of 6800 ng/m(2)/day in September 2010. This work represents additional evidence of the DWH incident contributing to air contamination, and provides one of the first quantitative air-water chemical flux determinations with passive sampling technology. PMID:25412353

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. Experimental verification of the four-sensor probe model for flow diagnosis in air water flow in vertical pipe

    NASA Astrophysics Data System (ADS)

    Pradhan, S.; Mishra, R.

    2012-05-01

    Measuring the volumetric flow rate of each of the flowing components is required to be monitored in production logging applications. Hence it is necessary to measure the flow rates of gas, oil and water in vertical and inclined oil wells. An increasing level of interest has been shown by the researchers in developing system for the flow rate measurement in multiphase flows. This paper describes the experimental methodology using a miniature, local four-sensor probe for the measurement of dispersed flow parameters in bubbly two-phase flow for spherical bubbles. To establish interdependent among different parameters corresponding to dispersed flow, the available model has been used to experimentally obtain different parameters such as volume fraction, velocity and bubble shape of the dispersed phase in the bubbly air-water flow.

  6. A dual-surfactant approach for the interfacial partitioning tracer test measurement of air-water interfacial area

    NASA Astrophysics Data System (ADS)

    El Ouni, A.; Brusseau, M. L.

    2013-12-01

    Interfacial partitioning tracer tests (IPTT) are one method available for measuring air-water interfacial area (A_ia). The method has been shown to provide uncertain measurements that are influenced by surfactant-enhanced drainage. The purpose of this work is to test a revised method that minimizes formation of interfacial-tension gradients in order to prevent surfactant-induced drainage. The method employs a dual-surfactant injection under steady unsaturated-flow conditions. Sodium dodecylbezene sulfonate (SDBS) and pentafluorobenzoic acid (PFBA) were used as the partitioning and nonreactive tracers, respectively. Sodium dodecyl sulfate (SDS) was used as the surfactant in the background solution. Three types of porous media were used for the study: a sandy soil, a well-sorted sand, and glass beads. Water saturation was monitored gravimetrically during the experiments. The results obtained with the revised method are compared to those obtained with the standard IPTT method.

  7. 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).

  8. 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

  9. 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

  10. 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.

  11. OH-Radical Specific Addition to Glutathione S-Atom at the Air-Water Interface: Relevance to the Redox Balance of the Lung Epithelial Lining Fluid.

    PubMed

    Enami, Shinichi; Hoffmann, Michael R; Colussi, Agustín J

    2015-10-01

    Antioxidants in epithelial lining fluids (ELF) prevent inhaled air pollutants from reaching lung tissue. This process, however, may upset ELF's redox balance, which is deemed to be expressed by the ratio of the major antioxidant glutathione (GSH) to its putative oxidation product GSSG. Previously, we found that at physiological pH O3(g) rapidly oxidizes GS(2-)(aq) (but not GSH(-)) to GSO3(-) rather than GSSG. Here, we report that in moderately acidic pH ≤ 5 media ·OH(g) oxidizes GSH(-)(aq) to sulfenic GSOH(-), sulfinic GSO2(-), and sulfonic GSO3(-) acids via ·OH specific additions to reduced S-atoms. The remarkable specificity of ·OH on water versus its lack of selectivity in bulk water implicates an unprecedented steering process during [OH···GSH] interfacial encounters. Thus, both O3 and ·OH oxidize GSH to GSOH(-) under most conditions, and since GSOH(-) is reduced back to GSH in vivo by NADPH, redox balance may be in fact signaled by GSH/GSOH ratios. PMID:26722895

  12. Analysis of the Asymmetric Synergy in the Adsorption of Zwitterionic-Ionic Surfactant Mixtures at the Air-Water Interface below and above the Critical Micelle Concentration.

    PubMed

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

    2016-04-21

    Surface tension (ST) and neutron reflection (NR) measurements have been made on a series of mixtures of two ionic surfactants, one anionic (SDS) and one cationic (C12TAB), with the two zwitterionic surfactants dodecyldimethylammonium propanesulfonate (C12SB) and dodecyldimethylammonium acetate C12CB. The anionic surfactant SDS interacts equally strongly with both zwitterionics and the C12TAB less strongly. For the SDS-C12SB mixtures simultaneous fitting of ST and NR data made it possible to use the pseudophase approximation with an expansion of the excess free energy, GE, up to and including the quartic term. GE is asymmetric for the adsorbed layer and the minimum occurs at a surface mole fraction, xSDS, of 0.38 with a depth of -2.8RT. NR was also used to follow the adsorption above the CMC, and the changes showed that the intramicellar interaction is more asymmetric, but weaker than the surface interaction with a depth of GE of -2.2RT at the minimum of xSDS = 0.23. A strong synergy in the total surface excess was observed above the mixed CMC with an enhancement over the adsorption of the pure components of about 45%, which appears to result from a sharp variation of the packing with surface composition coupled with the effects of the strongly asymmetric micellization. NR data on SDS-C12CB showed that GE for both surface and micelles was similarly asymmetric to those for SDS-C12SB, but there is no strong synergy in adsorption. This is attributed to the more rigid headgroup. C12TAB-C12SB has an asymmetric GE for both surface and micelle similar to those for SDS-C12SB but the depths are smaller at -0.6RT and -0.5RT, respectively, and there is no synergy in the total adsorption. PMID:27029532

  13. Quantum chemical clarification of the alkyl chain length threshold of nonionic surfactants for monolayer formation at the air/water interface.

    PubMed

    Vysotsky, Yu B; Kartashynska, E S; Belyaeva, E A; Vollhardt, D; Fainerman, V B; Miller, R

    2016-03-21

    A theoretical basis is provided for the experimental fact that for various surfactant classes the alkyl chain length threshold varies for the formation of condensed monolayers. The existence of the alkyl chain length threshold for a surfactant enabling the formation of monolayers is determined by the entropy increment to the Gibbs' energy, assessed by using the quantum chemical semiempiric method PM3. The value of the clusterization threshold is not stipulated by the surfactant solubility in water, rather by the electron-donor and electron-seeking properties of the head groups. These properties in turn impact the value of the solubility threshold for surfactants. The value of the clusterization threshold depends quadratically on the substituent constants, i.e. it is independent of whether the functional group is a donor or an acceptor of electrons. Rather it depends only on the donor or the acceptor 'force' of the substituent. The square-law dependence of the surface clusterization threshold of the amphiphile on the solubility threshold is evidenced. PMID:26957020

  14. 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

    2016-01-01

    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

  15. 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

  16. 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

  17. 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

  18. 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

  19. 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.

  20. 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

  1. 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...

  2. 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.

  3. Reynolds and froude number effect on the flow past an interface-piercing circular cylinder

    NASA Astrophysics Data System (ADS)

    Koo, Bonguk; Yang, Jianming; Yeon, Seong Mo; Stern, Frederick

    2014-09-01

    The two-phase turbulent flow past an interface-piercing circular cylinder is studied using a high-fidelity orthogonal curvilinear grid solver with a Lagrangian dynamic subgrid-scale model for large-eddy simulation and a coupled level set and volume of fluid method for air-water interface tracking. The simulations cover the sub-critical and critical and post critical regimes of the Reynolds and sub and super-critical Froude numbers in order to investigate the effect of both dimensionless parameters on the flow. Significant changes in flow features near the air-water interface were observed as the Reynolds number was increased from the sub-critical to the critical regime. The interface makes the separation point near the interface much delayed for all Reynolds numbers. The separation region at intermediate depths is remarkably reduced for the critical Reynolds number regime. The deep flow resembles the single-phase turbulent flow past a circular cylinder, but includes the effect of the free-surface and the limited span length for sub-critical Reynolds numbers. At different Froude numbers, the air-water interface exhibits significantly changed structures, including breaking bow waves with splashes and bubbles at high Froude numbers. Instantaneous and mean flow features such as interface structures, vortex shedding, Reynolds stresses, and vorticity transport are also analyzed. The results are compared with reference experimental data available in the literature. The deep flow is also compared with the single-phase turbulent flow past a circular cylinder in the similar ranges of Reynolds numbers. Discussion is provided concerning the limitations of the current simulations and available experimental data along with future research

  4. 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

  5. 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

  6. 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)

  7. 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

  8. 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.

  9. 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

  10. 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.

  11. 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

  12. Orientational dynamics of water at an extended hydrophobic interface

    NASA Astrophysics Data System (ADS)

    Figge, Florian; Xiao, Shunhao; McGuire, John A.; Stirnemann, Guillaume; Laage, Damien

    Aqueous interfaces are central to many physical processes, but the dynamics of interfacial water molecules have been little studied. We have measured the orientational dynamics of water at its interface with a self-assembled monolayer of octadecylsilane on fused silica. A surface-sensitive sum-frequency probe generated by mixing a visible and a vibrationally resonant infrared (IR) pulse is used to monitor the dangling (non-hydrogen-bonded) OH stretch vibration after excitation with a resonant IR pump pulse. By measuring pure and isotopically diluted water with orthogonal pump polarizations, we find that relaxation of the dangling OH stretch excitation is dominated by the out-of-plane jump from a dangling to a hydrogen-bonded configuration and the subsequent redistribution of energy from the surface hydrogen-bonded OH stretch excitation. The out-of-plane jump time is 1.5(1)ps, 30% slower than that reported for the air-water interface and twice as short as the jump time between hydrogen bonded configurations in the bulk. Molecular dynamics simulations indicate that the slower dynamics at the hydrophobic interface compared to the water-air interface are due to the hydrogen bonds at the hydrophobic interface being stronger than those at the water-air interface. The authors acknowledge support from the National Science Foundation (Grant No. CHE- 1151590).

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. Adsorption of Bovine Serum Albumin (BSA) at the Oil/Water Interface: A Neutron Reflection Study.

    PubMed

    Campana, M; Hosking, S L; Petkov, J T; Tucker, I M; Webster, J R P; Zarbakhsh, A; Lu, J R

    2015-05-26

    The structure of the adsorbed protein layer at the oil/water interface is essential to the understanding of the role of proteins in emulsion stabilization, and it is important to glean the mechanistic events of protein adsorption at such buried interfaces. This article reports on a novel experimental methodology for probing protein adsorption at the buried oil/water interface. Neutron reflectivity was used with a carefully selected set of isotopic contrasts to study the adsorption of bovine serum albumin (BSA) at the hexadecane/water interface, and the results were compared to those for the air/water interface. The adsorption isotherm was determined at the isoelectric point, and the results showed that a higher degree of adsorption could be achieved at the more hydrophobic interface. The adsorbed BSA molecules formed a monolayer on the aqueous side of the interface. The molecules in this layer were partially denatured by the presence of oil, and once released from the spatial constraint by the globular framework they were free to establish more favorable interactions with the hydrophobic medium. Thus, a loose layer extending toward the oil phase was clearly observed, resulting in an overall broader interface. By analogy to the air/water interface, as the concentration of BSA increased to 1.0 mg mL(-1) a secondary layer extending toward the aqueous phase was observed, possibly resulting from the steric repulsion upon the saturation of the primary monolayer. Results clearly indicate a more compact arrangement of molecules at the oil/water interface: this must be caused by the loss of the globular structure as a consequence of the denaturing action of the hexadecane. PMID:25875917

  18. 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.

  19. Micrometeorological measurement of hexachlorobenzene and polychlorinated biphenyl compound air-water gas exchange in Lake Superior and comparison to model predictions

    NASA Astrophysics Data System (ADS)

    Rowe, M. D.; Perlinger, J. A.

    2012-01-01

    Air-water exchange fluxes of persistent, bioaccumulative and toxic (PBT) substances are frequently estimated using the Whitman two-film (W2F) method, but micrometeorological flux measurements of these compounds over water are rarely attempted. We measured air-water exchange fluxes of hexachlorobenzene (HCB) and polychlorinated biphenyls (PCBs) on 14 July 2006 in Lake Superior using the modified Bowen ratio (MBR) method. Measured fluxes were compared to estimates using the W2F method, and to estimates from an Internal Boundary Layer Transport and Exchange (IBLTE) model that implements the NOAA COARE bulk flux algorithm and gas transfer model. We reveal an inaccuracy in the estimate of water vapor transfer velocity that is commonly used with the W2F method for PBT flux estimation, and demonstrate the effect of use of an improved estimation method. Flux measurements were conducted at three stations with increasing fetch in offshore flow (15, 30, and 60 km) in southeastern Lake Superior. This sampling strategy enabled comparison of measured and predicted flux, as well as modification in near-surface atmospheric concentration with fetch, using the IBLTE model. Fluxes estimated using the W2F model were compared to fluxes measured by MBR. In five of seven cases in which the MBR flux was significantly greater than zero, concentration increased with fetch at 1-m height, which is qualitatively consistent with the measured volatilization flux. As far as we are aware, these are the first reported micrometeorological air-water exchange flux measurements of PCBs.

  20. Polarization charge: Theory and applications to aqueous interfaces.

    PubMed

    Shi, Bobo; Agnihotri, Mithila V; Chen, Si-Han; Black, Richie; Singer, Sherwin J

    2016-04-28

    When an electric field is applied across an interface, a dielectric will acquire a polarization charge layer, assumed infinitely thin in the theory of macroscopic dielectrics and also in most treatments of electrokinetic phenomena in nanoscale structures. In this work we explore the polarization charge layer in molecular detail. Various formal relations and a linear response theory for the polarization charge are presented. Properties of the polarization charge layer are studied for three aqueous interfaces: air-water, a crystalline silica surface with water, and an amorphous silica surface with water. The polarization charge is calculated from equilibrium simulations via linear response theory and from non-equilibrium simulations, and the results are within statistical error. The polarization charge is found to be distributed within a region whose width is on the order of a nanometer. PMID:27131558

  1. Polarization charge: Theory and applications to aqueous interfaces

    NASA Astrophysics Data System (ADS)

    Shi, Bobo; Agnihotri, Mithila V.; Chen, Si-Han; Black, Richie; Singer, Sherwin J.

    2016-04-01

    When an electric field is applied across an interface, a dielectric will acquire a polarization charge layer, assumed infinitely thin in the theory of macroscopic dielectrics and also in most treatments of electrokinetic phenomena in nanoscale structures. In this work we explore the polarization charge layer in molecular detail. Various formal relations and a linear response theory for the polarization charge are presented. Properties of the polarization charge layer are studied for three aqueous interfaces: air-water, a crystalline silica surface with water, and an amorphous silica surface with water. The polarization charge is calculated from equilibrium simulations via linear response theory and from non-equilibrium simulations, and the results are within statistical error. The polarization charge is found to be distributed within a region whose width is on the order of a nanometer.

  2. 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).

  3. Developing Oxidized Nitrogen Atmospheric Deposition Source Attribution from CMAQ for Air-Water Trading for Chesapeake Bay

    NASA Astrophysics Data System (ADS)

    Dennis, R. L.; Napelenok, S. L.; Linker, L. C.; Dudek, M.

    2012-12-01

    Estuaries are adversely impacted by excess reactive nitrogen, Nr, from many point and nonpoint sources, including atmospheric deposition to the watershed and the estuary itself as a nonpoint source. For effective mitigation, trading among sources of Nr is being considered. The Chesapeake Bay Program is working to bring air into its trading scheme, which requires some special air computations. Airsheds are much larger than watersheds; thus, wide-spread or national emissions controls are put in place to achieve major reductions in atmospheric Nr deposition. The tributary nitrogen load reductions allocated to the states to meet the TMDL target for Chesapeake Bay are large and not easy to attain via controls on water point and nonpoint sources. It would help the TMDL process to take advantage of air emissions reductions that would occur with State Implementation Plans that go beyond the national air rules put in place to help meet national ambient air quality standards. There are still incremental benefits from these local or state-level controls on atmospheric emissions. The additional air deposition reductions could then be used to offset water quality controls (air-water trading). What is needed is a source to receptor transfer function that connects air emissions from a state to deposition to a tributary. There is a special source attribution version of the Community Multiscale Air Quality model, CMAQ, (termed DDM-3D) that can estimate the fraction of deposition contributed by labeled emissions (labeled by source or region) to the total deposition across space. We use the CMAQ DDM-3D to estimate simplified state-level delta-emissions to delta-atmospheric-deposition transfer coefficients for each major emission source sector within a state, since local air regulations are promulgated at the state level. The CMAQ 4.7.1 calculations are performed at a 12 km grid size over the airshed domain covering Chesapeake Bay for 2020 CAIR emissions. For results, we first present

  4. An experimental and analytical investigation into the performance of centrifugal pumps operating with air-water mixtures

    NASA Astrophysics Data System (ADS)

    Sterrett, John Douglas

    1994-01-01

    An investigation was made into the performance of centrifugal pumps when two-phase non-condensable mixtures of gas and liquid are flowing. This problem is encountered during loss-of-coolant accidents in nuclear reactor systems and in the pumping of oil where natural gas may be present in the mixture. Analytical and experimental techniques were used to address the issues of scaling between a model and a prototype pump and the validity of the single-phase pump affinity laws when two-phase flows are present. The results from this effort have also provided insight into the physical phenomena which cause the degradation in pump performance. An analytical model for the motion of a single bubble through a pump impeller is provided. The results from this fundamental problem show that the Coriolis and buoyancy forces are important in describing the kinematics of a gas phase. These results show that dynamic similitude is not preserved between a model and prototype impeller when the standard single-phase pump scaling relationships are used. The motion of a single bubble is also shown to be influenced by the magnitude of the pump suction pressure. The results from an extensive series of air-water two phase pump tests are provided. A 1/4 scale pump, modeled after the Savannah River Site K-reactor pumps, was tested over a wide range of pump speeds, flow rates, and suction pressures. These results indicate that the single-phase pump affinity laws are not applicable to two-phase pump flows and that the magnitude of the pump suction pressure is an important quantity in determining the pump performance. A second analytical model is developed for two-phase flow through a pump impeller. The results from this one-dimensional, two-fluid, non-homogeneous streamline model show good agreement with the experimental data. The model results support the experimental data in showing that the single-phase pump affinity relationships are not valid for two-phase pump flows and that dynamic

  5. Association of alkanes with the aqueous liquid-vapor interface: a reference system for interpreting hydrophobicity generally through interfacial fluctuations

    PubMed Central

    Ou, Shu-Ching; Cui, Di; Patel, Sandeep

    2014-01-01

    We report free energy calculations and fluctuation profiles of single alkanes (from methane to pentane) along the direction normal to the air-water interface. The induced fluctuations and alkanes’ interfacial stabilities are found to be correlated and similar with the results regarding inorganic monovalent ions (Ou et al., J. Phys. Chem. B, 2013, 117, 11732). This suggests that hydrophobic solvation of solutes and ions is important in determining the adsorption behavior. PMID:25372502

  6. 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

  7. 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.

  8. Dynamics of a bubble bouncing at a compound interface

    NASA Astrophysics Data System (ADS)

    Feng, Jie; Muradoglu, Metin; Stone, Howard A.

    2014-11-01

    Bubbly flow is extensively involved in a wide range of technological applications, which generate a great demand for understanding of bubble physics. The collision, bouncing and coalescence of moving bubbles with liquid/gas and liquid/solid interfaces, as the first stage for the formation of foams and flotation aggregates, have been the subject of many studies, but there are still unanswered questions related to how the properties of the interface influence the dynamics. For example, Zawala et al. 2013 have tried to investigate how the kinetic energy of the bubble affects the liquid film drainage during the collision with an air-water interface. Inspired by Feng et al. 2014, we study the dynamics of an air bubble bouncing at a liquid/liquid/gas interface, in which a thin layer of oil is put on top of the water. The presence of the oil layer changes the interfacial properties and thus the entire process. Combined with direct numerical simulations, extensive experiments were carried out to investigate the effects of the oil layer thickness, oil viscosity, bubble size and initial impact velocity on the bouncing of the bubble at the compound interface. In addition, a mass-spring model is proposed to describe the bubble dynamics and interactions with the oil layer.

  9. 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

  10. Micrometeorological measurement of hexachlorobenzene and polychlorinated biphenyl compound air-water gas exchange in Lake Superior and comparison to model predictions

    NASA Astrophysics Data System (ADS)

    Rowe, M. D.; Perlinger, J. A.

    2012-05-01

    Air-water exchange fluxes of persistent, bioaccumulative and toxic (PBT) substances are frequently estimated using the Whitman two-film (W2F) method, but micrometeorological flux measurements of these compounds over water are rarely attempted. We measured air-water exchange fluxes of hexachlorobenzene (HCB) and polychlorinated biphenyls (PCBs) on 14 July 2006 in Lake Superior using the modified Bowen ratio (MBR) method. Measured fluxes were compared to estimates using the W2F method, and to estimates from an Internal Boundary Layer Transport and Exchange (IBLTE) model that implements the NOAA COARE bulk flux algorithm and gas transfer model. We reveal an inaccuracy in the estimate of water vapor transfer velocity that is commonly used with the W2F method for PBT flux estimation, and demonstrate the effect of use of an improved estimation method. Flux measurements were conducted at three stations with increasing fetch in offshore flow (15, 30, and 60 km) in southeastern Lake Superior. This sampling strategy enabled comparison of measured and predicted flux, as well as modification in near-surface atmospheric concentration with fetch, using the IBLTE model. Fluxes estimated using the W2F model were compared to fluxes measured by MBR. In five of seven cases in which the MBR flux was significantly greater than zero, concentration increased with fetch at 1-m height, which is qualitatively consistent with the measured volatilization flux. As far as we are aware, these are the first reported ship-based micrometeorological air-water exchange flux measurements of PCBs.

  11. A Lagrangian Model to Predict the Modification of Near-Surface Scalar Mixing Ratios and Air-Water Exchange Fluxes in Offshore Flow

    NASA Astrophysics Data System (ADS)

    Rowe, Mark D.; Perlinger, Judith A.; Fairall, Christopher W.

    2011-07-01

    A model was developed to predict the modification with fetch in offshore flow of mixing ratio, air-water exchange flux, and near-surface vertical gradients in mixing ratio of a scalar due to air-water exchange. The model was developed for planning and interpretation of air-water exchange flux measurements in the coastal zone. The Lagrangian model applies a mass balance over the internal boundary layer (IBL) using the integral depth scale approach, previously applied to development of the nocturnal boundary layer overland. Surface fluxes and vertical profiles in the surface layer were calculated using the NOAA COARE bulk algorithm and gas transfer model (e.g., Blomquist et al. 2006, Geophys Res Lett 33:1-4). IBL height was assumed proportional to the square root of fetch, and estimates of the IBL growth rate coefficient, α, were obtained by three methods: (1) calibration of the model to a large dataset of air temperature and humidity modification over Lake Ontario in 1973, (2) atmospheric soundings from the 2004 New England Air Quality Study and (3) solution of a simplified diffusion equation and an estimate of eddy diffusivity from Monin-Obukhov similarity theory (MOST). Reasonable agreement was obtained between the calibrated and MOST values of α for stable, neutral, and unstable conditions, and estimates of α agreed with previously published parametrizations that were valid for the stable IBL only. The parametrization of α provides estimates of IBL height, and the model estimates modification of scalar mixing ratio, fluxes, and near-surface gradients, under conditions of coastal offshore flow (0-50 km) over a wide range in stability.

  12. Measurement of air distribution and void fraction of an upwards air-water flow using electrical resistance tomography and a wire-mesh sensor

    NASA Astrophysics Data System (ADS)

    Olerni, Claudio; Jia, Jiabin; Wang, Mi

    2013-03-01

    Measurements on an upwards air-water flow are reported that were obtained simultaneously with a dual-plane electrical resistance tomograph (ERT) and a wire-mesh sensor (WMS). The ultimate measurement target of both ERT and WMS is the same, the electrical conductivity of the medium. The ERT is a non-intrusive device whereas the WMS requires a net of wires that physically crosses the flow. This paper presents comparisons between the results obtained simultaneously from the ERT and the WMS for evaluation and calibration of the ERT. The length of the vertical testing pipeline section is 3 m with an internal diameter of 50 mm. Two distinct sets of air-water flow rate scenarios, bubble and slug regimes, were produced in the experiments. The fast impedance camera ERT recorded the data at an approximate time resolution of 896 frames per second (fps) per plane in contrast with the 1024 fps of the wire-mesh sensor WMS200. The set-up of the experiment was based on well established knowledge of air-water upwards flow, particularly the specific flow regimes and wall peak effects. The local air void fraction profiles and the overall air void fraction were produced from two systems to establish consistency for comparison of the data accuracy. Conventional bulk flow measurements in air mass and electromagnetic flow metering, as well as pressure and temperature, were employed, which brought the necessary calibration to the flow measurements. The results show that the profiles generated from the two systems have a certain level of inconsistency, particularly in a wall peak and a core peak from the ERT and WMS respectively, whereas the two tomography instruments achieve good agreement on the overall air void fraction for bubble flow. For slug flow, when the void fraction is over 30%, the ERT underestimates the void fraction, but a linear relation between ERT and WMS is still observed.

  13. 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

  14. 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

  15. Gas-phase molecular halogen production from sea-salt particles via interface reactions

    NASA Astrophysics Data System (ADS)

    Jimenez-Aranda, A.; Thomas, J.; Finlayson-Pitts, B. J.; Dabdub, D.

    2005-12-01

    Interface reactions at the surface of sea-salt particles have been suggested as an important source of photolyzable gas-phase halogen species in the troposphere. Such reactions are plausible, given theoretical evidence for ions at interfaces, predicted enhancements of some gases at the air-water interface, and the results of a number of experiments in which interface reactions had to be invoked to explain the data. Because of the contributions of halogen chemistry in determining ozone and other trace species in the troposphere, elucidating the roles of interface and bulk chemistry in generating photolyzable halogen gases is important. A revised version of the model of aerosol, gas and interfacial chemistry (MAGIC 2.0) is used in this work to examine the reactions of chloride and bromide ions with OH and O3. The goal is to understand the factors that determine the relative importance of bulk compared to interface chemistry in the most simple chloride and bromide systems represented by deliquesced aerosols of NaCl or NaBr. Results show the interface process involving Cl- and OH(g) is the main source of Cl2(g). For the analogous oxidation of bromide by OH, gaseous Br2 is formed mainly in the bulk aqueous phase and transferred across the interface. However, the reaction of Br- with O3(g) at the interface is the primary source of Br2(g) under dark conditions.

  16. Implicit-Solvent Coarse-Grained Simulation with a Fluctuating Interface Reveals a Molecular Mechanism for Peptoid Monolayer Buckling.

    PubMed

    Haxton, Thomas K; Zuckermann, Ronald N; Whitelam, Stephen

    2016-01-12

    Peptoid polymers form extended two-dimensional nanostructures via an interface-mediated assembly process: the amphiphilic peptoids first adsorb to an air-water interface as a monolayer, then buckle and collapse into free-floating bilayer nanosheets when the interface is compressed. Here, we investigate the molecular mechanism of monolayer buckling by developing a method for incorporating interface fluctuations into an implicit-solvent coarse-grained model. Representing the interface with a triangular mesh controlled by surface tension and surfactant adsorption, we predict the direction of buckling for peptoids with a segregated arrangement of charged side chains and predict that peptoids with with an alternating charge pattern should buckle less easily than peptoids with a segregated charge pattern. PMID:26647143

  17. 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.

  18. A new flooding correlation development and its critical heat flux predictions under low air-water flow conditions in Savannah River Site assembly channels

    SciTech Connect

    Lee, S.Y. )

    1993-10-01

    The upper limit to countercurrent flow, namely, flooding, is important to analyze the reactor coolability during an emergency cooling system (ECS) phase as a result of a large-break loss-of-coolant accident (LOCA) such as a double-ended guillotine break in the Savannah River Site (SRS) reactor system. During normal operation, the reactor coolant system utilizes downward flow through concentric heated tubes with ribs, which subdivided each annular channel into four subchannels. In this paper, a new flooding correlation has been developed based on the analytical models and literature data for adiabatic, steady-state, one-dimensional, air-water flow to predict flooding phenomenon in the SRS reactor assembly channel, which may have a counter-current air-water flow pattern during the ECS phase. In addition, the correlation was benchmarked against the experimental data conducted under the Oak Ridge National Laboratory multislit channel, which is close to the SRS assembly geometry. Furthermore, the correlation has also been used as a constitutive relationship in a new two-component two-phase thermal-hydraulics code FLOWTRAN-TF, which has been developed for a detailed analysis of SRS reactor assembly behavior during LOCA scenarios. Finally, the flooding correlation was applied to the predictions of critical heat flux, and the results were compared with the data taken by the SRS heat transfer laboratory under a single annular channel with ribs and a multiannular prototypic test rig.

  19. 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. PMID:25540847

  20. 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.

  1. 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

  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. Dosimetry of interface region near closed air cavities for Co-60, 6 MV and 15 MV photon beams using Monte Carlo simulations.

    PubMed

    Joshi, Chandra P; Darko, Johnson; Vidyasagar, P B; Schreiner, L John

    2010-04-01

    Underdosing of treatment targets can occur in radiation therapy due to electronic disequilibrium around air-tissue interfaces when tumors are situated near natural air cavities. These effects have been shown to increase with the beam energy and decrease with the field size. Intensity modulated radiation therapy (IMRT) and tomotherapy techniques employ combinations of multiple small radiation beamlets of varying intensities to deliver highly conformal radiation therapy. The use of small beamlets in these techniques may therefore result in underdosing of treatment target in the air-tissue interfaces region surrounding an air cavity. This work was undertaken to investigate dose reductions near the air-water interfaces of 1x1x1 and 3x3x3 cm(3) air cavities, typically encountered in the treatment of head and neck cancer utilizing radiation therapy techniques such as IMRT and tomotherapy using small fields of Co-60, 6 MV and 15 MV photons. Additional investigations were performed for larger photon field sizes encompassing the entire air-cavity, such as encountered in conventional three dimensional conformal radiation therapy (3DCRT) techniques. The EGSnrc/DOSXYZnrc Monte Carlo code was used to calculate the dose reductions (in water) in air-water interface region for single, parallel opposed and four field irradiations with 2x2 cm(2) (beamlet), 10x2 cm(2) (fan beam), 5x5 and 7x7 cm(2) field sizes. The magnitude of dose reduction in water near air-water interface increases with photon energy; decreases with distance from the interface as well as decreases as the number of beams are increased. No dose reductions were observed for large field sizes encompassing the air cavities. The results demonstrate that Co-60 beams may provide significantly smaller interface dose reductions than 6 MV and 15 MV irradiations for small field irradiations such as used in IMRT and tomotherapy. PMID:20589116

  4. 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

  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. PMID:26779953

  6. 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.

  7. 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.

  8. 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.

  9. The kinked interface crack

    NASA Astrophysics Data System (ADS)

    Heitzer, Joerg

    1992-05-01

    Two methods for the numerical solution of the integral equation describing the kinked interface crack, one proposed by Erdogan et al. (1973) and the other by Theokaris and Iokimidis (1979), are examined. The method of Erdogan et al. is then used to solve the equation in order to determine the kinking angle of the interface crack. Results are presented for two material combinations, aluminum/epoxy and glass/ceramic, under uniaxial tension in the direction normal to the interface.

  10. Persistent interface fluid syndrome.

    PubMed

    Hoffman, Richard S; Fine, I Howard; Packer, Mark

    2008-08-01

    We present an unusual case of persistent interface fluid that would not resolve despite normal intraocular pressure and corneal endothelial replacement with Descemet-stripping endothelial keratoplasty. Dissection, elevation, and repositioning of the laser in situ keratomileusis flap were required to resolve the interface fluid. Circumferential corneal graft-host margin scar formation acting as a mechanical strut may have been the cause of the intractable interface fluid. PMID:18655997

  11. 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.

  12. 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.

  13. TSF Interface Package

    SciTech Connect

    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 soerator 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.

  14. 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

  15. Interface dynamics under nonequilibrium conditions: from a self-propelled droplet to dynamic pattern evolution.

    PubMed

    Chen, Y-J; Yoshikawa, K

    2011-04-01

    In this article, we describe the instability of a contact line under nonequilibrium conditions mainly based on the results of our recent studies. Two experimental examples are presented: the self-propelled motion of a liquid droplet and spontaneous dynamic pattern formation. For the self-propelled motion of a droplet, we introduce an experiment in which a droplet of aniline sitting on an aqueous layer moves spontaneously at an air-water interface. The spontaneous symmetry breaking of Marangoni-driven spreading causes regular motion. In a circular Petri dish, the droplet exhibits either beeline motion or circular motion. On the other hand, we show the emergence of a dynamic labyrinthine pattern caused by dewetting of a metastable thin film from the air-water interface. The contact line between the organic phase and the aqueous phase forms a unique spatio-temporal pattern characterized as a dynamic labyrinth. Motion of the contact line is controlled by diffusion processes. We propose a theoretical model to interpret essential aspects of the observed dynamic behavior. PMID:21509663

  16. 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. PMID:27285780

  17. 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.

  18. Interface Conductance Modal Analysis

    NASA Astrophysics Data System (ADS)

    Gordiz, Kiarash; Henry, Asegun

    2015-03-01

    Reliably and quantitatively calculating the conductance of phonons across an interface between two materials has been one of the major unresolved questions in thermal transport physics for the last century. Theories have been presented in this regard, but their predictive power is limited. A new formalism to extract the modal contributions to thermal interface conductance with full inclusion of temperature dependent anharmonicity and all of the atom level topography is presented. The results indicate that when two materials are joined a new set of vibrational modes are required to correctly describe the transport across the interface. The new set of vibrational modes is inconsistent with the physical picture described by phonon gas model (PGM), because some of the most important modes are localized and non-propagating and therefore do not have a well-defined velocity nor do they impinge on the interface. Among these new modes, certain classifications emerge, as most modes extend at least partially into the other material. Localized interfacial modes are also present and exhibit a high conductance contribution on a per mode basis by strongly coupling to other types of vibrational modes. We apply our formalism to different interfaces and present thermal interface conductance accumulation functions, two-dimensional cross-correlation matrices, and a quantitative determination of the contributions arising from inelastic effects. The provided new perspective on interface thermal transport can open new gates towards deeper understanding of phonon-phonon and electron-phonon interactions around interfaces.

  19. 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.

  20. 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…

  1. Interfaces in Perovskite Heterostructures

    SciTech Connect

    Christen, Hans M; Kim, Dae Ho; Rouleau, Christopher M

    2008-01-01

    Recent advances in film synthesis have made it possible to investigate the properties of well-controlled interfaces in perovskite metal-oxides. A review of published experimental data and computational results indicate that so far most interfaces that have been analyzed in ferroelectric materials - while necessary to impose large lattice strain on the polar material - contribute little to the ferroelectricity and may instead be detrimental to the desired properties. In contrast, a very different situation arises at interfaces that show changes in the electronic configuration as a consequence of a compositional discontinuity. Data is shown for LaMnO3/SrTiO 3 superlattices as an example of electronic effects that produce enhanced properties, further illustrating the richness of interfacial properties that can be obtained at interfaces (as shown in numerous published results for different but related interfaces).

  2. 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.

  3. 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. PMID:23033988

  4. 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.

  5. 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. PMID:25019318

  6. 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)

  7. Experimental Study of the Morphology and Dynamics of Gas-Laden Layers Under the Anodes in an Air-Water Model of Aluminum Reduction Cells

    NASA Astrophysics Data System (ADS)

    Vékony, Klára; Kiss, László I.

    2012-10-01

    The bubble layer formed under an anode and the bubble-induced flow play a significant role in the aluminum electrolysis process. The bubbles covering the anode bottom reduce the efficient surface that can carry current. In our experiments, we filmed and studied the bubble layer under the anode in a real-size air-water electrolysis cell model. Three different flow regimes were found depending on the gas generation rate. The covering factor was found to be proportional to the gas generation rate and inversely proportional to the angle of inclination. A correlation between the average height of the entire bubble layer and the position under the anode was determined. From this correlation and the measured contact sizes, the volume of the accumulated gas was calculated. The sweeping effect of large bubbles was observed. Moreover, the small bubbles under the inner edge of the anode were observed to move backward as a result of the escape of huge gas pockets, which means large momentum transport occurs in the bath.

  8. Vapour pressures, aqueous solubility, Henry's law constants and air/water partition coefficients of 1,8-dichlorooctane and 1,8-dibromooctane.

    PubMed

    Sarraute, Sabine; Mokbel, Ilham; Costa Gomes, Margarida F; Majer, Vladimir; Delepine, Hervé; Jose, Jacques

    2006-09-01

    New data on the vapour pressures and aqueous solubility of 1,8-dichlorooctane and 1,8-dibromooctane are reported as a function of temperature between 20 degrees C and 80 degrees C and 1 degrees C and 40 degrees C, respectively. For the vapour pressures, a static method was used during the measurements which have an estimated uncertainty between 3% and 5%. The aqueous solubilities were determined using a dynamic saturation column method and the values are accurate to within +/-10%. 1,8-Dichlorooctane is more volatile than 1,8-dibromooctane in the temperature range covered (p(sat) varies from 3 to 250 Pa and from 0.53 to 62 Pa, respectively) and is also approximately three times more soluble in water (mole fraction solubilities at 25 degrees C of 5.95 x 10(-7) and 1.92 x 10(-7), respectively). A combination of the two sets of data allowed the calculation of the Henry's law constants and the air water partition coefficients. A simple group contribution concept was used to rationalize the data obtained. PMID:16530806

  9. Time-resolved fast-neutron radiography of air-water two-phase flows in a rectangular channel by an improved detection system

    NASA Astrophysics Data System (ADS)

    Zboray, Robert; Dangendorf, Volker; Mor, Ilan; Bromberger, Benjamin; Tittelmeier, Kai

    2015-07-01

    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.

  10. Time-resolved fast-neutron radiography of air-water two-phase flows in a rectangular channel by an improved detection system.

    PubMed

    Zboray, Robert; Dangendorf, Volker; Mor, Ilan; Bromberger, Benjamin; Tittelmeier, Kai

    2015-07-01

    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. PMID:26233413

  11. 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.

  12. High intensity ultrasound modified ovalbumin: Structure, interface and gelation properties.

    PubMed

    Xiong, Wenfei; Wang, Yuntao; Zhang, Chunlan; Wan, Jiawei; Shah, Bakht Ramin; Pei, Yaqiong; Zhou, Bin; Li, Jin; Li, Bin

    2016-07-01

    Influence of high intensity ultrasound (HIUS) on the structure and properties of ovalbumin (OVA) were investigated. It was found that the subunits and secondary structure of OVA did not change significantly with HIUS treatment from the electrophoretic patterns and circular dichroism (CD) spectrum. The amount of free sulfhydryl groups increased and intrinsic fluorescence spectra analysis indicated changes in the tertiary structure and partial unfold of OVA after sonication increased. Compared with the untreated OVA, HIUS treatment increased the emulsifying activity and foaming ability, and decreased interface tension (oil-water and air-water interface), which due to the increased surface hydrophobicity and decreased the surface net charge in OVA, while the emulsifying and foaming stability had no remarkable differences. The increased particle size may be attributed to formation of protein aggregates. Moreover, the gelation temperatures of HIUS-treated samples were higher than the untreated OVA according to the temperature sweep model rheology, and this effect was consistent with the increased in surface hydrophobicity for ultrasound treated OVA. These changes in functional properties of OVA would promote its application in food industry. PMID:26964953

  13. Oxidation of oleic acid at air/liquid interfaces

    NASA Astrophysics Data System (ADS)

    Voss, Laura F.; Bazerbashi, Mohamad F.; Beekman, Christopher P.; Hadad, Christopher M.; Allen, Heather C.

    2007-03-01

    Oxidation of oleic acid monolayers by ozone was studied to understand the fate of fat-coated aerosols from both freshwater and saltwater sources. Oleic acid monolayers at the air/water interface and at the air/sodium chloride solution interface were investigated using surface-specific, broad-bandwidth, sum frequency generation spectroscopy. Complementary techniques of infrared reflection adsorption spectroscopy and surface pressure measurements taken during monolayer oxidation confirmed the sum frequency results. Using this nonlinear optical technique coupled with a Langmuir trough, concurrent spectroscopic and thermodynamic data were collected to obtain a molecular picture of the monolayers. No substantial difference was observed between oxidation of monolayers spread on water and on 0.6 M sodium chloride solutions. Results indicate that depending on the size of the aerosol and the extent of oxidation, the subsequent oxidation products may not remain at the surface of these films, but instead be dissolved in the aqueous subphase of the aerosol particle. Results also indicate that oxidation of oleic acid could produce monolayers containing species that have no oxidized acyl chains.

  14. Air-water centrifugal convection

    NASA Astrophysics Data System (ADS)

    Herrada, Miguel; Shtern, Vladimir

    2014-07-01

    A sealed cylindrical container is filled with air and water. The container rotation and the axial gradient of temperature induce the steady axisymmetric meridional circulation of both fluids due to the thermal buoyancy and surface-tension (Marangoni) effects. If the temperature gradient is small, the water circulation is one-cellular while the air circulation can be one- or two-cellular depending on water fraction Wf. The numerical simulations are performed for the cylinder length-to-radius ratio l = 1 and l = 4. The l = 4 results and the analytical solution for l → ∞ agree in the cylinder's middle part. As the temperature gradient increases, the water circulation becomes one-, two-, or three-cellular depending on Wf. The results are of fundamental interest and can be applied for bioreactors.

  15. Operator interface for vehicles

    DOEpatents

    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.

  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. 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

  18. Implantable microscale neural interfaces.

    PubMed

    Cheung, Karen C

    2007-12-01

    Implantable neural microsystems provide an interface to the nervous system, giving cellular resolution to physiological processes unattainable today with non-invasive methods. Such implantable microelectrode arrays are being developed to simultaneously sample signals at many points in the tissue, providing insight into processes such as movement control, memory formation, and perception. These electrode arrays have been microfabricated on a variety of substrates, including silicon, using both surface and bulk micromachining techniques, and more recently, polymers. Current approaches to achieving a stable long-term tissue interface focus on engineering the surface properties of the implant, including coatings that discourage protein adsorption or release bioactive molecules. The implementation of a wireless interface requires consideration of the necessary data flow, amplification, signal processing, and packaging. In future, the realization of a fully implantable neural microsystem will contribute to both diagnostic and therapeutic applications, such as a neuroprosthetic interface to restore motor functions in paralyzed patients. PMID:17252207

  19. Polarizable Ions at Interfaces

    NASA Astrophysics Data System (ADS)

    Levin, Yan

    2009-04-01

    A nonperturbative theory is presented which allows us to calculate the solvation free energy of polarizable ions near water-vapor and water-oil interfaces. The theory predicts that larger halogen anions are adsorbed at the interface, while the alkali metal cations are repelled from it. The density profiles calculated theoretically are similar to those obtained using molecular dynamics simulations with polarizable force fields.

  20. 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.

  1. Representative elementary volume estimation for porosity, moisture saturation, and air-water interfacial areas in unsaturated porous media: Data quality implications

    SciTech Connect

    Costanza-Robinson, Molly S.; Estabrook, Benjamin D.; Fouhey, David F.

    2011-09-16

    Achieving a representative elementary volume (REV) has become a de facto criterion for demonstrating the quality of {mu}CT measurements in porous media systems. However, the data quality implications of an REV requirement have not been previously examined. In this work, deterministic REVs for porosity, moisture saturation (S{sub W}), and air-water interfacial area (A{sub I}) were estimated using a set of 49 {mu}CT images of eight unsaturated homogeneous porous media with heterogeneity in moisture distributions present in varying degrees. Estimated porosity REVs were <8 mm{sup 3} for all cases, smaller than typical CT image sizes ({approx}100 mm{sup 3}). Estimated S{sub W} and A{sub I} REVs were <55 mm{sup 3} for cases with homogeneous moisture distributions but could not be estimated for cases with heterogeneous moisture distributions, due to the absence of a distinct 'REV plateau' within the maximum imaged volume. Conventionally, S{sub W} and A{sub I} data from such non-REV cases would be excluded. The implications of excluding data on the basis of REV were examined by comparing A{sub I}-S{sub W} data measured on image windows of increasing size against the expected linear A{sub I}-S{sub W} relationship. At measurement scales exceeding porosity REV, random fluctuations in A{sub I}-S{sub W} data were excluded, even for cases containing heterogeneous moisture distributions. In contrast, requiring measurement scales to exceed S{sub W} and A{sub I} REV appeared overly restrictive and resulted in visible loss of reliable A{sub I}-S{sub W} data. We attribute these findings to overestimation of REVs due to inherently problematic estimation of deterministic REVs in real systems. Implications of these findings for ensuring CT data quality and the efficient use of CT data are discussed.

  2. 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

  3. VIRTUAL FRAME BUFFER INTERFACE

    NASA Technical Reports Server (NTRS)

    Wolfe, T. L.

    1994-01-01

    Large image processing systems use multiple frame buffers with differing architectures and vendor supplied user interfaces. This variety of architectures and interfaces creates software development, maintenance, and portability problems for application programs. The Virtual Frame Buffer Interface program makes all frame buffers appear as a generic frame buffer with a specified set of characteristics, allowing programmers to write code which will run unmodified on all supported hardware. The Virtual Frame Buffer Interface converts generic commands to actual device commands. The virtual frame buffer consists of a definition of capabilities and FORTRAN subroutines that are called by application programs. The virtual frame buffer routines may be treated as subroutines, logical functions, or integer functions by the application program. Routines are included that allocate and manage hardware resources such as frame buffers, monitors, video switches, trackballs, tablets and joysticks; access image memory planes; and perform alphanumeric font or text generation. The subroutines for the various "real" frame buffers are in separate VAX/VMS shared libraries allowing modification, correction or enhancement of the virtual interface without affecting application programs. The Virtual Frame Buffer Interface program was developed in FORTRAN 77 for a DEC VAX 11/780 or a DEC VAX 11/750 under VMS 4.X. It supports ADAGE IK3000, DEANZA IP8500, Low Resolution RAMTEK 9460, and High Resolution RAMTEK 9460 Frame Buffers. It has a central memory requirement of approximately 150K. This program was developed in 1985.

  4. Interfaces: nanometric dielectrics

    NASA Astrophysics Data System (ADS)

    Lewis, T. J.

    2005-01-01

    The incorporation of nanometric size particles in a matrix to form dielectric composites shows promise of materials (nanodielectrics) with new and improved properties. It is argued that the properties of the interfaces between the particles and the matrix, which will themselves be of nanometric dimensions, will have an increasingly dominant role in determining dielectric performance as the particle size decreases. The forces that determine the electrical and dielectric properties of interfaces are considered, with emphasis on the way in which they might influence composite behaviour. A number of examples are given in which interfaces at the nanometric level exercise both passive and active control over dielectric, optical and conductive properties. Electromechanical properties are also considered, and it is shown that interfaces have important electrostrictive and piezoelectric characteristics. It is demonstrated that the process of poling, namely subjecting macroscopic composite materials to electrical stress and raised temperatures to create piezoelectric materials, can be explained in terms of optimizing the collective response of the nanometric interfaces involved. If the electrical and electromechanical features are coupled to the long-established electrochemical properties, interfaces represent highly versatile active elements with considerable potential in nanotechnology.

  5. MER SPICE Interface

    NASA Technical Reports Server (NTRS)

    Sayfi, Elias

    2004-01-01

    MER SPICE Interface is a software module for use in conjunction with the Mars Exploration Rover (MER) mission and the SPICE software system of the Navigation and Ancillary Information Facility (NAIF) at NASA's Jet Propulsion Laboratory. (SPICE is used to acquire, record, and disseminate engineering, navigational, and other ancillary data describing circumstances under which data were acquired by spaceborne scientific instruments.) Given a Spacecraft Clock value, MER SPICE Interface extracts MER-specific data from SPICE kernels (essentially, raw data files) and calculates values for Planet Day Number, Local Solar Longitude, Local Solar Elevation, Local Solar Azimuth, and Local Solar Time (UTC). MER SPICE Interface was adapted from a subroutine, denoted m98SpiceIF written by Payam Zamani, that was intended to calculate SPICE values for the Mars Polar Lander. The main difference between MER SPICE Interface and m98SpiceIf is that MER SPICE Interface does not explicitly call CHRONOS, a time-conversion program that is part of a library of utility subprograms within SPICE. Instead, MER SPICE Interface mimics some portions of the CHRONOS code, the advantage being that it executes much faster and can efficiently be called from a pipeline of events in a parallel processing environment.

  6. Serial interface controller

    SciTech Connect

    Kandasamy, A.

    1995-04-14

    The idea of building a Serial Interface Controller (SIC) proposed by Paul O`Connor, Instrumentation Division, BNL is to determine the feasibility of incorporating a Serial Interface Controlled CMOS IC`s for charge amplification, shaping, analog storage and multiplexing used in particle detectors for high energy physics experiments. The serial data pumped into the CMOS ICs will be used to control many circuit parameters like digitally controlled gain, shaping time, precision preamplifier calibration circuits and many other parameters like timing discriminators mode of operation. The SIC board built will be tested on a Serial Interface Controlled Digital - to - Analog Convertor, which follows either Motorola`s SPI/QSPI or National Semiconductors Microwire interface technique. The DAC chosen for this was MAXIM`s MAX537, a Quad, 12-bit DAC. The function of this controller can be achieved by using some on-shelf micro-controllers like the Motorola`s MC68HC11, which offers dedicated SPI ports. The drawback encountered in using this controller is the overhead involved in putting together an user interface where the user can dynamically change its settings and load the SIC device. This is very critical in testing fewer number of CMOS IC`s having SIC. The SIC board described here takes care of this dynamic user interface issue.

  7. Approach and landing test network interface processor interface control document

    NASA Technical Reports Server (NTRS)

    1976-01-01

    The design requirements are established for all external or interproject interfaces to the Network Interface Processor located in Building 30 at the Lyndon B. Johnson Space Center, Houston, Texas. In addition to external interfaces, software/hardware and special interfaces are also described.

  8. Concentrations, atmospheric partitioning, and air-water/soil surface exchange of polychlorinated dibenzo-p-dioxin and dibenzofuran along the upper reaches of the Haihe River basin, North China.

    PubMed

    Nie, Zhiqiang; Die, Qingqi; Yang, Yufei; Tang, Zhenwu; Wang, Qi; Huang, Qifei

    2014-01-01

    Polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/PCDF) were overall measured and compared in ambient air, water, soils, and sediments along the upper reaches of the Haihe River of North China, so as to evaluate their concentrations, profiles, and to understand the processes of gas-particle partitioning and air-water/soil exchange. The following results were obtained: (1) The average concentrations (toxic equivalents, TEQs) of 2,3,7,8-PCDD/PCDF in air, water, sediment, and soil samples were 4,855 fg/m(3), 9.5 pg/L, 99.2 pg/g dry weight (dw), and 56.4 pg/g (203 fg TEQ/m(3), 0.46 pg TEQ/L, 2.2 pg TEQ/g dw, and 1.3 pg TEQ/g, respectively), respectively. (2) Although OCDF, 1,2,3,4,6,7,8-HpCDF, OCDD, and 1,2,3,4,6,7,8-HpCDD were the dominant congeners among four environmental sinks, obvious discrepancies of these congener and homologue patterns of PCDD/PCDF were observed still. (3) Significant linear correlations for PCDD/PCDF were observed between the gas-particle partition coefficient (K p) and the subcooled liquid vapor pressure (P L (0)) and octanol-air partition coefficient (K oa). (4) Fugacity fraction values of air-water exchange indicated that most of PCDD/PCDF homologues were dominated by net volatilization from water into air. The low-chlorinated PCDD/PCDF (tetra- to hexa-) presented a strong net volatilization from the soil into air, while high-chlorinated PCDD/PCDF (hepta- to octa-) were mainly close to equilibrium for air-soil exchange. PMID:24643387

  9. Contact line extraction and length measurements in model sediments and sedimentary rocks.

    PubMed

    Rodriguez, Elena; Prodanović, Maša; Bryant, Steven L

    2012-02-15

    The mechanisms that govern the transport of colloids in the unsaturated zone of soils are still poorly understood, because of the complexity of processes that occur at pore scale. These mechanisms are of specific interest in quantifying water quality with respect to pathogen transport (e.g. Escherichia coli, Cryptosporidium) between the source (e.g. farms) and human users. Besides straining in pore throats and constrictions of smaller or equivalent size, the colloids can be retained at the interfaces between air, water, and grains. Theories competing to explain this mechanism claim that retention can be caused by adhesion at the air-water-interface (AWI) between sediment grains or by straining at the air-water-solid (AWS) contact line. Currently, there are no established methods for the estimation of pathogen retention in unsaturated media because of the intricate influence of AWI and AWS on transport and retention. What is known is that the geometric configuration and connectivity of the aqueous phase is an important factor in unsaturated transport. In this work we develop a computational method based on level set functions to identify and quantify the AWS contact line (in general the non-wetting-wetting-solid contact line) in any porous material. This is the first comprehensive report on contact line measurement for fluid configurations from both level-set method based fluid displacement simulation and imaged experiments. The method is applicable to any type of porous system, as long as the detailed pore scale geometry is available. We calculated the contact line length in model sediments (packs of spheres) as well as in real porous media, whose geometry is taken from high-resolution images of glass bead packs and sedimentary rocks. We observed a strong dependence of contact line length on the geometry of the sediment grains and the arrangement of the air and water phases. These measurements can help determine the relative contribution of the AWS line to pathogen

  10. The effect of shear and confinement on the buckling of particle-laden interfaces.

    PubMed

    Kassuga, Theo D; Rothstein, Jonathan P

    2016-01-20

    In this paper, we investigate the buckling of an air-water interface populated by lycopodium powder particles using a specially designed Langmuir trough with side walls that deformed affinely with the particle-laden interface in order to minimize the effect of shear during compression. Confinement effects from the side walls were studied by systematically reducing the width of the Langmuir trough and measuring the buckling wavelength. For interfaces wider than 20 mm, the bulk wavelength was found to be independent of interface width. Due to the presence of contact line friction along the sidewall, the amplitude and wavelength of the wrinkles near the side walls were found to be reduced by a factor two compared with the bulk. A cascade in wavelength was observed as one moved from the center of the particle-laden interface towards the sidewalls similar to what has been observed for thin floating polymer films. For interface widths less than 20 mm, the wavelength of the wrinkles in the bulk was found to decrease eventually approaching the wavelength measured along the side walls. The wavelength at the walls was not affected by confinement. At large compressive strains, a transition from wrinkles to folds was observed. These regions of strain localization formed as a train of folds shortly after the onset of wrinkling and grew in amplitude with increasing compression. Confinement was also found to have an impact on folding. To study the impact of shear during interface compression, a series of objects including circular cylinders and rectangular prisms were placed through the center of the particle-laden interface before compression. These objects enhanced wrinkling and folding upstream of the object, eliminated wrinkling and folding in a broad region downstream of the object, and realigned the wrinkles along the side of the immobile obstacles where shear strains were maximum. PMID:26658075

  11. The effect of shear and confinement on the buckling of particle-laden interfaces

    NASA Astrophysics Data System (ADS)

    Kassuga, Theo D.; Rothstein, Jonathan P.

    2016-01-01

    In this paper, we investigate the buckling of an air-water interface populated by lycopodium powder particles using a specially designed Langmuir trough with side walls that deformed affinely with the particle-laden interface in order to minimize the effect of shear during compression. Confinement effects from the side walls were studied by systematically reducing the width of the Langmuir trough and measuring the buckling wavelength. For interfaces wider than 20 mm, the bulk wavelength was found to be independent of interface width. Due to the presence of contact line friction along the sidewall, the amplitude and wavelength of the wrinkles near the side walls were found to be reduced by a factor two compared with the bulk. A cascade in wavelength was observed as one moved from the center of the particle-laden interface towards the sidewalls similar to what has been observed for thin floating polymer films. For interface widths less than 20 mm, the wavelength of the wrinkles in the bulk was found to decrease eventually approaching the wavelength measured along the side walls. The wavelength at the walls was not affected by confinement. At large compressive strains, a transition from wrinkles to folds was observed. These regions of strain localization formed as a train of folds shortly after the onset of wrinkling and grew in amplitude with increasing compression. Confinement was also found to have an impact on folding. To study the impact of shear during interface compression, a series of objects including circular cylinders and rectangular prisms were placed through the center of the particle-laden interface before compression. These objects enhanced wrinkling and folding upstream of the object, eliminated wrinkling and folding in a broad region downstream of the object, and realigned the wrinkles along the side of the immobile obstacles where shear strains were maximum.

  12. The AirWaterGas Teacher Professional Development Program: Lessons Learned by Pairing Scientists and Teachers to Develop Curriculum on Global Climate Change and Regional Unconventional Oil and Gas Development

    NASA Astrophysics Data System (ADS)

    Gardiner, L. S.; Hatheway, B.; Rogers, J. D.; Casey, J. G.; Lackey, G.; Birdsell, D.; Brown, K.; Polmear, M.; Capps, S.; Rosenblum, J.; Sitterley, K.; Hafich, K. A.; Hannigan, M.; Knight, D.

    2015-12-01

    The AirWaterGas Teacher Professional Development Program, run by the UCAR Center for Science Education, brought together scientists and secondary science teachers in a yearlong program culminating in the development of curriculum related to the impacts of unconventional oil and gas development. Graduate students and research scientists taught about their research area and its relationship to oil and gas throughout three online courses during the 2015-16 school year, during which teachers and scientists engaged in active online discussions. Topics covered included climate change, oil and gas infrastructure, air quality, water quality, public health, and practices and policies relating to oil and gas development. Building upon their initial online interactions and a face-to-face meeting in March, teachers were paired with appropriate AirWaterGas team members as science advisors during a month-long residency in Boulder, Colorado. During the residency, graduate student scientists provided resources and feedback as teachers developed curriculum projects in collaboration with each other and UCAR science educators. Additionally, teachers and AirWaterGas researchers shared experiences on an oil and gas well site tour, and a short course on drilling methods with a drilling rig simulator. Here, we share lessons learned from both sides of the aisle, including initial results from program assessment conducted with the participating teachers.

  13. Binding of the Cationic Peptide (KL)4K to Lipid Monolayers at the Air-Water Interface: Effect of Lipid Headgroup Charge, Acyl Chain Length, and Acyl Chain Saturation.

    PubMed

    Hädicke, André; Blume, Alfred

    2016-04-28

    The binding of the cationic peptide (KL)4K to monolayers of different anionic lipids was determined by adsorption experiments. The chemical structure of the anionic phospholipids was changed in different ways. First, the hydrophobic region of phosphatidylglycerols was altered by elongation of the acyl chain length. Second, an unsaturated chain was introduced. Third, lipids with negatively charged headgroups of different chemical structure were compared. (KL)4K itself shows no surface activity and does not bind to monolayers of zwitterionic lipids. Analysis of (KL)4K binding to anionic lipid monolayers reveals a competition between two binding processes: (i) incorporation of the peptide into the acyl chain region (surface pressure increase) and (ii) electrostatic interaction screening the negative charges with reduction of charge repulsion (surface pressure decrease due to monolayer condensation). The lipid acyl chain length and the chemical structure of the headgroup have minor effects on the binding properties. However, a strong dependence on the phase state of the monolayer was observed. In the liquid-expanded (LE) phase, the fluid monolayer provides enough space, so that peptide insertion due to hydrophobic interactions dominates. For monolayers in the liquid-condensed (LC) phase, peptide binding followed by monolayer condensation is the main effect. PMID:27049846

  14. X-ray reflectivity and grazing incidence diffraction studies of interaction between human adhesion/growth-regulatory galectin-1 and DPPE-GM1 lipid monolayer at an air/water interface.

    PubMed

    Majewski, J; André, S; Jones, E; Chi, E; Gabius, H-J

    2015-07-01

    The specific interaction of ganglioside GM1 with the homodimeric (prototype) endogenous lectin galectin-1 triggers growth regulation in tumor and activated effector T cells. This proven biorelevance directed interest to studying association of the lectin to a model surface, i.e. a 1,2-dihexadecanoyl-sn-glycero-3-phosphoethanolamine/ganglioside GM1 (80 : 20 mol%) monolayer, at a bioeffective concentration. Surface expansion by the lectin insertion was detected at a surface pressure of 20 mN/m. On combining the methods of grazing incidence X-ray diffraction and X-ray reflectivity, a transient decrease in lipid-ordered phase of the monolayer was observed. The measured electron density distribution indicated that galectin-1 is oriented with its long axis in the surface plane, ideal for cis-crosslinking. The data reveal a conspicuous difference to the way the pentameric lectin part of the cholera toxin, another GM1-specific lectin, is bound to the monolayer. They also encourage further efforts to monitor effects of structurally different members of the galectin family such as the functionally antagonistic chimera-type galectin-3. PMID:26542007

  15. Environmental materials and interfaces

    SciTech Connect

    Not Available

    1991-11-01

    A workshop that explored materials and interfaces research needs relevant to national environmental concerns was conducted at Pacific Northwest Laboratory. The purposes of the workshop were to refine the scientific research directions being planned for the Materials and Interface Program in the Molecular Science Research Center (MSRC) and further define the research and user equipment to the included as part of the proposed Environmental and Molecular Science Laboratory (EMSL). Three plenary information sessions served to outline the background, objectives, and status of the MSRC and EMSL initiatives; selected specific areas with environmentally related materials; and the status of capabilities and facilities planned for the EMSL. Attention was directed to four areas where materials and interface science can have a significant impact on prevention and remediation of environmental problems: in situ detection and characterization of hazardous wastes (sensors), minimization of hazardous waste (separation membranes, ion exchange materials, catalysts), waste containment (encapsulation and barrier materials), and fundamental understanding of contaminant transport mechanisms. During all other sessions, the participants were divided into three working groups for detailed discussion and the preparation of a written report. The working groups focused on the areas of interface structure and chemistry, materials and interface stability, and materials synthesis. These recommendations and suggestions for needed research will be useful for other researchers in proposing projects and for suggesting collaborative work with MSRC researchers. 1 fig.

  16. The apparent charge of nanoparticles trapped at a water interface.

    PubMed

    Bossa, Guilherme Volpe; Roth, Joseph; Bohinc, Klemen; May, Sylvio

    2016-05-14

    Charged spherical nanoparticles trapped at the interface between water and air or water and oil exhibit repulsive electrostatic forces that contain a long-ranged dipolar and a short-ranged exponentially decaying component. The former are induced by the unscreened electrostatic field through the non-polar low-permittivity medium, and the latter result from the overlap of the diffuse ion clouds that form in the aqueous phase close to the nanoparticles. The magnitude of the long-ranged dipolar interaction is largely determined by the residual charges that remain attached to the air- (or oil-) exposed region of the nanoparticle. In the present work we address the question to what extent the charges on the water-immersed part of the nanoparticle provide an additional contribution to the dipolar interaction. To this end, we model the electrostatic properties of a spherical particle - a nanoparticle or a colloid - that partitions equatorially to the air-water interface, thereby employing nonlinear Poisson-Boltzmann theory in the aqueous solution and accounting for the propagation of the electric field through the interior of the particle. We demonstrate that the apparent charge density on the air-exposed region of the particle, which determines the dipole potential, is influenced by the electrostatic properties in the aqueous solution. We also show that this electrostatic coupling through the particle can be reproduced qualitatively by a simple analytic planar capacitor model. Our results help to rationalize the experimentally observed weak but non-vanishing salt dependence of the forces that stabilize ordered two-dimensional arrays of interface-trapped nanoparticles or colloids. PMID:27049110

  17. [Emergency Department Interfaces].

    PubMed

    Fleischmann, Thomas

    2016-01-01

    Emergency Departments ED may be an exceptionally good example of an interface within a hospital. EDs have no patients of their own but pass them over to other institutions, either to specialist departments within the hospital or to primary care providers. Moreover, many doctors, nurses, attendants and institutions take part in the care of emergency department patients, and thus the number of its interfaces is very high. The characteristics of working in an ED, for example shortage of time, high work load, taking care of several patients at the same time and frequently crowding, may compromise the transfer of information via interfaces, sometimes including even vital data. The best way to secure handoff of information may be the formalization and standardization of this process, assuring patient safety and quality of care. Further study is required. PMID:26710198

  18. High temperature interface superconductivity

    DOE PAGESBeta

    Gozar, A.; Bozovic, I.

    2016-01-20

    High-Tc superconductivity at interfaces has a history of more than a couple of decades. In this review we focus our attention on copper-oxide based heterostructures and multi-layers. We first discuss the technique, atomic layer-by-layer molecular beam epitaxy (ALL-MBE) engineering, that enabled High-Tc Interface Superconductivity (HT-IS), and the challenges associated with the realization of high quality interfaces. Then we turn our attention to the experiments which shed light on the structure and properties of interfacial layers, allowing comparison to those of single-phase films and bulk crystals. Both ‘passive’ hetero-structures as well as surface-induced effects by external gating are discussed. Here, wemore » conclude by comparing HT-IS in cuprates and in other classes of materials, especially Fe-based superconductors, and by examining the grand challenges currently laying ahead for the field.« less

  19. High temperature interface superconductivity

    NASA Astrophysics Data System (ADS)

    Gozar, A.; Bozovic, I.

    2016-02-01

    High-Tc superconductivity at interfaces has a history of more than a couple of decades. In this review we focus our attention on copper-oxide based heterostructures and multi-layers. We first discuss the technique, atomic layer-by-layer molecular beam epitaxy (ALL-MBE) engineering, that enabled High-Tc Interface Superconductivity (HT-IS), and the challenges associated with the realization of high quality interfaces. Then we turn our attention to the experiments which shed light on the structure and properties of interfacial layers, allowing comparison to those of single-phase films and bulk crystals. Both 'passive' hetero-structures as well as surface-induced effects by external gating are discussed. We conclude by comparing HT-IS in cuprates and in other classes of materials, especially Fe-based superconductors, and by examining the grand challenges currently laying ahead for the field.

  20. Magnetic multilayer interface anisotropy

    SciTech Connect

    Pechan, M.J.

    1992-01-01

    Ni/Mo and Ni/V multilayer magnetic anisotropy has been investigated as a function of Ni layer thickness, frequency and temperature. Variable frequency ferromagnetic resonance (FMR) measurements show, for the first time, significant frequency dependence associated with the multilayer magnetic anisotropy. The thickness dependence allows one to extract the interface contribution from the total anisotropy. Temperature dependent FMR (9 GHz) and room temperature magnetization indicate that strain between Ni and the non-magnetic layers is contributing significantly to the source of the interface anisotropy and the state of the interfacial magnetization. In order to examine the interface properties of other transition metal multilayer systems, investigations on Fe/Cu are underway and CoCr/Ag is being proposed. ESR measurements have been reported on Gd substituted YBaCuO superconductors and a novel quasi-equilibrium method has been developed to determine quickly and precisely the ransition temperature.

  1. Urban water interfaces

    NASA Astrophysics Data System (ADS)

    Gessner, M. O.; Hinkelmann, R.; Nützmann, G.; Jekel, M.; Singer, G.; Lewandowski, J.; Nehls, T.; Barjenbruch, M.

    2014-06-01

    Urban water systems consist of large-scale technical systems and both natural and man-made water bodies. The technical systems are essential components of urban infrastructure for water collection, treatment, storage and distribution, as well as for wastewater and runoff collection and subsequent treatment. Urban aquatic ecosystems are typically subject to strong human influences, which impair the quality of surface and ground waters, often with far-reaching impacts on downstream aquatic ecosystems and water users. The various surface and subsurface water bodies in urban environments can be viewed as interconnected compartments that are also extensively intertwined with a range of technical compartments of the urban water system. As a result, urban water systems are characterized by fluxes of water, solutes, gases and energy between contrasting compartments of a technical, natural or hybrid nature. Referred to as urban water interfaces, boundaries between and within these compartments are often specific to urban water systems. Urban water interfaces are generally characterized by steep physical and biogeochemical gradients, which promote high reaction rates. We hypothesize that they act as key sites of processes and fluxes with notable effects on overall system behaviour. By their very nature, urban water interfaces are heterogeneous and dynamic. Therefore, they increase spatial heterogeneity in urban areas and are also expected to contribute notably to the temporal dynamics of urban water systems, which often involve non-linear interactions and feedback mechanisms. Processes at and fluxes across urban water interfaces are complex and less well understood than within well-defined, homogeneous compartments, requiring both empirical investigations and new modelling approaches at both the process and system level. We advocate an integrative conceptual framework of the urban water system that considers interfaces as a key component to improve our fundamental

  2. Nonlinear optics at interfaces

    SciTech Connect

    Chen, C.K.

    1980-12-01

    Two aspects of surface nonlinear optics are explored in this thesis. The first part is a theoretical and experimental study of nonlinear intraction of surface plasmons and bulk photons at metal-dielectric interfaces. The second part is a demonstration and study of surface enhanced second harmonic generation at rough metal surfaces. A general formulation for nonlinear interaction of surface plasmons at metal-dielectric interfaces is presented and applied to both second and third order nonlinear processes. Experimental results for coherent second and third harmonic generation by surface plasmons and surface coherent antiStokes Raman spectroscopy (CARS) are shown to be in good agreement with the theory.

  3. Modal Interfaces in Hawaii

    NASA Technical Reports Server (NTRS)

    Wright, E. Alvey

    1974-01-01

    Hawaii, an archipelago where transportation distances are short but the interfaces are many, seeks elimination of modal changes by totally-submerged hydrofoil craft operating at the water surface directly between tourist resort destinations, by dual mode rapid transit vehicles operating directly between the deplaning bridges at Honolulu International Airport and hotel porte-cochere at Waikiki, by demand responsive vehicles for collection and distribution operating on fixed guideways for line haul, and by roll-on/roll-off inter-island ferries for all models of manually operated ground vehicles. The paper also describes facilitation of unavoidable interfaces by innovative sub-systems.

  4. Interfacing to accelerator instrumentation

    SciTech Connect

    Shea, T.J.

    1995-12-31

    As the sensory system for an accelerator, the beam instrumentation provides a tremendous amount of diagnostic information. Access to this information can vary from periodic spot checks by operators to high bandwidth data acquisition during studies. In this paper, example applications will illustrate the requirements on interfaces between the control system and the instrumentation hardware. A survey of the major accelerator facilities will identify the most popular interface standards. The impact of developments such as isochronous protocols and embedded digital signal processing will also be discussed.

  5. Optical encryption interface

    NASA Technical Reports Server (NTRS)

    Jackson, Deborah J. (Inventor)

    1998-01-01

    An analog optical encryption system based on phase scrambling of two-dimensional optical images and holographic transformation for achieving large encryption keys and high encryption speed. An enciphering interface uses a spatial light modulator for converting a digital data stream into a two dimensional optical image. The optical image is further transformed into a hologram with a random phase distribution. The hologram is converted into digital form for transmission over a shared information channel. A respective deciphering interface at a receiver reverses the encrypting process by using a phase conjugate reconstruction of the phase scrambled hologram.

  6. Profile Interface Generator

    2013-11-09

    The Profile Interface Generator (PIG) is a tool for loosely coupling applications and performance tools. It enables applications to write code that looks like standard C and Fortran functions calls, without requiring that applications link to specific implementations of those function calls. Performance tools can register with PIG in order to listen to only the calls that give information they care about. This interface reduces the build and configuration burden on application developers and allowsmore » semantic instrumentation to live in production codes without interfering with production runs.« less

  7. Profile Interface Generator

    SciTech Connect

    2013-11-09

    The Profile Interface Generator (PIG) is a tool for loosely coupling applications and performance tools. It enables applications to write code that looks like standard C and Fortran functions calls, without requiring that applications link to specific implementations of those function calls. Performance tools can register with PIG in order to listen to only the calls that give information they care about. This interface reduces the build and configuration burden on application developers and allows semantic instrumentation to live in production codes without interfering with production runs.

  8. Unstable nonlocal interface dynamics.

    PubMed

    Nicoli, Matteo; Cuerno, Rodolfo; Castro, Mario

    2009-06-26

    Nonlocal effects occur in many nonequilibrium interfaces, due to diverse physical mechanisms like diffusive, ballistic, or anomalous transport, with examples from flame fronts to thin films. While dimensional analysis describes stable nonlocal interfaces, we show the morphologically unstable condition to be nontrivial. This is the case for a family of stochastic equations of experimental relevance, paradigmatically including the Michelson-Sivashinsky system. For a whole parameter range, the asymptotic dynamics is scale invariant with dimension-independent exponents reflecting a hidden Galilean symmetry. The usual Kardar-Parisi-Zhang nonlinearity, albeit irrelevant in that parameter range, plays a key role in this behavior. PMID:19659099

  9. Liquid-Vapor Interfacial Properties of Aqueous Solutions of Guanidinium and Methyl Guanidinium Chloride: Influence of Molecular Orientation on Interface Fluctuations

    PubMed Central

    Ou, Shuching; Cui, Di; Patel, Sandeep

    2014-01-01

    The guanidinium cation (C(NH2)3+) is a highly stable cation in aqueous solution due to its efficient solvation by water molecules and resonance stabilization of the charge. Its salts increase the solubility of nonpolar molecules (”salting-in”) and decrease the ordering of water. It is one of the strongest denaturants used in biophysical studies of protein folding. We investigate the behavior of guanidinium and its derivative, methyl guanidinium (an amino acid analogue) at the air-water surface, using atomistic molecular dynamics (MD) simulations and calculation of potentials of mean force. Methyl guanidinium cation is less excluded from the air-water surface than guanidinium cation, but both cations show orientational dependence of surface affinity. Parallel orientations of the guanidinium ring (relative to the Gibbs dividing surface) show pronounced free energy minima in the interfacial region, while ring orientations perpendicular to the GDS exhibit no discernible surface stability. Calculations of surface fluctuations demonstrate that near the air-water surface, the parallel-oriented cations generate significantly greater interfacial fluctuations compared to other orientations, which induces more long-ranged perturbations and solvent density redistribution. Our results suggest a strong correlation with induced interfacial fluctuations and ion surface stability. These results have implications for interpreting molecular-level, mechanistic action of this osmolyte’s interaction with hydrophobic interfaces as they impact protein denaturation (solubilization). PMID:23937431

  10. Direct Manipulation Interfaces.

    ERIC Educational Resources Information Center

    Hutchins, Edwin L.; And Others

    This paper presents a cognitive account of both the advantages and disadvantages of direct manipulation interfaces, i.e., the use of icons to manipulate and interact directly with data rather than writing programs or calling on a set of statistical subroutines. Two underlying phenomena that give rise to the sensation of directness are identified.…

  11. Interfacing with a DMM.

    ERIC Educational Resources Information Center

    Beatty, Jim

    1985-01-01

    Suggests purchasing a digital multimer (DMM) with an IEEE-488 option to interface an instrument to a microcomputer, indicating that a DMM is well protected from overloads and is easy to connect. An example of its use in an experiment involving hydrolysis of tertiary butyl alcohol (with program listing) is given. (JN)

  12. A Thermistor Interface.

    ERIC Educational Resources Information Center

    Kamin, Gary D.; Dowden, Edward

    1987-01-01

    Describes the use of a precalibrated stainless steel thermistor, interfaced with an Apple computer, in chemistry experiments. Discusses the advantages of "instant" temperature readings in experiments requiring that readings be taken at certain intervals. Outlines such an experiment which investigates freezing point depressions. (TW)

  13. Photochemistry at Interfaces

    SciTech Connect

    Eisenthal, Kenneth B

    2015-02-24

    We have advanced our capabilities to investigate ultrafast excited state dynamics at a liquid interface using a pump to excite molecules to higher electronic states and then probe the subsequent time evolution of the interfacial molecules with femtosecond time delayed vibrational SFG.

  14. Videodisc-Computer Interfaces.

    ERIC Educational Resources Information Center

    Zollman, Dean

    1984-01-01

    Lists microcomputer-videodisc interfaces currently available from 26 sources, including home use systems connected through remote control jack and industrial/educational systems utilizing computer ports and new laser reflective and stylus technology. Information provided includes computer and videodisc type, language, authoring system, educational…

  15. the EXFOR interface

    2011-03-10

    The x4i package is an interface to the EXFOR nuclear data library. It simplifies retrieval of EXFOR entries and can automatically parse them, allowing one to extract cross-section (and other) data in a simple, plot-able format. x4i also understands and can parse the entire reaction string, allowing one to build a strategy for processing the data

  16. Virtual interface environment

    NASA Technical Reports Server (NTRS)

    Fisher, Scott S.

    1988-01-01

    A head-mounted, wide-angle, stereoscopic display system controlled by operator position, voice and gesture is under development for use as a multipurpose interface environment. Initial applications of the system are in telerobotics, data-management and human factors research. System configuration and research directions are described.

  17. Correlation of average hydrophobicity, water/air interface surface rheological properties and foaming properties of proteins.

    PubMed

    Medrano, A; Abirached, C; Araujo, A C; Panizzolo, L A; Moyna, P; Añón, M C

    2012-04-01

    A comparative study on the behavior in the air-water interface of β-lactoglobulin, α-lactoalbumin, glycinin and β-conglycinin was performed. The behavior at the interface was evaluated by equilibrium surface tension and surface rheological properties of adsorbed films. There were significant differences (α ≤ 0.05) in the values of the constants of adsorption to the interface of the four proteins. The glycinin had the slowest rate of adsorption, due to its low average hydrophobicity, low molecular flexibility and large molecular size. Smaller proteins like β-lactoglobulin and α-lactoalbumin tended to greater equilibrium pressure values than the larger proteins because of its higher rate of adsorption to the interface. The foam capacity of proteins showed a positive correlation with the average hydrophobicity; the maximal retained liquid volume or the initial rate of passage of liquid to foam were significantly lower (α ≤ 0.05) when protein was glycinin. The dilatational modulus of glycinin was the lowest, which implies lowest resistance to disruption of the film. Glycinin protein has lower proportion of gravitational drainage and higher disproportionation having perhaps a less resistant film. In conclusion, β-conglycinin and whey proteins showed a similar behavior, so β-conglycinin might be the best soybean protein to replace milk proteins in food formulations. PMID:22414931

  18. Simulation and Theory of Ions at Atmospherically Relevant Aqueous Liquid-Air Interfaces

    SciTech Connect

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

    2013-04-01

    Chemistry occurring at or near the surfaces 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 that is capable of reproducing simulation and experimental data on ion behavior at aqueous interfaces. MDB and CJM acknowledge support from the US Department of Energy's 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. MDB is supported by the Linus Pauling Distinguished Postdoctoral Fellowship Program at PNNL.

  19. Fluorinated monolayers at liquid-liquid and liquid-vapor interfaces

    NASA Astrophysics Data System (ADS)

    Zhang, Zhongjian

    Microscopic structure of several fluorinated monolayers at water-vapor and water-oil interfaces were examined using x-ray specular reflectivity and grazing incidence diffraction (GID) techniques. Grazing incidence x-ray diffraction measurements of monolayers of perfluoro-n-eicosane (F(CFsb2)sb{20}F) and F(CFsb2)sb{m}(CHsb2)sb{n}H (denoted as Fsb{m}Hsb{n}) supported at the air-water interface demonstrated that even without the conventional polar head group, the surfactant molecules are capable of forming ordered in-plane structures defined by hexagonal close packing of the fluorinated blocks of adsorbed molecules due to the stronger chain-chain interaction between fluorocarbon chains than the corresponding hydrocarbons. The specular reflectivity data reveals a hydrocarbon-down, fluorocarbon-up orientation for Fsb{12}Hsb{18}. In contrast to the conventional expectation that soluble surfactants form disordered monolayers at the liquid-liquid interface, the studies on a fluoroalcohol (F(CFsb2)sb{10}(CHsb2)sb2OH) monolayer at water-hexane interface indicate that the surfactants are in a close packed hexagonal phase, similar to the in-plane structure of other fluorocarbon molecules at water-air interface. Above a transition temperature the monolayer is in a low density gas phase. Preliminary study shows that hysteresis effect occurs around the transition temperature. The first measurements of microscopic structure at common high interfacial tension liquid-liquid interfaces such as a simple oil-water (hexane-water) interface is also reported. Thermal expansion coefficient measurements indicate subtle structural differences in these monolayers.

  20. Self-consistent quantum mechanical model for the description of excitation energy transfers in molecules at interfaces.

    PubMed

    Curutchet, Carles; Cammi, Roberto; Mennucci, Benedetta; Corni, Stefano

    2006-08-01

    In this paper we present a quantum mechanical model to study excitation energy transfers in molecular systems located in the vicinity of an interface. The model is based on an approximate solution of the time-dependent density functional theory equations and solvent effects are introduced in terms of the integral equation formalism version of the polarizable continuum model. A unique characteristic of this model is that environment induced polarizing effects on the interacting molecules and screening effects on their interaction are included in a coherent and self-consistent way. The model is applied to different situations of the ethylene dimer in the vicinity of an air/water interface and compared with an alternative quantum electrodynamics approach. PMID:16942244

  1. PREFACE: Water at interfaces Water at interfaces

    NASA Astrophysics Data System (ADS)

    Gallo, P.; Rovere, M.

    2010-07-01

    This special issue is devoted to illustrating important aspects and significant results in the field of modeling and simulation of water at interfaces with solutes or with confining substrates, focusing on a range of temperatures from ambient to supercooled. Understanding the behavior of water, in contact with different substrates and/or in solutions, is of pivotal importance for a wide range of applications in physics, chemistry and biochemistry. Simulations of confined and/or interfacial water are also relevant for testing how different its behavior is with respect to bulk water. Simulations and modeling in this field are of particular importance when studying supercooled regions where water shows anomalous properties. These considerations motivated the organization of a workshop at CECAM in the summer of 2009 which aimed to bring together scientists working with computer simulations on the properties of water in various environments with different methodologies. In this special issue, we collected a variety of interesting contributions from some of the speakers of the workshop. We have roughly classified the contributions into four groups. The papers of the first group address the properties of interfacial and confined water upon supercooling in an effort to understand the relation with anomalous behavior of supercooled bulk water. The second group deals with the specific problem of solvation. The next group deals with water in different environments by considering problems of great importance in technological and biological applications. Finally, the last group deals with quantum mechanical calculations related to the role of water in chemical processes. The first group of papers is introduced by the general paper of Stanley et al. The authors discuss recent progress in understanding the anomalies of water in bulk, nanoconfined, and biological environments. They present evidence that liquid water may display 'polymorphism', a property that can be present in

  2. Easy-to-use interface

    SciTech Connect

    Blattner, M M; Blattner, D O; Tong, Y

    1999-04-01

    Easy-to-use interfaces are a class of interfaces that fall between public access interfaces and graphical user interfaces in usability and cognitive difficulty. We describe characteristics of easy-to-use interfaces by the properties of four dimensions: selection, navigation, direct manipulation, and contextual metaphors. Another constraint we introduced was to include as little text as possible, and what text we have will be in at least four languages. Formative evaluations were conducted to identify and isolate these characteristics. Our application is a visual interface for a home automation system intended for a diverse set of users. The design will be expanded to accommodate the visually disabled in the near future.

  3. Interface Configuration Experiment: Preliminary results

    SciTech Connect

    Concus, P.; Finn, R.; Weislogel, M.

    1993-09-01

    The Interface Configuration Experiment (ICE) was carried out on USML-1 to investigate liquid-gas interfaces in certain rotationally-symmetric containers having prescribed, mathematically derived shapes. These containers have the property that they admit an entire continuum of distinct equilibrium rotationally-symmetric interfaces for a given liquid volume and contact angle. Furthermore, it can be shown that none of these interfaces can be stable. It was found, after the containers were filled in orbit, that an initial equilibrium interface from the symmetric continuum reoriented, when perturbed, to a stable interface that was not rotationally symmetric, in accordance with the mathematical theory.

  4. Interface Configuration Experiment: Preliminary Results

    NASA Technical Reports Server (NTRS)

    Concus, Paul; Finn, Robert; Weislogel, Mark

    1994-01-01

    The Interface Configuration Experiment (ICE) was carried out on USML-1 to investigate liquid-gas interfaces in certain rotationally-symmetric containers having prescribed, mathematically derived shapes. These containers have the property that they admit an entire continuum of distinct equilibrium rotationally-symmetric interfaces for a given liquid volume and contact angle. Furthermore, it can be shown that none of these interfaces can be stable. It was found, after the containers were filled in orbit, that an initial equilibrium interface from the symmetric continuum re-oriented, when perturbed, to a stable interface that was not rotationally symmetric, in accordance with the mathematical theory.

  5. Proteins at flowing interfaces: From understanding structure to treating disease

    NASA Astrophysics Data System (ADS)

    Posada, David; Young, James; Hirsa, Amir

    2012-11-01

    The field of soft matter offers vast opportunities for scientific and technological developments, with many challenges that need to be addressed by various disciplines. Fluid dynamics has a tremendous potential for greater impact, from broadening fundamental understanding to treating disease. Here we demonstrate the use of fluid dynamics in two biotechnology problems involving proteins at the air/water interface: a) 2-Dimensional protein crystallization and b) amyloid fibril formation. Protein crystallization is usually the most challenging step in X-ray diffraction analysis of protein structure. Recently it was demonstrated that flow can induce 2-D protein crystallization at conditions under which quiescent systems do not form crystals. A different form of protein structuring, namely amyloid fibrillization, is also of interest due to its association with several neurodegenerative diseases such as Alzheimer's and Parkinson's disease. Protein denaturation, which is the root of the fibrillization process, is also a significant concern in biotherapeutics production. Both problems are studied by using shearing free-surface flows in simple geometries. The common finding is that flow can significantly enhance the growth of protein structures.

  6. Oxidation of oleic acid monolayers at air/liquid interfaces

    NASA Astrophysics Data System (ADS)

    Voss, L. F.; Bazerbashi, M. F.; Beekman, C. P.; Hadad, C. M.; Allen, H. C.

    2006-12-01

    Field studies of marine and continental aerosols find that fatty acid films form on aqueous tropospheric aerosols. Oxidation of the acyl chains is thought to be key to aerosol growth. Oxidation of oleic acid monolayers by ozone was studied to understand the fate of fat-coated aerosols from both fresh and salt water sources. Using vibrational sum frequency generation spectroscopy and reflection absorption infrared spectroscopy, we present a molecular-level investigation of fatty acid monolayers at the air-water and air- sodium chloride solution interface and explore reactions with atmospheric oxidants by these model systems. Using sum frequency generation spectroscopy coupled with a Langmuir trough, concurrent spectroscopic and thermodynamic data were collected to obtain a molecular picture of the monolayers. No substantial difference was observed between oxidation of monolayers spread on water and on 0.6 molar sodium chloride solutions. Results indicate that depending on the size of the aerosol and the extent of oxidation, the subsequent oxidation products may not remain at the surface of these films, but instead be dissolved in the aqueous sub-phase of the aerosol particle. Results also indicate that oxidation of oleic acid could produce monolayers containing species that have no oxidized acyl chains.

  7. Oxidation of oleic acid monolayers at air/liquid interfaces

    NASA Astrophysics Data System (ADS)

    Voss, Laura

    2008-03-01

    Field studies of marine and continental aerosols find that fatty acid films form on aqueous tropospheric aerosols. Oxidation of oleic acid monolayers by ozone was studied to understand the fate of fat-coated aerosols from both fresh and salt water sources. Using vibrational sum frequency generation spectroscopy and reflection absorption infrared spectroscopy, we present a molecular-level investigation of fatty acid monolayers at the air-water and air-sodium chloride solution interface and explore reactions with atmospheric oxidants by these model systems. Coupling sum frequency generation spectroscopy with a Langmuir trough, concurrent spectroscopic and thermodynamic data were collected to obtain a molecular picture of the monolayers. No substantial difference was observed between oxidation of monolayers spread on water and on 0.6 molar sodium chloride solutions. Results indicate that depending on the size of the aerosol and the extent of oxidation, the subsequent oxidation products may not remain at the surface of these films, but instead be dissolved in the aqueous sub-phase of the aerosol particle. Results also indicate that oxidation of oleic acid could produce monolayers containing species that have no oxidized acyl chains.

  8. Photosensitized production of functionalized and unsaturated organic compounds at the air-sea interface

    NASA Astrophysics Data System (ADS)

    Ciuraru, Raluca; Fine, Ludovic; van Pinxteren, Manuela; D'Anna, Barbara; Herrmann, Hartmut; George, Christian

    2015-08-01

    The sea-surface microlayer (SML) has different physical, chemical and biological properties compared to the subsurface water, with an enrichment of organic matter i.e., dissolved organic matter including UV absorbing humic substances, fatty acids and many others. Here we present experimental evidence that dissolved organic matter, such as humic acids, when exposed to sunlight, can photosensitize the chemical conversion of linear saturated fatty acids at the air-water interface into unsaturated functionalized gas phase products (i.e. saturated and unsaturated aldehydes and acids, alkenes and dienes,…) which are known precursors of secondary organic aerosols. These functionalized molecules have previously been thought to be of biological origin, but here we demonstrate that abiotic interfacial photochemistry has the potential to produce such molecules. As the ocean is widely covered by the SML, this new understanding will impact on our ability to describe atmospheric chemistry in the marine environment.

  9. Gas transfer - A gas tension method for studying equilibration across a gas-water interface

    NASA Astrophysics Data System (ADS)

    Anderson, Meredith L.; Johnson, Bruce D.

    1992-11-01

    New strategies are required in the study of gas exchange under energetic and changeable conditions where current techniques are limited, especially in their ability to represent the contribution of injected bubbles. We have developed a gas tension device (GTD) that uses a solid-state differential pressure sensor to make continuous in situ measurements of the difference between pressure of dissolved gas (gas tension, for succinctness) and pressure of gas in the gas phase above a water parcel. This information allows the determination of the rate of approach to a dynamic equilibrium and of the degree of water phase saturation at steady state. The method is demonstrated in the lab by following the invasion of CO2 into seawater with bubble injection. The GTD introduces a new and versatile measurement method for the study of gas transfer across air-water interfaces, one which avoids many of the sampling and bias problems of traditional approaches.

  10. Photosensitized production of functionalized and unsaturated organic compounds at the air-sea interface

    PubMed Central

    Ciuraru, Raluca; Fine, Ludovic; van Pinxteren, Manuela; D’Anna, Barbara; Herrmann, Hartmut; George, Christian

    2015-01-01

    The sea-surface microlayer (SML) has different physical, chemical and biological properties compared to the subsurface water, with an enrichment of organic matter i.e., dissolved organic matter including UV absorbing humic substances, fatty acids and many others. Here we present experimental evidence that dissolved organic matter, such as humic acids, when exposed to sunlight, can photosensitize the chemical conversion of linear saturated fatty acids at the air-water interface into unsaturated functionalized gas phase products (i.e. saturated and unsaturated aldehydes and acids, alkenes and dienes,…) which are known precursors of secondary organic aerosols. These functionalized molecules have previously been thought to be of biological origin, but here we demonstrate that abiotic interfacial photochemistry has the potential to produce such molecules. As the ocean is widely covered by the SML, this new understanding will impact on our ability to describe atmospheric chemistry in the marine environment. PMID:26244712

  11. Thyra Abstract Interface Package

    2005-09-01

    Thrya primarily defines a set of abstract C++ class interfaces needed for the development of abstract numerical atgorithms (ANAs) such as iterative linear solvers, transient solvers all the way up to optimization. At the foundation of these interfaces are abstract C++ classes for vectors, vector spaces, linear operators and multi-vectors. Also included in the Thyra package is C++ code for creating concrete vector, vector space, linear operator, and multi-vector subclasses as well as other utilitiesmore » to aid in the development of ANAs. Currently, very general and efficient concrete subclass implementations exist for serial and SPMD in-core vectors and multi-vectors. Code also currently exists for testing objects and providing composite objects such as product vectors.« less

  12. Popeye Project: ROV interfaces

    SciTech Connect

    Scates, C.R.; Hickok, D.D.; Hernandez, D.A.

    1997-04-01

    The Popeye Project in the Gulf of Mexico helped advance the technology and standardization of ROV interfaces for deepwater subsea production systems. Some of the many successful ROV operations during installation and completion were {open_quotes}first-of-it`s-kind{close_quotes} activities-enabled by many technical advances. The use and reliance upon ROV systems for support of deepwater drilling and installation operations significantly increased in the past 10 years. Shell Offshore Inc.`s (SOI) confidence in this increased capability was an important factor in many of the design decisions which characterized the innovative system. Technology advancements, which depended on effective ROV intervention, were implemented with no significant difficulties. These advancements, in particular the flying leads and seabed position methods, are available to the industry for other deepwater subsea systems. In addition, several Popeye ROV interfaces have helped advance the subsea standardization initiative; e.g., hot stabs, torque-tool end effectors, and paint color.

  13. Standard interface file handbook

    SciTech Connect

    Shapiro, A.; Huria, H.C. )

    1992-10-01

    This handbook documents many of the standard interface file formats that have been adopted by the US Department of Energy to facilitate communications between and portability of, various large reactor physics and radiation transport software packages. The emphasis is on those files needed for use of the VENTURE/PC diffusion-depletion code system. File structures, contents and some practical advice on use of the various files are provided.

  14. Virtual button interface

    DOEpatents

    Jones, J.S.

    1999-01-12

    An apparatus and method of issuing commands to a computer by a user interfacing with a virtual reality environment are disclosed. To issue a command, the user directs gaze at a virtual button within the virtual reality environment, causing a perceptible change in the virtual button, which then sends a command corresponding to the virtual button to the computer, optionally after a confirming action is performed by the user, such as depressing a thumb switch. 4 figs.

  15. Virtual button interface

    DOEpatents

    Jones, Jake S.

    1999-01-01

    An apparatus and method of issuing commands to a computer by a user interfacing with a virtual reality environment. To issue a command, the user directs gaze at a virtual button within the virtual reality environment, causing a perceptible change in the virtual button, which then sends a command corresponding to the virtual button to the computer, optionally after a confirming action is performed by the user, such as depressing a thumb switch.

  16. SNE Industrial Fieldbus Interface

    NASA Technical Reports Server (NTRS)

    Lucena, Angel; Raines, Matthew; Oostdyk, Rebecca; Mata, Carlos

    2011-01-01

    Programmable logic controllers (PLCs) have very limited diagnostic and no prognostic capabilities, while current smart sensor designs do not have the capability to communicate over Fieldbus networks. The aim is to interface smart sensors with PLCs so that health and status information, such as failure mode identification and measurement tolerance, can be communicated via an industrial Fieldbus such as ControlNet. The SNE Industrial Fieldbus Interface (SIFI) is an embedded device that acts as a communication module in a networked smart sensor. The purpose is to enable a smart sensor to communicate health and status information to other devices, such as PLCs, via an industrial Fieldbus networking protocol. The SNE (Smart Network Element) is attached to a commercial off-the-shelf Any bus-S interface module through the SIFI. Numerous Anybus-S modules are available, each one designed to interface with a specific Fieldbus. Development of the SIFI focused on communications using the ControlNet protocol, but any of the Anybus-S modules can be used. The SIFI communicates with the Any-bus module via a data buffer and mailbox system on the Anybus module, and supplies power to the module. The Anybus module transmits and receives data on the Fieldbus using the proper protocol. The SIFI is intended to be connected to other existing SNE modules in order to monitor the health and status of a transducer. The SIFI can also monitor aspects of its own health using an onboard watchdog timer and voltage monitors. The SIFI also has the hardware to drive a touchscreen LCD (liquid crystal display) unit for manual configuration and status monitoring.

  17. Optical Neural Interfaces

    PubMed Central

    Warden, Melissa R.; Cardin, Jessica A.; Deisseroth, Karl

    2014-01-01

    Genetically encoded optical actuators and indicators have changed the landscape of neuroscience, enabling targetable control and readout of specific components of intact neural circuits in behaving animals. Here, we review the development of optical neural interfaces, focusing on hardware designed for optical control of neural activity, integrated optical control and electrical readout, and optical readout of population and single-cell neural activity in freely moving mammals. PMID:25014785

  18. The THOSE remote interface

    NASA Astrophysics Data System (ADS)

    Klawon, Kevin; Gold, Josh; Bachman, Kristen

    2013-05-01

    The DIA, in conjunction with the Army Research Lab (ARL), wants to create an Unmanned Ground Sensor (UGS) controller that is (a) interoperable across all controller platforms, (b) capable of easily adding new sensors, radios, and processes and (c) backward compatible with existing UGS systems. To achieve this, a Terra Harvest controller was created that used Java JRE 1.6 and an Open Services Gateway initiative (OSGi) platform, named Terra Harvest Open Software Environment (THOSE). OSGi is an extensible framework that provides a modularized environment for deploying functionality in "bundles". These bundles can publish, discover, and share services available from other external bundles or bundles provided by the controller core. With the addition of a web GUI used for interacting with THOSE, a natural step was then to create a common remote interface that allows 3rd party real-time interaction with the controller. This paper provides an overview of the THOSE system and its components as well as a description of the architectural structure of the remote interface, highlighting the interactions occurring between the controller and the remote interface and its role in providing a positive user experience for managing UGSS functions.

  19. Lessons from the biophysics of interfaces: lung surfactant and tear fluid.

    PubMed

    Rantamäki, Antti H; Telenius, Jelena; Koivuniemi, Artturi; Vattulainen, Ilpo; Holopainen, Juha M

    2011-05-01

    The purpose of this review is to provide insight into the biophysical properties and functions of tear fluid and lung surfactant--two similar fluids covering the epithelium of two distinctive organs. Both fluids form a layer-like structure that essentially comprise of an aqueous layer next to the epithelium and an anterior lipid layer at the air-water interface. The aqueous layers contain soluble proteins and metabolites, and they are responsible for the host defence system and nutrition of the organ. However, many proteins also interact with the lipid layer and are important for the surface-active function of the fluid film. The lipid layer of lung surfactant comprises mainly of phospholipids, especially phosphatidylcholines, and only small amounts of non-polar lipids, mainly cholesterol. In contrast, tear fluid lipid layer comprises of a mixture of polar and non-polar lipids. However, the relative proportion and the spectrum of different polar and non-polar lipids seem to be more extensive in tear fluid than in lung surfactant. The differing lipid compositions generate distinctive lipid layer structures. Despite the structural differences, these lipid layers decrease the surface tension of the air-water interface. The structure of the tear film lipid layer also minimises the evaporation of the tear fluid. In lung surfactant surface activity is crucial for the function of the organ, as the lipid layer prevents the collapse of the lung alveoli during the compression-expansion cycle of breathing. Similarly the tear film experiences a compression-expansion cycle during blinking. The dynamics of this cycle have been studied to a lesser extent and are not as clear as those of lung surfactant. The common structure and properties suggest a similar behaviour under rapid compression-expansion for both fluids. PMID:21352946

  20. Shear rheology of hydrophobin adsorption layers at oil/water interfaces and data interpretation in terms of a viscoelastic thixotropic model.

    PubMed

    Radulova, Gergana M; Danov, Krassimir D; Kralchevsky, Peter A; Petkov, Jordan T; Stoyanov, Simeon D

    2014-08-21

    Here, we investigate the surface shear rheology of class II HFBII hydrophobin layers at the oil/water interface. Experiments in two different dynamic regimes, at a fixed rate of strain and oscillations, have been carried out with a rotational rheometer. The rheological data obtained in both regimes comply with the same viscoelastic thixotropic model, which is used to determine the surface shear elasticity and viscosity, E(sh) and η(sh). Their values for HFBII at oil/water interfaces are somewhat lower than those at the air/water interface. Moreover, E(sh) and η(sh) depend on the nature of oil, being smaller for hexadecane in comparison with soybean-oil. It is remarkable that E(sh) is independent of the rate of strain in the whole investigated range of shear rates. For oil/water interfaces, E(sh) and η(sh) determined for HFBII layers are considerably greater than for other proteins, like lysozyme and β-casein. It is confirmed that the hydrophobin forms the most rigid surface layers among all investigated proteins not only for the air/water, but also for the oil/water interface. The wide applicability of the used viscoelastic thixotropic model is confirmed by analyzing data for adsorption layers at oil/water interfaces from lysozyme and β-casein - both native and cross-linked by enzyme, as well as for films from asphaltene. This model turns out to be a versatile tool for determining the surface shear elasticity and viscosity, E(sh) and η(sh), from experimental data for the surface storage and loss moduli, G' and G''. PMID:24981289