An energy balance model exploration of the impacts of interactions between surface albedo, cloud cover and water vapor on polar amplification

NASA Astrophysics Data System (ADS)

Södergren, A. Helena; McDonald, Adrian J.; Bodeker, Gregory E.

2017-11-01

We examine the effects of non-linear interactions between surface albedo, water vapor and cloud cover (referred to as climate variables) on amplified warming of the polar regions, using a new energy balance model. Our simulations show that the sum of the contributions to surface temperature changes due to any variable considered in isolation is smaller than the temperature changes from coupled feedback simulations. This non-linearity is strongest when all three climate variables are allowed to interact. Surface albedo appears to be the strongest driver of this non-linear behavior, followed by water vapor and clouds. This is because increases in longwave radiation absorbed by the surface, related to increases in water vapor and clouds, and increases in surface absorbed shortwave radiation caused by a decrease in surface albedo, amplify each other. Furthermore, our results corroborate previous findings that while increases in cloud cover and water vapor, along with the greenhouse effect itself, warm the polar regions, water vapor also significantly warms equatorial regions, which reduces polar amplification. Changes in surface albedo drive large changes in absorption of incoming shortwave radiation, thereby enhancing surface warming. Unlike high latitudes, surface albedo change at low latitudes are more constrained. Interactions between surface albedo, water vapor and clouds drive larger increases in temperatures in the polar regions compared to low latitudes. This is in spite of the fact that, due to a forcing, cloud cover increases at high latitudes and decreases in low latitudes, and that water vapor significantly enhances warming at low latitudes.

Molecular origins of fluorocarbon hydrophobicity

PubMed Central

Dalvi, Vishwanath H.; Rossky, Peter J.

2010-01-01

We have undertaken atomistic molecular simulations to systematically determine the structural contributions to the hydrophobicity of fluorinated solutes and surfaces compared to the corresponding hydrocarbon, yielding a unified explanation for these phenomena. We have transformed a short chain alkane, n-octane, to n-perfluorooctane in stages. The free-energy changes and the entropic components calculated for each transformation stage yield considerable insight into the relevant physics. To evaluate the effect of a surface, we have also conducted contact-angle simulations of water on self-assembled monolayers of hydrocarbon and fluorocarbon thiols. Our results, which are consistent with experimental observations, indicate that the hydrophobicity of the fluorocarbon, whether the interaction with water is as solute or as surface, is due to its “fatness.” In solution, the extra work of cavity formation to accommodate a fluorocarbon, compared to a hydrocarbon, is not offset by enhanced energetic interactions with water. The enhanced hydrophobicity of fluorinated surfaces arises because fluorocarbons pack less densely on surfaces leading to poorer van der Waals interactions with water. We find that interaction of water with a hydrophobic solute/surface is primarily a function of van der Waals interactions and is substantially independent of electrostatic interactions. This independence is primarily due to the strong tendency of water at room temperature to maintain its hydrogen bonding network structure at an interface lacking hydrophilic sites. PMID:20643968

Monitoring groundwater-surface water interaction using time-series and time-frequency analysis of transient three-dimensional electrical resistivity changes

USGS Publications Warehouse

Johnson, Timothy C.; Slater, Lee D.; Ntarlagiannis, Dimitris; Day-Lewis, Frederick D.; Elwaseif, Mehrez

2012-01-01

Time-lapse resistivity imaging is increasingly used to monitor hydrologic processes. Compared to conventional hydrologic measurements, surface time-lapse resistivity provides superior spatial coverage in two or three dimensions, potentially high-resolution information in time, and information in the absence of wells. However, interpretation of time-lapse electrical tomograms is complicated by the ever-increasing size and complexity of long-term, three-dimensional (3-D) time series conductivity data sets. Here we use 3-D surface time-lapse electrical imaging to monitor subsurface electrical conductivity variations associated with stage-driven groundwater-surface water interactions along a stretch of the Columbia River adjacent to the Hanford 300 near Richland, Washington, USA. We reduce the resulting 3-D conductivity time series using both time-series and time-frequency analyses to isolate a paleochannel causing enhanced groundwater-surface water interactions. Correlation analysis on the time-lapse imaging results concisely represents enhanced groundwater-surface water interactions within the paleochannel, and provides information concerning groundwater flow velocities. Time-frequency analysis using the Stockwell (S) transform provides additional information by identifying the stage periodicities driving groundwater-surface water interactions due to upstream dam operations, and identifying segments in time-frequency space when these interactions are most active. These results provide new insight into the distribution and timing of river water intrusion into the Hanford 300 Area, which has a governing influence on the behavior of a uranium plume left over from historical nuclear fuel processing operations.

Interaction of SO2 with the Surface of a Water Nanodroplet.

PubMed

Zhong, Jie; Zhu, Chongqin; Li, Lei; Richmond, Geraldine L; Francisco, Joseph S; Zeng, Xiao Cheng

2017-11-29

We present a comprehensive computational study of interaction of a SO 2 with water molecules in the gas phase and with the surface of various sized water nanodroplets to investigate the solvation behavior of SO 2 in different atmospheric environments. Born-Oppenheimer molecular dynamics (BOMD) simulation shows that, in the gas phase and at a temperature of 300 K, the dominant interaction between SO 2 and H 2 O is (SO 2 ) S···O (H 2 O) , consistent with previous density-functional theory (DFT) computation at 0 K. However, at the surface of a water nanodroplet, BOMD simulation shows that the hydrogen-bonding interaction of (SO 2 ) O···H (H 2 O) becomes increasingly important with the increase of droplet size, reflecting a marked effect of the water surface on the SO 2 solvation. This conclusion is in good accordance with spectroscopy evidence obtained previously (J. Am. Chem. Soc. 2005, 127, 16806; J. Am. Chem. Soc. 2006, 128, 3256). The prevailing interaction (SO 2 ) O···H (H 2 O) on a large droplet is mainly due to favorable exposure of H atoms of H 2 O at the air-water interface. Indeed, the conversion of the dominant interaction in the gas phase (SO 2 ) S···O (H 2 O) to the dominant interaction on the water nanodroplet (SO 2 ) O···H (H 2 O) may incur effects on the SO 2 chemistry in atmospheric aerosols because the solvation of SO 2 at the water surface can affect the reactive sites and electrophilicity of SO 2 . Hence, the solvation of SO 2 on the aerosol surface may have new implications when studying SO 2 chemistry in the aerosol-containing troposphere.

Ground-water/surface-water interaction in nearshore areas of Three Lakes on the Grand Portage Reservation, northeastern Minnesota, 2003-04

USGS Publications Warehouse

Jones, Perry M.

2006-01-01

Knowledge of general water-flow directions in lake watersheds and how they may change seasonally can help water-quality specialists and lake managers address a variety of water-quality and aquatic habitat protection issues for lakes. Results from this study indicate that ground-water and surface-water interactions at the study lakes are complex, and the ability of the applied techniques to identify ground-water inflow and surface-water outseepage locations varied among the lakes. Measurement of lake-sediment temperatures proved to be a reliable and relatively inexpensive reconnaissance technique that lake managers may apply in complex settings to identify general areas of ground-water inflow and surface-water outseepage.

Interaction of surface water and groundwater in the Nile River basin: isotopic and piezometric evidence

NASA Astrophysics Data System (ADS)

Kebede, Seifu; Abdalla, Osman; Sefelnasr, Ahmed; Tindimugaya, Callist; Mustafa, Osman

2017-05-01

Past discussions around water-resources management and development in the River Nile basin disregard groundwater resources from the equation. There is an increasing interest around factoring the groundwater resources as an integral part of the Nile Basin water resources. This is hampered by knowledge gap regarding the groundwater resources dynamics (recharge, storage, flow, quality, surface-water/groundwater interaction) at basin scale. This report provides a comprehensive analysis of the state of surface-water/groundwater interaction from the headwater to the Nile Delta region. Piezometric and isotopic (δ18O, δ2H) evidence reveal that the Nile changes from a gaining stream in the headwater regions to mostly a loosing stream in the arid lowlands of Sudan and Egypt. Specific zones of Nile water leakage to the adjacent aquifers is mapped using the two sources of evidence. Up to 50% of the surface-water flow in the equatorial region of the Nile comes from groundwater as base flow. The evidence also shows that the natural direction and rate of surface-water/groundwater interaction is largely perturbed by human activities (diversion, dam construction) particularly downstream of the Aswan High Dam in Egypt. The decrease in discharge of the Nile River along its course is attributed to leakage to the aquifers as well as to evaporative water loss from the river channel. The surface-water/groundwater interaction occurring along the Nile River and its sensitivity to infrastructure development calls for management strategies that account groundwater as an integral part of the Nile Basin resources.

Suppression of ENSO in a coupled model without water vapor feedback

NASA Astrophysics Data System (ADS)

Hall, A.; Manabe, S.

We examine 800-year time series of internally generated variability in both a coupled ocean-atmosphere model where water vapor anomalies are not allowed to interact with longwave radiation and one where they are. The ENSO-like phenomenon in the experiment without water vapor feedback is drastically suppressed both in amplitude and geographic extent relative to the experiment with water vapor feedback. Surprisingly, the reduced amplitude of ENSO-related sea surface temperature anomalies in the model without water vapor feedback cannot be attributed to greater longwave damping of sea surface temperature. (Differences between the two experiments in radiative feedback due to clouds counterbalance almost perfectly the differences in radiative feedback due to water vapor.) Rather, the interaction between water vapor anomalies and longwave radiation affects the ENSO-like phenomenon through its influence on the vertical structure of radiative heating: Because of the changes in water vapor associated with it, a given warm equatorial Pacific sea surface temperature anomaly is associated with a radiative heating profile that is much more gravitationally unstable when water vapor feedback is present. The warm sea surface temperature anomaly therefore results in more convection in the experiment with water vapor feedback. The increased convection, in turn, is related to a larger westerly wind-stress anomaly, which creates a larger decrease in upwelling of cold water, thereby enhancing the magnitude of the original warm sea surface temperature anomaly. In this manner, the interaction between water vapor anomalies and longwave radiation magnifies the air-sea interactions at the heart of the ENSO phenomenon; without this interaction, the coupling between sea surface temperature and wind stress is effectively reduced, resulting in smaller amplitude ENSO episodes with a more limited geographical extent.

Modeling decadal timescale interactions between surface water and ground water in the central Everglades, Florida, USA

USGS Publications Warehouse

Harvey, J.W.; Newlin, J.T.; Krupa, S.L.

2006-01-01

Surface-water and ground-water flow are coupled in the central Everglades, although the remoteness of this system has hindered many previous attempts to quantify interactions between surface water and ground water. We modeled flow through a 43,000 ha basin in the central Everglades called Water Conservation Area 2A. The purpose of the model was to quantify recharge and discharge in the basin's vast interior areas. The presence and distribution of tritium in ground water was the principal constraint on the modeling, based on measurements in 25 research wells ranging in depth from 2 to 37 m. In addition to average characteristics of surface-water flow, the model parameters included depth of the layer of 'interactive' ground water that is actively exchanged with surface water, average residence time of interactive ground water, and the associated recharge and discharge fluxes across the wetland ground surface. Results indicated that only a relatively thin (8 m) layer of the 60 m deep surfical aquifer actively exchanges surface water and ground water on a decadal timescale. The calculated storage depth of interactive ground water was 3.1 m after adjustment for the porosity of peat and sandy limestone. Modeling of the tritium data yielded an average residence time of 90 years in interactive ground water, with associated recharge and discharge fluxes equal to 0.01 cm d -1. 3H/3He isotopic ratio measurements (which correct for effects of vertical mixing in the aquifer with deeper, tritium-dead water) were available from several wells, and these indicated an average residence time of 25 years, suggesting that residence time was overestimated using tritium measurements alone. Indeed, both residence time and storage depth would be expected to be overestimated due to vertical mixing. The estimate of recharge and discharge (0.01 cm d-1) that resulted from tritium modeling therefore is still considered reliable, because the ratio of residence time and storage depth (used to calculated recharge and discharge) is much less sensitive to vertical mixing compared with residence time alone. We conclude that a small but potentially significant component of flow through the Everglades is recharged to the aquifer and stored there for years to decades before discharged back to surface water. Long-term storage of water and solutes in the ground-water system beneath the wetlands has implications for restoration of Everglades water quality.

Modeling decadal timescale interactions between surface water and ground water in the central Everglades, Florida, USA

NASA Astrophysics Data System (ADS)

Harvey, Judson W.; Newlin, Jessica T.; Krupa, Steven L.

2006-04-01

Surface-water and ground-water flow are coupled in the central Everglades, although the remoteness of this system has hindered many previous attempts to quantify interactions between surface water and ground water. We modeled flow through a 43,000 ha basin in the central Everglades called Water Conservation Area 2A. The purpose of the model was to quantify recharge and discharge in the basin's vast interior areas. The presence and distribution of tritium in ground water was the principal constraint on the modeling, based on measurements in 25 research wells ranging in depth from 2 to 37 m. In addition to average characteristics of surface-water flow, the model parameters included depth of the layer of 'interactive' ground water that is actively exchanged with surface water, average residence time of interactive ground water, and the associated recharge and discharge fluxes across the wetland ground surface. Results indicated that only a relatively thin (8 m) layer of the 60 m deep surfical aquifer actively exchanges surface water and ground water on a decadal timescale. The calculated storage depth of interactive ground water was 3.1 m after adjustment for the porosity of peat and sandy limestone. Modeling of the tritium data yielded an average residence time of 90 years in interactive ground water, with associated recharge and discharge fluxes equal to 0.01 cm d -1. 3H/ 3He isotopic ratio measurements (which correct for effects of vertical mixing in the aquifer with deeper, tritium-dead water) were available from several wells, and these indicated an average residence time of 25 years, suggesting that residence time was overestimated using tritium measurements alone. Indeed, both residence time and storage depth would be expected to be overestimated due to vertical mixing. The estimate of recharge and discharge (0.01 cm d -1) that resulted from tritium modeling therefore is still considered reliable, because the ratio of residence time and storage depth (used to calculated recharge and discharge) is much less sensitive to vertical mixing compared with residence time alone. We conclude that a small but potentially significant component of flow through the Everglades is recharged to the aquifer and stored there for years to decades before discharged back to surface water. Long-term storage of water and solutes in the ground-water system beneath the wetlands has implications for restoration of Everglades water quality.

Linear relationship between water wetting behavior and microscopic interactions of super-hydrophilic surfaces.

PubMed

Liu, Jian; Wang, Chunlei; Guo, Pan; Shi, Guosheng; Fang, Haiping

2013-12-21

Using molecular dynamics simulations, we show a fine linear relationship between surface energies and microscopic Lennard-Jones parameters of super-hydrophilic surfaces. The linear slope of the super-hydrophilic surfaces is consistent with the linear slope of the super-hydrophobic, hydrophobic, and hydrophilic surfaces where stable water droplets can stand, indicating that there is a universal linear behavior of the surface energies with the water-surface van der Waals interaction that extends from the super-hydrophobic to super-hydrophilic surfaces. Moreover, we find that the linear relationship exists for various substrate types, and the linear slopes of these different types of substrates are dependent on the surface atom density, i.e., higher surface atom densities correspond to larger linear slopes. These results enrich our understanding of water behavior on solid surfaces, especially the water wetting behaviors on uncharged super-hydrophilic metal surfaces.

Anomalous water dynamics at surfaces and interfaces: synergistic effects of confinement and surface interactions

NASA Astrophysics Data System (ADS)

Biswas, Rajib; Bagchi, Biman

2018-01-01

In nature, water is often found in contact with surfaces that are extended on the scale of molecule size but small on a macroscopic scale. Examples include lipid bilayers and reverse micelles as well as biomolecules like proteins, DNA and zeolites, to name a few. While the presence of surfaces and interfaces interrupts the continuous hydrogen bond network of liquid water, confinement on a mesoscopic scale introduces new features. Even when extended on a molecular scale, natural and biological surfaces often have features (like charge, hydrophobicity) that vary on the scale of the molecular diameter of water. As a result, many new and exotic features, which are not seen in the bulk, appear in the dynamics of water close to the surface. These different behaviors bear the signature of both water-surface interactions and of confinement. In other words, the altered properties are the result of the synergistic effects of surface-water interactions and confinement. Ultrafast spectroscopy, theoretical modeling and computer simulations together form powerful synergistic approaches towards an understanding of the properties of confined water in such systems as nanocavities, reverse micelles (RMs), water inside and outside biomolecules like proteins and DNA, and also between two hydrophobic walls. We shall review the experimental results and place them in the context of theory and simulations. For water confined within RMs, we discuss the possible interference effects propagating from opposite surfaces. Similar interference is found to give rise to an effective attractive force between two hydrophobic surfaces immersed and kept fixed at a separation of d, with the force showing an exponential dependence on this distance. For protein and DNA hydration, we shall examine a multitude of timescales that arise from frustration effects due to the inherent heterogeneity of these surfaces. We pay particular attention to the role of orientational correlations and modification of the same due to interaction with the surfaces.

USE OF CONTINUOUS DATALOGGERS TO ASSESS THE TEMPORAL AND SPATIAL VARIATION OF GROUND WATER/SURFACE WATER INTERACTION BEFORE AND AFTER STREAM RESTORATION

EPA Science Inventory

Minebank Run is a degraded second-order flashy urban stream in Baltimore County which is slated to undergo restoration in August 2003 to re-establish geomorphic stability. We are currently conducting an intensive investigation of surface water/ground water interaction and nutrien...

Investigating the Interaction of Water Vapour with Aminopropyl Groups on the Surface of Mesoporous Silica Nanoparticles.

PubMed

Paul, Geo; Musso, Giorgia Elena; Bottinelli, Emanuela; Cossi, Maurizio; Marchese, Leonardo; Berlier, Gloria

2017-04-05

The interaction of water molecules with the surface of hybrid silica-based mesoporous materials is studied by 29 Si, 1 H and 13 C solid-state NMR and IR spectroscopy, with the support of ab initio calculations. The surface of aminopropyl-grafted mesoporous silica nanoparticles is studied in the dehydrated state and upon interaction with controlled doses of water vapour. Former investigations described the interactions between aminopropyl and residual SiOH groups; the present study shows the presence of hydrogen-bonded species (SiOH to NH 2 ) and weakly interacting "free" aminopropyl chains with restricted mobility, together with a small amount of protonated NH 3 + groups. The concentration of the last-named species increased upon interaction with water, and this indicates reversible and fast proton exchange from water molecules to a fraction of the amino groups. Herein, this is discussed and explained for the first time, by a combination of experimental and theoretical approaches. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modeling the Surface Water-Groundwater Interaction in Arid and Semi-Arid Regions Impacted by Agricultural Activities

NASA Astrophysics Data System (ADS)

Tian, Y.; Wu, B.; Zheng, Y.

2013-12-01

In many semi-arid and arid regions, interaction between surface water and groundwater plays an important role in the eco-hydrological system. The interaction is often complicated by agricultural activities such as surface water diversion, groundwater pumping, and irrigation. In existing surface water-groundwater integrated models, simulation of the interaction is often simplified, which could introduce significant simulation uncertainty under certain circumstance. In this study, GSFLOW, a USGS model coupling PRMS and MODFLOW, was improved to better characterize the surface water-groundwater interaction. The practices of water diversion from rivers, groundwater pumping and irrigation are explicitly simulated. In addition, the original kinematic wave routing method was replaced by a dynamic wave routing method. The improved model was then applied in Zhangye Basin (the midstream part of Heihe River Baisn), China, where the famous 'Silk Road' came through. It is a typical semi-arid region of the western China, with extensive agriculture in its oasis. The model was established and calibrated using the data in 2000-2008. A series of numerical experiments were conducted to evaluate the effect of those improvements. It has been demonstrated that with the improvements, the observed streamflow and groundwater level were better reproduced by the model. The improvements have a significant impact on the simulation of multiple fluxes associated with the interaction, such as groundwater discharge, riverbed seepage, infiltration, etc. Human activities were proved to be key elements of the water cycle in the study area. The study results have important implications to the water resources modeling and management in semi-arid and arid basins.

Simulated effects of development on regional ground-water/surface-water interactions in the northern Coastal Plain of New Jersey

NASA Astrophysics Data System (ADS)

Pucci, Amleto A.; Pope, Daryll A.

1995-05-01

Stream flow in the Coastal Plain of New Jersey is primarily controlled by ground-water discharge. Ground-water flow in a 400 square mile area (1035 km 2) of the Potomac-Raritan-Magothy aquifer system (PRMA) in the northern Coastal Plain of New Jersey was simulated to examine development effects on water resources. Simulations showed that historical development caused significant capture of regional ground-water discharge to streams and wetlands. The Cretaceous PRMA primarily is composed of fine to coarse sand, clays and silts which form the Upper and Middle aquifers and their confining units. The aquifer outcrops are the principal areas of recharge and discharge for the regional flow system and have many traversing streams and surface-water bodies. A quasi-three-dimensional numerical model that incorporated ground-water/surface-water interactions and boundary flows from a larger regional model was used to represent the PRMA. To evaluate the influence of ground-water development on interactions in different areas, hydrogeologically similar and contiguous model stream cells were aggregated as 'stream zones'. The model representation of surface-water and ground-water interaction was limited in the areas of confining unit outcrops and because of this, simulated ground-water discharge could not be directly compared with base flow. Significant differences in simulated ground-water and surface-water interactions between the predevelopment and developed system, include; (1) redistribution of recharge and discharge areas; (2) reduced ground-water discharge to streams. In predevelopment, the primary discharge for the Upper and Middle aquifers is to low-lying streams and wetlands; in the developed system, the primary discharge is to ground-water withdrawals. Development reduces simulated ground-water discharge to streams in the Upper Aquifer from 61.4 to 10% of the Upper Aquifer hydrologic budget (28.9%, if impounded stream flow is included). Ground-water discharge to streams in the Middle Aquifer decreases from 80.0 to 22% of the Middle Aquifer hydrologic budget. The utility of assessing ground-water/surface-water interaction in a regional hydrogeologic system by simulation responses to development is demonstrated and which can compensate for lack of long-term stream-gaging data in determining management decisions.

Influence of water on the surface of graphene

NASA Astrophysics Data System (ADS)

Kaya, Yunus; Kalkan, Yalçin; Veenhof, Rob

2018-02-01

We have studied how water modifies the surface of graphene and in particular how the surface conductivity of graphene is affected. According to the literature, two types of interactions should be distinguished: physical, where a water molecule remains intact and is located at some distance from the mesh, and chemical, where a water molecule is imbricated in the graphene bond structure. We have developed theoretical models for both types of interactions using the density functional theory (DFT) with the B3LYP hybrid functional combined with the 6-31G(d) basis set. Our calculations show that the surface conductivity of graphene is reduced in the presence of water.

Evidence for phase separation of ethanol-water mixtures at the hydrogen terminated nanocrystalline diamond surface.

PubMed

Janssens, Stoffel D; Drijkoningen, Sien; Saitner, Marc; Boyen, Hans-Gerd; Wagner, Patrick; Larsson, Karin; Haenen, Ken

2012-07-28

Interactions between ethanol-water mixtures and a hydrophobic hydrogen terminated nanocrystalline diamond surface, are investigated by sessile drop contact angle measurements. The surface free energy of the hydrophobic surface, obtained with pure liquids, differs strongly from values obtained by ethanol-water mixtures. Here, a model which explains this difference is presented. The model suggests that, due to a higher affinity of ethanol for the hydrophobic surface, when compared to water, a phase separation occurs when a mixture of both liquids is in contact with the H-terminated diamond surface. These results are supported by a computational study giving insight in the affinity and related interaction at the liquid-solid interface.

Enthalpic Breakdown of Water Structure on Protein Active-Site Surfaces

PubMed Central

Haider, Kamran; Wickstrom, Lauren; Ramsey, Steven; Gilson, Michael K.; Kurtzman, Tom

2016-01-01

The principles underlying water reorganization around simple non-polar solutes are well understood and provide the framework for classical hydrophobic effect, whereby water molecules structure themselves around solutes so that they maintain favorable energetic contacts with both the solute and with other water molecules. However, for certain solute surface topographies, water molecules, due to their geometry and size, are unable to simultaneously maintain favorable energetic contacts with both the surface and neighboring water molecules. In this study, we analyze the solvation of ligand-binding sites for six structurally diverse proteins using hydration site analysis and measures of local water structure, in order to identify surfaces at which water molecules are unable to structure themselves in a way that maintains favorable enthalpy relative to bulk water. These surfaces are characterized by a high degree of enclosure, weak solute-water interactions, and surface constraints that induce unfavorable pair interactions between neighboring water molecules. Additionally, we find that the solvation of charged side-chains in an active site generally results in favorable enthalpy but can also lead to pair interactions between neighboring water molecules that are significantly unfavorable relative to bulk water. We find that frustrated local structure can occur not only in apolar and weakly polar pockets, where overall enthalpy tends to be unfavorable, but also in charged pockets, where overall water enthalpy tends to be favorable. The characterization of local water structure in these terms may prove useful for evaluating the displacement of water from diverse protein active-site environments. PMID:27169482

Water interactions with condensed organic phases: a combined experimental and theoretical study of molecular-level processes

NASA Astrophysics Data System (ADS)

Johansson, Sofia M.; Kong, Xiangrui; Thomson, Erik S.; Papagiannakopoulos, Panos; Pettersson, Jan B. C.; Lovrić, Josip; Toubin, Céline

2016-04-01

Water uptake on aerosol particles modifies their chemistry and microphysics with important implications for air quality and climate. A large fraction of the atmospheric aerosol consists of organic aerosol particles or inorganic particles with condensed organic components. Here, we combine laboratory studies using the environmental molecular beam (EMB) method1 with molecular dynamics (MD) simulations to characterize water interactions with organic surfaces in detail. The over-arching aim is to characterize the mechanisms that govern water uptake, in order to guide the development of physics-based models to be used in atmospheric modelling. The EMB method enables molecular level studies of interactions between gases and volatile surfaces at near ambient pressure,1 and the technique may provide information about collision dynamics, surface and bulk accommodation, desorption and diffusion kinetics. Molecular dynamics simulations provide complementary information about the collision dynamics and initial interactions between gas molecules and the condensed phase. Here, we focus on water interactions with condensed alcohol phases that serve as highly simplified proxies for systems in the environment. Gas-surface collisions are in general found to be highly inelastic and result in efficient surface accommodation of water molecules. As a consequence, surface accommodation of water can be safely assumed to be close to unity under typical ambient conditions. Bulk accommodation is inefficient on solid alcohol and the condensed materials appear to produce hydrophobic surface structures, with limited opportunities for adsorbed water to form hydrogen bonds with surface molecules. Accommodation is significantly more efficient on the dynamic liquid alcohol surfaces. The results for n-butanol (BuOH) are particularly intriguing where substantial changes in water accommodation taking place over a 10 K interval below and above the BuOH melting point.2 The governing mechanisms for the observed water accommodation are discussed based on the combined EMB and MD results. The studies illustrate that the detailed surface properties of the condensed organic phase may substantially modify water uptake, with potential implications for the properties and action of aerosols and clouds in the Earth system. References: 1. X.R. Kong, E. S. Thomson, P. Papagiannakopoulos, S.M. Johansson, and J.B.C. Pettersson, Water Accommodation on Ice and Organic Surfaces: Insights from Environmental Molecular Beam Experiments. J. Phys. Chem. B 118 (2014) 13378-13386. 2. P. Papagiannakopoulos, X. Kong, E. S. Thomson, N. Marković, and J. B. C. Pettersson, Surface Transformations and Water Uptake on Liquid and Solid Butanol near the Melting Temperature. J. Phys. Chem. C 117 (2013) 6678-6685.

Some physicochemical aspects of water-soluble mineral flotation.

PubMed

Wu, Zhijian; Wang, Xuming; Liu, Haining; Zhang, Huifang; Miller, Jan D

2016-09-01

Some physicochemical aspects of water-soluble mineral flotation including hydration phenomena, associations and interactions between collectors, air bubbles, and water-soluble mineral particles are presented. Flotation carried out in saturated salt solutions, and a wide range of collector concentrations for effective flotation of different salts are two basic aspects of water-soluble mineral flotation. Hydration of salt ions, mineral particle surfaces, collector molecules or ions, and collector aggregates play an important role in water-soluble mineral flotation. The adsorption of collectors onto bubble surfaces is suggested to be the precondition for the association of mineral particles with bubbles. The association of collectors with water-soluble minerals is a complicated process, which may include the adsorption of collector molecules or ions onto such surfaces, and/or the attachment of collector precipitates or crystals onto the mineral surfaces. The interactions between the collectors and the minerals include electrostatic and hydrophobic interactions, hydrogen bonding, and specific interactions, with electrostatic and hydrophobic interactions being the common mechanisms. For the association of ionic collectors with minerals with an opposite charge, electrostatic and hydrophobic interactions could have a synergistic effect, with the hydrophobic interactions between the hydrophobic groups of the previously associated collectors and the hydrophobic groups of oncoming collectors being an important attractive force. Association between solid particles and air bubbles is the key to froth flotation, which is affected by hydrophobicity of the mineral particle surfaces, surface charges of mineral particles and bubbles, mineral particle size and shape, temperature, bubble size, etc. The use of a collector together with a frother and the use of mixed surfactants as collectors are suggested to improve flotation. Copyright © 2016 Elsevier B.V. All rights reserved.

Farm water budgets for semiarid irrigated floodplains of northern New Mexico: characterizing the surface water-groundwater interactions

NASA Astrophysics Data System (ADS)

Gutierrez, K. Y.; Fernald, A.; Ochoa, C. G.; Guldan, S. J.

2013-12-01

KEY WORDS - Hydrology, Water budget, Deep percolation, Surface water-Groundwater interactions. With the recent projections for water scarcity, water balances have become an indispensable water management tool. In irrigated floodplains, deep percolation from irrigation can represent one of the main aquifer recharge sources. A better understanding of surface water and groundwater interactions in irrigated valleys is needed for properly assessing the water balances in these systems and estimating potential aquifer recharge. We conducted a study to quantify the parameters and calculate the water budgets in three flood irrigated hay fields with relatively low, intermediate and, high water availability in northern New Mexico. We monitored different hydrologic parameters including total amount of water applied, change in soil moisture, drainage below the effective root zone, and shallow water level fluctuations in response to irrigation. Evapotranspiration was calculated from weather station data collected in-situ using the Samani-Hargreaves. Previous studies in the region have estimated deep percolation as a residual parameter of the water balance equation. In this study, we used both, the water balance method and actual measurements of deep percolation using passive lysimeters. Preliminary analyses for the three fields show a relatively rapid movement of water through the upper 50 cm of the vadose zone and a quick response of the shallow aquifer under flood irrigation. Further results from this study will provide a better understanding of surface water-groundwater interactions in flood irrigated valleys in northern New Mexico.

Role of air-water interfaces in colloid transport in porous media: A review

NASA Astrophysics Data System (ADS)

Flury, Markus; Aramrak, Surachet

2017-07-01

Air-water interfaces play an important role in unsaturated porous media, giving rise to phenomena like capillarity. Less recognized and understood are interactions of colloids with the air-water interface in porous media and the implications of these interactions for fate and transport of colloids. In this review, we discuss how colloids, both suspended in the aqueous phase and attached at pore walls, interact with air-water interfaces in porous media. We discuss the theory of colloid/air-water interface interactions, based on the different forces acting between colloids and the air-water interface (DLVO, hydrophobic, capillary forces) and based on thermodynamic considerations (Gibbs free energy). Subsurface colloids are usually electrostatically repelled from the air-water interface because most subsurface colloids and the air-water are negatively charged. However, hydrophobic interactions can lead to attraction to the air-water interface. When colloids are at the air-water interface, capillary forces are usually dominant over other forces. Moving air-water interfaces are effective in mobilizing and transporting colloids from surfaces. Thermodynamic considerations show that, for a colloid, the air-water interface is the favored state as compared with the suspension phase, except for hydrophilic colloids in the nanometer size range. Experimental evidence indicates that colloid mobilization in soils often occurs through macropores, although matrix transport is also prevalent in absence of macropores. Moving air-water interfaces, e.g., occurring during infiltration, imbibition, or drainage, have been shown to scour colloids from surfaces and translocate colloids. Colloids can also be pinned to surfaces by thin water films and capillary menisci at the air-water-solid interface line, causing colloid retention and immobilization. Air-water interfaces thus can both mobilize or immobilize colloids in porous media, depending on hydrodynamics and colloid and surface chemistry.

Mathematical modelling of surface water-groundwater flow and salinity interactions in the coastal zone

NASA Astrophysics Data System (ADS)

Spanoudaki, Katerina; Kampanis, Nikolaos A.

2014-05-01

Coastal areas are the most densely-populated areas in the world. Consequently water demand is high, posing great pressure on fresh water resources. Climatic change and its direct impacts on meteorological variables (e.g. precipitation) and indirect impact on sea level rise, as well as anthropogenic pressures (e.g. groundwater abstraction), are strong drivers causing groundwater salinisation and subsequently affecting coastal wetlands salinity with adverse effects on the corresponding ecosystems. Coastal zones are a difficult hydrologic environment to represent with a mathematical model due to the large number of contributing hydrologic processes and variable-density flow conditions. Simulation of sea level rise and tidal effects on aquifer salinisation and accurate prediction of interactions between coastal waters, groundwater and neighbouring wetlands requires the use of integrated surface water-groundwater models. In the past few decades several computer codes have been developed to simulate coupled surface and groundwater flow. In these numerical models surface water flow is usually described by the 1-D Saint Venant equations (e.g. Swain and Wexler, 1996) or the 2D shallow water equations (e.g. Liang et al., 2007). Further simplified equations, such as the diffusion and kinematic wave approximations to the Saint Venant equations, are also employed for the description of 2D overland flow and 1D stream flow (e.g. Gunduz and Aral, 2005). However, for coastal bays, estuaries and wetlands it is often desirable to solve the 3D shallow water equations to simulate surface water flow. This is the case e.g. for wind-driven flows or density-stratified flows. Furthermore, most integrated models are based on the assumption of constant fluid density and therefore their applicability to coastal regions is questionable. Thus, most of the existing codes are not well-suited to represent surface water-groundwater interactions in coastal areas. To this end, the 3D integrated surface water-groundwater model IRENE (Spanoudaki et al., 2009; Spanoudaki, 2010) has been modified in order to simulate surface water-groundwater flow and salinity interactions in the coastal zone. IRENE, in its original form, couples the 3D, non-steady state Navier-Stokes equations, after Reynolds averaging and with the assumption of hydrostatic pressure distribution, to the equations describing 3D saturated groundwater flow of constant density. A semi-implicit finite difference scheme is used to solve the surface water flow equations, while a fully implicit finite difference scheme is used for the groundwater equations. Pollution interactions are simulated by coupling the advection-diffusion equation describing the fate and transport of contaminants introduced in a 3D turbulent flow field to the partial differential equation describing the fate and transport of contaminants in 3D transient groundwater flow systems. The model has been further developed to include the effects of density variations on surface water and groundwater flow, while the already built-in solute transport capabilities are used to simulate salinity interactions. Initial results show that IRENE can accurately predict surface water-groundwater flow and salinity interactions in coastal areas. Important research issues that can be investigated using IRENE include: (a) sea level rise and tidal effects on aquifer salinisation and the configuration of the saltwater wedge, (b) the effects of surface water-groundwater interaction on salinity increase of coastal wetlands and (c) the estimation of the location and magnitude of groundwater discharge to coasts. Acknowledgement The work presented in this paper has been funded by the Greek State Scholarships Foundation (IKY), Fellowships of Excellence for Postdoctoral Studies (Siemens Program), 'A simulation-optimization model for assessing the best practices for the protection of surface water and groundwater in the coastal zone', (2013 - 2015). References Gunduz, O. and Aral, M.M. (2005). River networks and groundwater flow: a simultaneous solution of a coupled system. Journal of Hydrology 301 (1-4), 216-234. Liang, D., Falconer, R.A. and Lin, B. (2007). Coupling surface and subsurface flows in a depth-averaged flood wave model. Journal of Hydrology 337, 147-158. Spanoudaki, K., Stamou, A.I. and Nanou-Giannarou, A. (2009). Development and verification of a 3-D integrated surface water-groundwater model. Journal of Hydrology, 375 (3-4), 410-427. Spanoudaki, K. (2010). Integrated numerical modelling of surface water groundwater systems (in Greek). Ph.D. Thesis, National Technical University of Athens, Greece. Swain, E.D. and Wexler, E.J. (1996). A coupled surface water and groundwater flow model (Modbranch) for simulation of stream-aquifer interaction. United States Geological Survey, Techniques of Water Resources Investigations (Book 6, Chapter A6).

Characterizing the interaction of groundwater and surface water in the karst aquifer of Fangshan, Beijing (China)

NASA Astrophysics Data System (ADS)

Chu, Haibo; Wei, Jiahua; Wang, Rong; Xin, Baodong

2017-03-01

Correct understanding of groundwater/surface-water (GW-SW) interaction in karst systems is of greatest importance for managing the water resources. A typical karst region, Fangshan in northern China, was selected as a case study. Groundwater levels and hydrochemistry analyses, together with isotope data based on hydrogeological field investigations, were used to assess the GW-SW interaction. Chemistry data reveal that water type and the concentration of cations in the groundwater are consistent with those of the surface water. Stable isotope ratios of all samples are close to the local meteoric water line, and the 3H concentrations of surface water and groundwater samples are close to that of rainfall, so isotopes also confirm that karst groundwater is recharged by rainfall. Cross-correlation analysis reveals that rainfall leads to a rise in groundwater level with a lag time of 2 months and groundwater exploitation leads to a fall within 1 month. Spectral analysis also reveals that groundwater level, groundwater exploitation and rainfall have significantly similar response periods, indicating their possible inter-relationship. Furthermore, a multiple nonlinear regression model indicates that groundwater level can be negatively correlated with groundwater exploitation, and positively correlated with rainfall. The overall results revealed that groundwater level has a close correlation with groundwater exploitation and rainfall, and they are indicative of a close hydraulic connection and interaction between surface water and groundwater in this karst system.

A modification of the finite-difference model for simulation of two dimensional ground-water flow to include surface-ground water relationships

USGS Publications Warehouse

Ozbilgin, M.M.; Dickerman, D.C.

1984-01-01

The two-dimensional finite-difference model for simulation of groundwater flow was modified to enable simulation of surface-water/groundwater interactions during periods of low streamflow. Changes were made to the program code in order to calculate surface-water heads for, and flow either to or from, contiguous surface-water bodies; and to allow for more convenient data input. Methods of data input and output were modified and entries (RSORT and HDRIVER) were added to the COEF and CHECKI subroutines to calculate surface-water heads. A new subroutine CALC was added to the program which initiates surface-water calculations. If CALC is not specified as a simulation option, the program runs the original version. The subroutines which solve the ground-water flow equations were not changed. Recharge, evapotranspiration, surface-water inflow, number of wells, pumping rate, and pumping duration can be varied for any time period. The Manning formula was used to relate stream depth and discharge in surface-water streams. Interactions between surface water and ground water are represented by the leakage term in the ground-water flow and surface-water mass balance equations. Documentation includes a flow chart, data deck instructions, input data, output summary, and program listing. Numerical results from the modified program are in good agreement with published analytical results. (USGS)

Utilizing Temperature and Resistivity Data as a Way to Characterize Water and Solute Movement and Groundwater-Surface Water Interaction in Variably Saturated Porous Media

NASA Astrophysics Data System (ADS)

Scotch, C.; Murgulet, D.; Hay, R.

2012-12-01

This study utilizes a multidisciplinary approach to better analyze the extent to which groundwater and surface water interact in the Oso Creek water shed of South Texas using temperature data, electrical resistivity and numerical modeling methods. The three primary objectives of this study are to: (1) identify primary areas of streambed groundwater-surface water interaction using temperature time series and resistivity soundings; (2) improve understanding of solute flow and groundwater, surface water, and sediment interaction in a semiarid, urban coastal area; (3) improve our understanding of groundwater contribution to contaminant transport and discharge to the bays and estuaries and ultimately the Gulf of Mexico. Temperature data was acquired over a one year period, using temperature loggers, from June 11, 2009 to May 18, 2010 at 15-minute intervals from 17 monitoring sites along Oso Creek and its tributaries. Each monitoring site consisted of 4 temperature loggers equally vertically spaced from the stream surface down to a depth of one meter. Furthermore, groundwater temperatures and water levels were collected from wells adjacent to the temperature monitoring sites. In order to fulfill the objectives of this study, existing hydrogeologic, stratigraphic, and other ancillary data are being integrated into a finite difference model developed using the USGS VS2DT software for the Oso Creek Watershed. The model will be calibrated using existing temperature and water level data and a resistivity component will also be added to assure accuracy of the model and temperature data by helping to identify varying lithologies and water conductivities. Compiling a time-series of temperature data and incorporating available hydrostratigraphic, geomorphologic and water level data will enable the development of a comprehensive database. This database is necessary to develop the detailed flow model that will enable an understanding of the extent of groundwater surface water interaction and their associated flow regimes.

The impacts of surface polarity on the solubility of nanoparticle

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Jianzhuo; Su, Jiguo, E-mail: jiguosu@ysu.edu.cn; Ou, Xinwen

In order to study the dependence of water solubility and hydration behavior of nanoparticles on their surface polarity, we designed polar nanoparticles with varying surface polarity by assigning atomic partial charge to the surface of C60. The water solubility of the nanoparticle is enhanced by several orders of magnitude after the introduction of surface polarity. Nevertheless, when the atomic partial charge grows beyond a certain value (q{sub M}), the solubility continuously decreases to the level of nonpolar nanoparticle. It should be noted that such q{sub M} is comparable with atomic partial charge of a variety of functional groups. The hydrationmore » behaviors of nanoparticles were then studied to investigate the non-monotonic dependence of solubility on the surface polarity. The interaction between the polar nanoparticle and the hydration water is stronger than the nonpolar counterpart, which should facilitate the dissolution of the nanoparticles. On the other hand, the surface polarity also reduces the interaction of hydration water with the other water molecules and enhances the interaction between the nanoparticles which may hinder their dispersion. Besides, the introduction of surface polarity disturbs and even rearranges the hydration structure of nonpolar nanoparticle. Interestingly, the polar nanoparticle with less ordered hydration structure tends to have higher water solubility.« less

An investigation of adhesive/adherend and fiber/matrix interactions. Part A: Surface characterization of titanium dioxide, titantium and titanium 6% Al to 4% V powders: Interaction with water, hydrogen chloride and polymers

NASA Technical Reports Server (NTRS)

Siriwardane, R. V.; Wightman, J. P.

1982-01-01

The titanium dioxide surface is discussed. Polymer adhesive are also discussed. Titanium powders are considered. Characterization techniques are also considered. Interactions with polymers, water vapor, and HCl are reported. Adsorbents are characterized.

Coastal groundwater/surface-water interactions: a Great Lakes case study

USGS Publications Warehouse

Neff, Brian P.; Haack, Sheridan K.; Rosenberry, Donald O.; Savino, Jacqueline F.; Lundstrom, Scott C.

2006-01-01

Key similarities exist between marine and Great Lakes coastal environments. Water and nutrient fluxes across lakebeds in the Great Lakes are influenced by seiche and wind set-up and set-down, analogous to tidal influence in marine settings. Groundwater/surface-water interactions also commonly involve a saline-fresh water interface, although in the Great-Lakes cases, it is groundwater that is commonly saline and surface water that is fresh. Evapotranspiration also affects nearshore hydrology in both settings. Interactions between groundwater and surface water have recently been identified as an important component of ecological processes in the Great Lakes. Water withdrawals and the reversal of the groundwater/surface water seepage gradient are also common to many coastal areas around the Great Lakes. As compared to surface water, regional groundwater that discharges to western Lake Erie from Michigan is highly mineralized. Studies conducted by the U.S. Geological Survey at Erie State Game Area in southeastern Michigan, describe groundwater flow dynamics and chemistry, shallow lake-water chemistry, and fish and invertebrate communities. Results presented here provide an overview of recent progress of ongoing interdisciplinary studies of Great Lakes nearshore systems and describe a conceptual model that identifies relations among geologic, hydrologic, chemical, and biological processes in the coastal habitats of Lake Erie. This conceptual model is based on analysis of hydraulic head in piezometers at the study site and chemical analysis of deep and shallow coastal groundwater.

Hydration water and bulk water in proteins have distinct properties in radial distributions calculated from 105 atomic resolution crystal structures.

PubMed

Chen, Xianfeng; Weber, Irene; Harrison, Robert W

2008-09-25

Water plays a critical role in the structure and function of proteins, although the experimental properties of water around protein structures are not well understood. The water can be classified by the separation from the protein surface into bulk water and hydration water. Hydration water interacts closely with the protein and contributes to protein folding, stability, and dynamics, as well as interacting with the bulk water. Water potential functions are often parametrized to fit bulk water properties because of the limited experimental data for hydration water. Therefore, the structural and energetic properties of the hydration water were assessed for 105 atomic resolution (

Intermolecular Casimir-Polder forces in water and near surfaces

NASA Astrophysics Data System (ADS)

Thiyam, Priyadarshini; Persson, Clas; Sernelius, Bo E.; Parsons, Drew F.; Malthe-Sørenssen, Anders; Boström, Mathias

2014-09-01

The Casimir-Polder force is an important long-range interaction involved in adsorption and desorption of molecules in fluids. We explore Casimir-Polder interactions between methane molecules in water, and between a molecule in water near SiO2 and hexane surfaces. Inclusion of the finite molecular size in the expression for the Casimir-Polder energy leads to estimates of the dispersion contribution to the binding energies between molecules and between one molecule and a planar surface.

Review: Groundwater management and groundwater/surface-water interaction in the context of South African water policy

NASA Astrophysics Data System (ADS)

Levy, Jonathan; Xu, Yongxin

2012-03-01

Groundwater/surface-water interaction is receiving increasing focus in Africa due to its importance to ecologic systems and sustainability. In South Africa's 1998 National Water Act (NWA), water-use licenses, including groundwater, are granted only after defining the Reserve, the amount of water needed to supply basic human needs and preserve some ecological integrity. Accurate quantification of groundwater contributions to ecosystems for successful implementation of the NWA proves challenging; many of South Africa's aquifers are in heterogeneous and anisotropic fractured-rock settings. This paper reviews the current conceptualizations and investigative approaches regarding groundwater/surface-water interactions in the context of South African policies. Some selected pitfall experiences are emphasized. The most common approach in South Africa is estimation of average annual fluxes at the scale of fourth-order catchments (˜500 km2) with baseflow separation techniques and then subtracting the groundwater discharge rate from the recharge rate. This approach might be a good start, but it ignores spatial and temporal variability, potentially missing local impacts associated with production-well placement. As South Africa's NWA has already been emulated in many countries including Zambia, Zimbabwe and Kenya, the successes and failures of the South African experience dealing with the groundwater/surface-water interaction will be analyzed to guide future policy directions.

PAHs behavior in surface water and groundwater of the Yellow River estuary: Evidence from isotopes and hydrochemistry.

PubMed

Li, Jing; Li, Fadong; Liu, Qiang

2017-07-01

Large-scale irrigation projects have impacted the regional surface-groundwater interactions in the North China Plain (NCP). Given this concern, the aim of this study is to evaluate levels of PAH pollution, identify the sources of the PAHs, analyze the influence of surface-groundwater interactions on PAH distribution, and propose urgent management strategies for PAHs in China's agricultural areas. PAH concentrations, hydrochemical indicators and stable isotopic compositions (δ 18 O and δ 2 H) were determined for surface water (SW) and groundwater (GW) samples. PAHs concentrations in surface water and groundwater varied from 11.84 to 393.12 ng/L and 8.51-402.84 ng/L, respectively, indicating mild pollution. The seasonal variations showed the following trend: PAHs in surface water at the low-water phase > PAHs in groundwater at the low-water phase > PAHs in surface water at the high-water phase > PAHs in groundwater at the high-water phase. Hydrochemical and δ 18 O value of most groundwater samples distributed between the Yellow River and seawater. The mean value of mixture ratio of the Yellow River water recharge to the groundwater was 65%, few anomalous sites can reach to 90%. Surface-groundwater interactions influence the spatial distribution of PAHs in the study area. In light of the ongoing serious pollution, management practices for source control, improved control technologies, and the construction of a monitoring network to warn of increased risk are urgently needed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fullerene C60: Surface Energy and Interfacial Interactions in Aqueous Systems

EPA Science Inventory

The underlying mechanisms of fullerene−fullerene, fullerene−water, and fullerene−soil surface interactions in aqueous systems are not well understood. To advance our understanding of these interfacial interactions, the surface properties of Buckminsterfullerene (C60) and quartz s...

Predicting Displaceable Water Sites Using Mixed-Solvent Molecular Dynamics.

PubMed

Graham, Sarah E; Smith, Richard D; Carlson, Heather A

2018-02-26

Water molecules are an important factor in protein-ligand binding. Upon binding of a ligand with a protein's surface, waters can either be displaced by the ligand or may be conserved and possibly bridge interactions between the protein and ligand. Depending on the specific interactions made by the ligand, displacing waters can yield a gain in binding affinity. The extent to which binding affinity may increase is difficult to predict, as the favorable displacement of a water molecule is dependent on the site-specific interactions made by the water and the potential ligand. Several methods have been developed to predict the location of water sites on a protein's surface, but the majority of methods are not able to take into account both protein dynamics and the interactions made by specific functional groups. Mixed-solvent molecular dynamics (MixMD) is a cosolvent simulation technique that explicitly accounts for the interaction of both water and small molecule probes with a protein's surface, allowing for their direct competition. This method has previously been shown to identify both active and allosteric sites on a protein's surface. Using a test set of eight systems, we have developed a method using MixMD to identify conserved and displaceable water sites. Conserved sites can be determined by an occupancy-based metric to identify sites which are consistently occupied by water even in the presence of probe molecules. Conversely, displaceable water sites can be found by considering the sites which preferentially bind probe molecules. Furthermore, the inclusion of six probe types allows the MixMD method to predict which functional groups are capable of displacing which water sites. The MixMD method consistently identifies sites which are likely to be nondisplaceable and predicts the favorable displacement of water sites that are known to be displaced upon ligand binding.

Molecular-level understanding of protein adsorption at the interface between water and a strongly interacting uncharged solid surface.

PubMed

Penna, Matthew J; Mijajlovic, Milan; Biggs, Mark J

2014-04-09

Although protein adsorption on solids is of immense relevance, experimental limitations mean there is still a remarkable lack of understanding of the adsorption mechanism, particularly at a molecular level. By subjecting 240+ molecular dynamics simulations of two peptide/water/solid surface systems to statistical analysis, a generalized molecular level mechanism for peptide adsorption has been identified for uncharged surfaces that interact strongly with the solution phase. This mechanism is composed of three phases: (1) biased diffusion of the peptide from the bulk phase toward the surface; (2) anchoring of the peptide to the water/solid interface via interaction of a hydrophilic group with the water adjacent to the surface or a strongly interacting hydrophobic group with the surface; and (3) lockdown of the peptide on the surface via a slow, stepwise and largely sequential adsorption of its residues, which we term 'statistical zippering'. The adsorption mechanism is dictated by the existence of water layers adjacent to the solid and orientational ordering therein. By extending the solid into the solution by ~8 Å and endowing it with a charged character, the water layers ensure the peptide feels the effect of the solid at a range well beyond the dispersion force that arises from it, thus inducing biased diffusion from afar. The charging of the interface also facilitates anchoring of the peptide near the surface via one of its hydrophilic groups, allowing it time it would otherwise not have to rearrange and lockdown. Finally, the slowness of the lockdown process is dictated by the need for the peptide groups to replace adjacent tightly bound interfacial water.

Approaches to characterizing biogeochemistry effects of groundwater and surface water interaction at the riparian interface

EPA Science Inventory

Groundwater-surface water interaction (GSI) in riparian ecosystems strongly influences biological activity that controls nutrient flux and processes. Shallow groundwater in riparian zones is a hot spot for nitrogen removal processes, a storage zone for solutes, and a target for ...

Behavior of severely supercooled water drops impacting on superhydrophobic surfaces

NASA Astrophysics Data System (ADS)

Maitra, Tanmoy; Antonini, Carlo; Tiwari, Manish K.; Mularczyk, Adrian; Imeri, Zulkufli; Schoch, Philippe; Poulikakos, Dimos

2014-11-01

Surface icing, commonplace in nature and technology, has broad implications to daily life. To prevent surface icing, superhydrophobic surfaces/coatings with rationally controlled roughness features (both at micro and nano-scale) are considered to be a promising candidate. However, to fabricate/synthesize a high performance icephobic surface or coating, understanding the dynamic interaction between water and the surface during water drop impact in supercooled state is necessary. In this work, we investigate the water/substrate interaction using drop impact experiments down to -17°C. It is found that the resulting increased viscous effect of water at low temperature significantly affects all stages of drop dynamics such as maximum spreading, contact time and meniscus penetration into the superhydrophobic texture. Most interestingly, the viscous effect on the meniscus penetration into roughness feature leads to clear change in the velocity threshold for rebounding to sticking transition by 25% of supercooled drops. Swiss National Science Foundation (SNF) Grant 200021_135479.

Water flow in carbon-based nanoporous membranes impacted by interactions between hydrated ions and aromatic rings.

PubMed

Liu, Jian; Shi, Guosheng; Fang, Haiping

2017-02-24

Carbon-based nanoporous membranes, such as carbon nanotubes (CNTs), graphene/graphene oxide and graphyne, have shown great potential in water desalination and purification, gas and ion separation, biosensors, and lithium-based batteries, etc. A deep understanding of the interaction between hydrated ions in an aqueous solution and the graphitic surface in systems composed of water, ions and a graphitic surface is essential for applications with carbon-based nanoporous membrane platforms. In this review, we describe the recent progress of the interaction between hydrated ions and aromatic ring structures on the carbon-based surface and its applications in the water flow in a carbon nanotube. We expect that these works can be extended to the understanding of water flow in other nanoporous membranes, such as nanoporous graphene, graphyne and stacked sheets of graphene oxide.

Phenomenological Model of Hydrophobic and Hydrophilic Interactions

NASA Astrophysics Data System (ADS)

Menshikov, L. I.; Menshikov, P. L.; Fedichev, P. O.

2017-12-01

Hydration forces acting between macroscopic bodies at distances L ≤ 3 nm in pure water are calculated based on the phenomenological model of polar liquids. It is shown that depending on the properties of the bodies, the interacting surfaces polarize the liquid differently, and wetting properties of the surfaces are completely characterized by two parameters. If the surfaces are hydrophilic, liquid molecules are polarized at right angles to the surfaces, and the interaction is the short-range repulsion (the forces of interaction decrease exponentially over the characteristic length λ ≈ 0.2 nm). The interaction between the hydrophobic surfaces is more diversified and has been studied less. For L ≤ 3 nm, the interaction exhibits universal properties, while for L ≤ 3 nm, it considerably depends on the properties of the surfaces and on the distances between them, as well as on the composition of the polar liquid. In full agreement with the available experimental results we find that if the interfaces are mostly hydrophobic, then the interaction is attractive and long-range (the interaction forces diminish exponentially with decay length 1.2 nm). In this case, the resultant polarization of water molecules is parallel to the surface. It is shown that hydration forces are determined by nonlinear effects of polarization of the liquid in the bulk or by analogous nonlinearity of the interaction of water with a submerged body. This means that the forces of interaction cannot be calculated correctly in the linear response approximation. The forces acting between hydrophobic or hydrophilic surfaces are of the entropy type or electrostatic, respectively. It is shown that hydrophobic and hydrophilic surfaces for L ≤ 3 nm repel each other. The calculated intensity of their interaction is in agreement with experimental data. We predict the existence of an intermediate regime in which a body cannot order liquid molecules, which results in a much weaker attraction that decreases in inverse proportion to the squared distance between the surfaces of bodies. The difference between the microscopic structures of liquids confined in nanovolumes from liquids in large volumes is considered. The proposed model is applicable for a quantitative description of the properties of water at temperatures T satisfying the condition 0 < ( T-T c )/ T c ≪ 1, where T c ≈ 230 K is the temperature of the ferroelectric phase transition observed in supercooled water. Under standard conditions, the model can be used for obtaining qualitative estimates.

Modeling the interaction Between Ethylene Diamine and Water Films on the Surface of a Carbon Nanotube

NASA Technical Reports Server (NTRS)

Jaffe, Richard L.; Walther, Jens H.; Zimmerli, Urs; Koumoutsakos, Petros

2004-01-01

It has been observed that a carbon nanotube (CNT) AFM tip coated with ethylene diamine (EDA) penetrates the liquid water-air interface more easily than an uncoated nanotube tip. The EDA coating remains intact through repeated cycles of dipping and removal. In order to understand the physical basis for this observation, we use ab initio quantum chemistry calculations to study the EDA-CNT-water interaction and to parameterize a force field describing this system. Molecular dynamics (MD) simulations are carried out for EDA-water mixtures and an EDA-coated carbon nanotube immmed in water. These simulations are similar to our earlier MD study that characterized the CNT-water interface. The attractive CNT-EDA and CNT-water interactions arise primarily from van der Waals forces, and the EDA-EDA, EDA-water and water-water interactions are mainly due to hydrogen bond formation. The binding energ of single EDA molecule to the nanotube is nearly three times larger than the corresponding value found for water (4.3 versus 1.5 kcal mol, respectively). The EDA molecules readily stick to and diffuse along the CNT surface. As a resulf mixing of the EDA and water films does not occur on the timescale of the MD simulations. The EDA film reduces the hydrophobicity of the nanotube surface and acts like a prototypical surfactant in stabilizing the suspension of carbon nanotubes in water. For this presentation, we use the MD simulations to determine how the presence of the carbon nanotube surface perturbs the properties of EDA-water mixtures.

Water vapor adsorption on goethite.

PubMed

Song, Xiaowei; Boily, Jean-François

2013-07-02

Goethite (α-FeOOH) is an important mineral contributing to processes of atmospheric and terrestrial importance. Their interactions with water vapor are particularly relevant in these contexts. In this work, molecular details of water vapor (0.0-19.0 Torr; 0-96% relative humidity at 25 °C) adsorption at surfaces of synthetic goethite nanoparticles reacted with and without HCl and NaCl were resolved using vibrational spectroscopy. This technique probed interactions between surface (hydr)oxo groups and liquid water-like films. Molecular dynamics showed that structures and orientations adopted by these waters are comparable to those adopted at the interface with liquid water. Particle surfaces reacted with HCl accumulated less water than acid-free surfaces due to disruptions in hydrogen bond networks by chemisorbed waters and chloride. Particles reacted with NaCl had lower loadings below ∼10 Torr water vapor but greater loadings above this value than salt-free surfaces. Water adsorption reactions were here affected by competitive hydration of coexisting salt-free surface regions, adsorbed chloride and sodium, as well as precipitated NaCl. Collectively, the findings presented in this study add further insight into the initial mechanisms of thin water film formation at goethite surfaces subjected to variations in water vapor pressure that are relevant to natural systems.

Miscibility of binary monolayers at the air-water interface and interaction of protein with immobilized monolayers by surface plasmon resonance technique.

PubMed

Wang, Yuchun; Du, Xuezhong

2006-07-04

The miscibility and stability of the binary monolayers of zwitterionic dipalmitoylphosphatidylcholine (DPPC) and cationic dioctadecyldimethylammonium bromide (DOMA) at the air-water interface and the interaction of ferritin with the immobilized monolayers have been studied in detail using surface pressure-area isotherms and surface plasmon resonance technique, respectively. The surface pressure-area isotherms indicated that the binary monolayers of DPPC and DOMA at the air-water interface were miscible and more stable than the monolayers of the two individual components. The surface plasmon resonance studies indicated that ferritin binding to the immobilized monolayers was primarily driven by the electrostatic interaction and that the amount of adsorbed protein at saturation was closely related not only to the number of positive charges in the monolayers but also to the pattern of positive charges at a given mole fraction of DOMA. The protein adsorption kinetics was determined by the properties of the monolayers (i.e., the protein-monolayer interaction) and the structure of preadsorbed protein molecules (i.e., the protein-protein interaction).

The glass-liquid transition of water on hydrophobic surfaces

NASA Astrophysics Data System (ADS)

Souda, Ryutaro

2008-09-01

Interactions of thin water films with surfaces of graphite and vitrified room-temperature ionic liquid [1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6])] were investigated using time-of-flight secondary ion mass spectrometry as a function of temperature and annealing time to elucidate the glass-liquid transition of water at the molecular level. Surface diffusion of water occurs at temperatures higher than 120K, thereby forming three-dimensional clusters (a two-dimensional layer) on the [bmim][PF6] (graphite) surface. The hydrophobic effect of the surface decreases with increasing coverage of water; the bulklike properties evolve up to 40 ML, as evidenced by the occurrence of film dewetting at around the conventional glass transition temperature (140K). Results also showed that aging is necessary for the water monolayer (a 40 ML water film) to dewet the graphite ([bmim][PF6]) surface. The occurrence of aging is explainable by the successive evolution of two distinct liquids during the glass-liquid transition: low density liquid is followed by supercooled liquid water. The water monolayer on graphite is characterized by the preferred orientation of unpaired OH groups toward the surface; this structure is arrested during the aging time despite the occurrence of surface diffusion. However, the water monolayer formed on the [bmim][PF6] surface agglomerates immediately after the commencement of surface diffusion. The structure of low density liquid tends to be arrested by the attractive interaction with the neighbors.

Groundwater surface water interactions and the role of phreatophytes in identifying recharge zones

USDA-ARS?s Scientific Manuscript database

Groundwater and surface water interactions within riparian corridors impact the distribution of phreatophytes that tap into groundwater stores. The changes in canopy area of phreatophytes over time is related to changes in depth to groundwater, distance from a stream or river, and hydrologic soil gr...

Increased porosity turns desorption to adsorption for gas bubbles near water-SiO2 interface

NASA Astrophysics Data System (ADS)

Boström, M.; Dou, M.; Thiyam, P.; Parsons, D. F.; Malyi, O. I.; Persson, C.

2015-02-01

We consider theoretically the retarded van der Waals interaction of a small gas bubble in water with a porous SiO2 surface. We predict a possible transition from repulsion to attraction as the surface is made more porous. It highlights that bubbles will interact differently with surface regions with different porosity (i.e., with different optical properties).

Analytical characterization of selective benthic flux components in estuarine and coastal waters

USGS Publications Warehouse

King, Jeffrey N.

2011-01-01

Benthic flux is the rate of flow across the bed of a water body, per unit area of bed. It is forced by component mechanisms, which interact. For example, pressure gradients across the bed, forced by tide, surface gravity waves, density gradients, bed–current interaction, turbulence, and terrestrial hydraulic gradients, drive an advective benthic flux of water and constituents between estuarine and coastal waters, and surficial aquifers. Other mechanisms also force benthic flux, such as chemical gradients, bioturbation, and dispersion. A suite of component mechanisms force a total benthic flux at any given location, where each member of the suite contributes a component benthic flux. Currently, the types and characteristics of component interactions are not fully understood. For example, components may interact linearly or nonlinearly, and the interaction may be constructive or destructive. Benthic flux is a surface water–groundwater interaction process. Its discharge component to a marine water body is referred to, in some literature, as submarine groundwater discharge. Benthic flux is important in characterizing water and constituent budgets of estuarine and coastal systems. Analytical models to characterize selective benthic flux components are reviewed. Specifically, these mechanisms are for the component associated with the groundwater tidal prism, and forced by surface gravity wave setup, surface gravity waves on a plane bed, and the terrestrial hydraulic gradient. Analytical models are applied to the Indian River Lagoon, Florida; Great South Bay, New York; and the South Atlantic Bight in South Carolina and portions of North Carolina.

Hydrogeology and ground-water/surface water interactions in the Des Moines River valley, southwestern Minnesota, 1997-2001

USGS Publications Warehouse

Cowdery, Timothy K.

2005-01-01

Long-term withdrawals of water for public supplies may cause a net decrease in ground-water discharge to surface water. Water that does not evaporate, or that is not exported, is discharged to the Des Moines River but with changed water quality. Because ground-water and surface-water qualities in the study area are similar, the ground-water discharge probably has little effect on river water quality.

Water adsorption on surface-modified cellulose nanocrystals

NASA Astrophysics Data System (ADS)

Wei, Zonghui; Sinko, Robert; Keten, Sinan; Luijten, Erik

Cellulose nanocrystals (CNCs) have attracted much attention as a filler phase for polymer nanocomposites due to their impressive mechanical properties, low cost, and environmental sustainability. Despite their promise for this application, there are still numerous obstacles that prevent optimal performance of CNC-polymer nanocomposites, such as poor filler dispersion and high levels of water absorption. One way to mitigate these negative effects is to modify CNC surfaces. Computational approaches can be utilized to obtain direct insight into the properties of modified CNC surfaces and probe the interactions of CNCs with other materials to facilitate the experimental design of nanocomposites. We use atomistic grand-canonical Monte Carlo simulations to study how surface modification of ion-exchanged sulfated cellulose nanocrystals (Na-CNCs) impacts water adsorption. We find that methyl(triphenyl)phosphonium-exchanged CNCs adsorb less water than Na-CNCs at the same relative humidity, supporting recent experimental dynamic vapor sorption measurements. By characterizing the distribution and configuration of water molecules near the modified CNC surfaces we determine how surface modifications disrupt CNC-water interactions.

Weakly bound water structure, bond valence saturation and water dynamics at the goethite (100) surface/aqueous interface: ab initio dynamical simulations.

PubMed

Chen, Ying; Bylaska, Eric J; Weare, John H

2017-03-31

Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite [α-Fe(OOH)]. Ab initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Several exchange correlation functionals were employed (PBE96, PBE96 + Grimme, and PBE0) in the simulations of a (3 × 2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a = 30 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick). The lowest energy goethite (100) surface termination model was determined to have an exposed surface Fe 3+ that was loosely capped by a water molecule and a shared hydroxide with a neighboring surface Fe 3+ . The water molecules capping surface Fe 3+ ions were found to be loosely bound at all DFT levels with and without Grimme corrections, indicative that each surface Fe 3+ was coordinated with only five neighbors. These long bonds were supported by bond valence theory calculations, which showed that the bond valence of the surface Fe 3+ was saturated and surface has a neutral charge. The polarization of the water layer adjacent to the surface was found to be small and affected only the nearest water. Analysis by density difference plots and localized Boys orbitals identified three types of water molecules: those loosely bound to the surface Fe 3+ , those hydrogen bonded to the surface hydroxyl, and bulk water with tetrahedral coordination. Boys orbital analysis showed that the spin down lone pair orbital of the weakly absorbed water interact more strongly with the spin up Fe 3+ ion. These weakly bound surface water molecules were found to rapidly exchange with the second water layer (~0.025 exchanges/ps) using a dissociative mechanism. Water molecules adjacent to the surface were found to only weakly interact with the surface and as a result were readily able to exchange with the bulk water. To account for the large surface Fe-OH 2 distances in the DFT calculations it was proposed that the surface Fe 3+ atoms, which already have their bond valence fully satisfied with only five neighbors, are under-coordinated with respect to the bulk coordination. Graphical abstract All first principle calculations, at all practically achievable levels, for the goethite 100 aqueous interface support a long bond and weak interaction between the exposed surface Fe 3+ and water molecules capping the surface. This result is supported by bond valence theory calculations and is indicative that each surface Fe 3+ is coordinated with only 5 neighbors.

Seasonal Influences on Ground-Surface Water Interactions in an Arsenic-Affected Aquifer in Cambodia

NASA Astrophysics Data System (ADS)

Richards, L. A.; Magnone, D.; Van Dongen, B.; Bryant, C.; Boyce, A.; Ballentine, C. J.; Polya, D. A.

2015-12-01

Millions of people in South and Southeast Asia consume drinking water daily which contains dangerous levels of arsenic exceeding health-based recommendations [1]. A key control on arsenic mobilization in aquifers in these areas has been controversially identified as the interaction of 'labile' organic matter contained in surface waters with groundwaters and sediments at depth [2-4], which may trigger the release of arsenic from the solid- to aqueous-phase via reductive dissolution of iron-(hyr)oxide minerals [5]. In a field site in Kandal Province, Cambodia, which is an arsenic-affected area typical to others in the region, there are strong seasonal patterns in groundwater flow direction, which are closely related to monsoonal rains [6] and may contribute to arsenic release in this aquifer. The aim of this study is to explore the implications of the high susceptibility of this aquifer system to seasonal changes on potential ground-surface water interactions. The main objectives are to (i) identify key zones where there are likely ground-surface water interactions, (ii) assess the seasonal impact of such interactions and (iii) quantify the influence of interactions using geochemical parameters (such as As, Fe, NO3, NH4, 14C, 3T/3He, δ18O, δ2H). Identifying the zones, magnitude and seasonal influence of ground-surface water interactions elucidates new information regarding potential locations/pathways of arsenic mobilization and/or transport in affected aquifers and may be important for water management strategies in affected areas. This research is supported by NERC (NE/J023833/1) to DP, BvD and CJB and a NERC PhD studentship (NE/L501591/1) to DM. References: [1] World Health Organization, 2008. [2] Charlet & Polya (2006), Elements, 2, 91-96. [3] Harvey et al. (2002), Science, 298, 1602-1606. [4] Lawson et al. (2013), Env. Sci. Technol. 47, 7085 - 7094. [5] Islam et al. (2004), Nature, 430, 68-71. [6] Benner et al. (2008) Appl. Geochem. 23(11), 3072 - 3087.

Effects of protein conformational motions in the native form and non-uniform distribution of electrostatic interaction sites on interfacial water

NASA Astrophysics Data System (ADS)

Pal, Somedatta; Bandyopadhyay, Sanjoy

2013-07-01

Protein-water interactions and their influence on surrounding water is a long-standing problem. Despite its importance, the origin of differential water behavior at the protein surface is still elusive. We have performed molecular simulations of the protein barstar in aqueous medium. Efforts have been made to explore how the conformational motions of the protein segments in the native form and the heterogeneous electrostatic interactions with the polar and charged groups of the protein affect the interfacial water properties. The calculations reveal that reduced dimension of the hydration layer on freezing the protein's degrees of freedom does not modify the heterogeneous water distributions around the protein. However, turning off the protein-water electrostatic contribution leads to non-preferential near-uniform water arrangements at the surface. It is further shown that with protein-water electrostatic interactions turned on, the local structuring of water molecules around the segments are correlated with their degree of exposure to the solvent.

Groundwater and surface-water interactions and impacts of human activities in the Hailiutu catchment, northwest China

NASA Astrophysics Data System (ADS)

Yang, Zhi; Zhou, Yangxiao; Wenninger, Jochen; Uhlenbrook, Stefan; Wang, Xusheng; Wan, Li

2017-08-01

The interactions between groundwater and surface water have been significantly affected by human activities in the semi-arid Hailiutu catchment, northwest China. Several methods were used to investigate the spatial and temporal interactions between groundwater and surface water. Isotopic and chemical analyses of water samples determined that groundwater discharges to the Hailiutu River, and mass balance equations were employed to estimate groundwater seepage rates along the river using chemical profiles. The hydrograph separation method was used to estimate temporal variations of groundwater discharges to the river. A numerical groundwater model was constructed to simulate groundwater discharges along the river and to analyze effects of water use in the catchment. The simulated seepage rates along the river compare reasonably well with the seepage estimates derived from a chemical profile in 2012. The impacts of human activities (river-water diversion and groundwater abstraction) on the river discharge were analyzed by calculating the differences between the simulated natural groundwater discharge and the measured river discharge. Water use associated with the Hailiutu River increased from 1986 to 1991, reached its highest level from 1992 to 2000, and decreased from 2001 onwards. The reduction of river discharge might have negative impacts on the riparian ecosystem and the water availability for downstream users. The interactions between groundwater and surface water as well as the consequences of human activities should be taken into account when implementing sustainable water resources management in the Hailiutu catchment.

Modelling wetland-groundwater interactions in the boreal Kälväsvaara esker, Northern Finland

NASA Astrophysics Data System (ADS)

Jaros, Anna; Rossi, Pekka; Ronkanen, Anna-Kaisa; Kløve, Bjørn

2016-04-01

Many types of boreal peatland ecosystems such as alkaline fens, aapa mires and Fennoscandia spring fens rely on the presence of groundwater. In these ecosystems groundwater creates unique conditions for flora and fauna by providing water, nutrients and constant water temperature enriching local biodiversity. The groundwater-peatland interactions and their dynamics are not, however, in many cases fully understood and their measurement and quantification is difficult due to highly heterogeneous structure of peatlands and large spatial extend of these ecosystems. Understanding of these interactions and their changes due to anthropogenic impact on groundwater resources would benefit the protection of the groundwater dependent peatlands. The groundwater-peatland interactions were investigated using the fully-integrated physically-based groundwater-surface water code HydroGeoSphere in a case study of the Kälväsvaara esker aquifer, Northern Finland. The Kälväsvaara is a geologically complex esker and it is surrounded by vast aapa mire system including alkaline and springs fens. In addition, numerous small springs occur in the discharge zone of the esker. In order to quantify groundwater-peatland interactions a simple steady-state model was built and results were evaluated using expected trends and field measurements. The employed model reproduced relatively well spatially distributed hydrological variables such as soil water content, water depths and groundwater-surface water exchange fluxes within the wetland and esker areas. The wetlands emerged in simulations as a result of geological and topographical conditions. They could be identified by high saturation levels at ground surface and by presence of shallow ponded water over some areas. The model outputs exhibited also strong surface water-groundwater interactions in some parts of the aapa system. These areas were noted to be regions of substantial diffusive groundwater discharge by the earlier studies. In contrast, the simulations were not able to capture small scale point groundwater discharge i.e. springs. This reflects that modelling small scale groundwater input to wetland ecosystems can be challenging without detailed information on the aquifer and wetland geology. Overall, the good consistency between simulations and observations demonstrated that wetland-groundwater interactions can be studied using fully-integrated physically-based groundwater-surface water models.

Interaction between ground water and surface water in Taylor Slough and vicinity, Everglades National Park, South Florida; study methods and appendixes

USGS Publications Warehouse

Harvey, Judson W.; Jackson, J.M.; Mooney, R.H.; Choi, Jungyill

2000-01-01

The data presented in this report are products of an investigation that quantified interactions between ground water and surface water in Taylor Slough in Everglades National Park. Determining the extent of hydrologic interactions between wetland surface water and ground water in Taylor Slough is important because the balance of freshwater flow in the lower part of the Slough is uncertain. Although freshwater flows through Taylor Slough are quite small in comparison to Shark Slough (the larger of the two major sloughs in Everglades National Park), flows through Taylor Slough are especially important to the ecology of estuarine mangrove embayments of northeastern Florida Bay. Also, wetland and ground- water interactions must be quantified if their role in affecting water quality is to be determined. In order to define basic hydrologic characteristics of the wetland, depth of wetland peat was mapped, and hydraulic conductivity and vertical hydraulic gradients in peat were determined. During specific time periods representing both wet and dry conditions in the area, the distribution of major ions, nutrients, and water stable isotopes throughout the slough were determined. The purpose of chemical measurements was to identify an environmental tracer could be used to quantify ground-water discharge.

The Character of the Solar Wind, Surface Interactions, and Water

NASA Technical Reports Server (NTRS)

Farrell, William M.

2011-01-01

We discuss the key characteristics of the proton-rich solar wind and describe how it may interact with the lunar surface. We suggest that solar wind can be both a source and loss of water/OH related volatiles, and review models showing both possibilities. Energy from the Sun in the form of radiation and solar wind plasma are in constant interaction with the lunar surface. As such, there is a solar-lunar energy connection, where solar energy and matter are continually bombarding the lunar surface, acting at the largest scale to erode the surface at 0.2 Angstroms per year via ion sputtering [1]. Figure 1 illustrates this dynamically Sun-Moon system.

A numerical study on the effects of wave-current-surge interactions on the height and propagation of sea surface waves in Charleston Harbor during Hurricane Hugo 1989

NASA Astrophysics Data System (ADS)

Liu, Huiqing; Xie, Lian

2009-06-01

The effects of wave-current interactions on ocean surface waves induced by Hurricane Hugo in and around the Charleston Harbor and its adjacent coastal waters are examined by using a three-dimensional (3D) wave-current coupled modeling system. The 3D storm surge modeling component of the coupled system is based on the Princeton Ocean Model (POM), the wave modeling component is based on the third generation wave model, Simulating WAves Nearshore (SWAN), and the inundation model is adopted from [Xie, L., Pietrafesa, L. J., Peng, M., 2004. Incorporation of a mass-conserving inundation scheme into a three-dimensional storm surge model. J. Coastal Res., 20, 1209-1223]. The results indicate that the change of water level associated with the storm surge is the primary cause for wave height changes due to wave-surge interaction. Meanwhile, waves propagating on top of surge cause a feedback effect on the surge height by modulating the surface wind stress and bottom stress. This effect is significant in shallow coastal waters, but relatively small in offshore deep waters. The influence of wave-current interaction on wave propagation is relatively insignificant, since waves generally propagate in the direction of the surface currents driven by winds. Wave-current interactions also affect the surface waves as a result of inundation and drying induced by the storm. Waves break as waters retreat in regions of drying, whereas waves are generated in flooded regions where no waves would have occurred without the flood water.

Solitary wave solutions and their interactions for fully nonlinear water waves with surface tension in the generalized Serre equations

NASA Astrophysics Data System (ADS)

Dutykh, Denys; Hoefer, Mark; Mitsotakis, Dimitrios

2018-04-01

Some effects of surface tension on fully nonlinear, long, surface water waves are studied by numerical means. The differences between various solitary waves and their interactions in subcritical and supercritical surface tension regimes are presented. Analytical expressions for new peaked traveling wave solutions are presented in the dispersionless case of critical surface tension. Numerical experiments are performed using a high-accurate finite element method based on smooth cubic splines and the four-stage, classical, explicit Runge-Kutta method of order 4.

IMPROVING THE QUALITY, AVAILABILITY AND SUSTAINABILITY OF DRINKING WATER SUPPLIES THROUGH ANTIFOULING AND ANTISCALING DESALINATION MEMBRANES

EPA Science Inventory

Surface modification with the selected polymers is expected to reduce the fouling and scaling propensity of desalination membranes by strongly binding water at the membrane surface. Foulants will interact with this bound water layer and not with the membrane surface itself....

Structure and energetics of hydrogen-bonded networks of methanol on close packed transition metal surfaces

NASA Astrophysics Data System (ADS)

Murphy, Colin J.; Carrasco, Javier; Lawton, Timothy J.; Liriano, Melissa L.; Baber, Ashleigh E.; Lewis, Emily A.; Michaelides, Angelos; Sykes, E. Charles H.

2014-07-01

Methanol is a versatile chemical feedstock, fuel source, and energy storage material. Many reactions involving methanol are catalyzed by transition metal surfaces, on which hydrogen-bonded methanol overlayers form. As with water, the structure of these overlayers is expected to depend on a delicate balance of hydrogen bonding and adsorbate-substrate bonding. In contrast to water, however, relatively little is known about the structures methanol overlayers form and how these vary from one substrate to another. To address this issue, herein we analyze the hydrogen bonded networks that methanol forms as a function of coverage on three catalytically important surfaces, Au(111), Cu(111), and Pt(111), using a combination of scanning tunneling microscopy and density functional theory. We investigate the effect of intermolecular interactions, surface coverage, and adsorption energies on molecular assembly and compare the results to more widely studied water networks on the same surfaces. Two main factors are shown to direct the structure of methanol on the surfaces studied: the surface coverage and the competition between the methanol-methanol and methanol-surface interactions. Additionally, we report a new chiral form of buckled hexamer formed by surface bound methanol that maximizes the interactions between methanol monomers by sacrificing interactions with the surface. These results serve as a direct comparison of interaction strength, assembly, and chirality of methanol networks on Au(111), Cu(111), and Pt(111) which are catalytically relevant for methanol oxidation, steam reforming, and direct methanol fuel cells.

First-principles molecular dynamics study of water dissociation on the γ-U(1 0 0) surface

NASA Astrophysics Data System (ADS)

Yang, Yu; Zhang, Ping

2015-05-01

Based on first-principles molecular dynamics simulations at finite temperatures, we systematically study the adsorption and dissociation of water molecules on the γ-U(1 0 0) surface. We predict that water molecules spontaneously dissociate upon approaching the native γ-U(1 0 0) surface. The dissociation results from electronic interactions between surface uranium 6d states and 1b2, 3a1, and 1b1 molecular orbitals of water. With segregated Nb atoms existing on the surface, adsorbing water molecules also dissociate spontaneously because Nb 3d electronic states can also interact with the molecular orbitals similarly. After dissociation, the isolated hydrogen atoms are found to diffuse fast on both the γ-U surface and that with a surface substitutional Nb atom, which is very similar to the ‘Hot-Atom’ dissociation of oxygen molecules on the Al(1 1 1) surface. From a series of consecutive molecular dynamics simulations, we further reveal that on both the γ-U surface and that with a surface substitutional Nb atom, one surface U atom will be pulled out to form the U-O-U structure after dissociative adsorption of 0.44 ML water molecules. This result indicates that oxide nucleus can form at low coverage of water adsorption on the two surfaces.

FIELD STUDY OF THE FATE OF ARSENIC, LEAD, AND ZINC AT THE GROUND-WATER/SURFACE-WATER INTERFACE

EPA Science Inventory

It is recognized that physical and chemical interactions between adjacent ground water and surface water bodies are an important factor impacting water budget and nutrient/contaminant transport within a watershed. This observation is also of importance for hazardous waste site c...

ARSENIC SORUCE IDENTIFICATION AT THE GROUND WATER-SURFACE WATER INTERACTION ZONE AT A CONTAMINATED SITE

EPA Science Inventory

One of the challenges in assessing the current impact of the discharge of arsenic contaminated ground water into a surface water body is differentiating the arsenic ground-water flux versus dissolution of in-place contaminated sediments. A field investigation has been carried ou...

Predictability and Quantification of Complex Groundwater Table Dynamics Driven by Irregular Surface Water Fluctuations

NASA Astrophysics Data System (ADS)

Xin, Pei; Wang, Shen S. J.; Shen, Chengji; Zhang, Zeyu; Lu, Chunhui; Li, Ling

2018-03-01

Shallow groundwater interacts strongly with surface water across a quarter of global land area, affecting significantly the terrestrial eco-hydrology and biogeochemistry. We examined groundwater behavior subjected to unimodal impulse and irregular surface water fluctuations, combining physical experiments, numerical simulations, and functional data analysis. Both the experiments and numerical simulations demonstrated a damped and delayed response of groundwater table to surface water fluctuations. To quantify this hysteretic shallow groundwater behavior, we developed a regression model with the Gamma distribution functions adopted to account for the dependence of groundwater behavior on antecedent surface water conditions. The regression model fits and predicts well the groundwater table oscillations resulting from propagation of irregular surface water fluctuations in both laboratory and large-scale aquifers. The coefficients of the Gamma distribution function vary spatially, reflecting the hysteresis effect associated with increased amplitude damping and delay as the fluctuation propagates. The regression model, in a relatively simple functional form, has demonstrated its capacity of reproducing high-order nonlinear effects that underpin the surface water and groundwater interactions. The finding has important implications for understanding and predicting shallow groundwater behavior and associated biogeochemical processes, and will contribute broadly to studies of groundwater-dependent ecology and biogeochemistry.

Influence of LaFeO 3 Surface Termination on Water Reactivity

DOE PAGES

Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R.; ...

2017-02-16

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular, with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry but are challenging to probe experimentally. Here, we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO 3 in humid conditions using ambient-pressure X-ray photoelectron spectroscopy. In comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO-terminated surface is more reactive toward water, forming hydroxyl species and adsorbing molecularmore » water at lower relative humidity than its FeO 2-terminated counterpart. But, the FeO 2-terminated surface forms more hydroxyl species during water adsorption at higher humidity, suggesting that adsorbate–adsorbate interactions may impact reactivity. These results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight that can aid in the design of catalyst materials.« less

Influence of LaFeO 3 Surface Termination on Water Reactivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R.

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular, with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry but are challenging to probe experimentally. Here, we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO 3 in humid conditions using ambient-pressure X-ray photoelectron spectroscopy. In comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO-terminated surface is more reactive toward water, forming hydroxyl species and adsorbing molecularmore » water at lower relative humidity than its FeO 2-terminated counterpart. But, the FeO 2-terminated surface forms more hydroxyl species during water adsorption at higher humidity, suggesting that adsorbate–adsorbate interactions may impact reactivity. These results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight that can aid in the design of catalyst materials.« less

Interaction between Air Bubbles and Superhydrophobic Surfaces in Aqueous Solutions.

PubMed

Shi, Chen; Cui, Xin; Zhang, Xurui; Tchoukov, Plamen; Liu, Qingxia; Encinas, Noemi; Paven, Maxime; Geyer, Florian; Vollmer, Doris; Xu, Zhenghe; Butt, Hans-Jürgen; Zeng, Hongbo

2015-07-07

Superhydrophobic surfaces are usually characterized by a high apparent contact angle of water drops in air. Here we analyze the inverse situation: Rather than focusing on water repellency in air, we measure the attractive interaction of air bubbles and superhydrophobic surfaces in water. Forces were measured between microbubbles with radii R of 40-90 μm attached to an atomic force microscope cantilever and submerged superhydrophobic surfaces. In addition, forces between macroscopic bubbles (R = 1.2 mm) at the end of capillaries and superhydrophobic surfaces were measured. As superhydrophobic surfaces we applied soot-templated surfaces, nanofilament surfaces, micropillar arrays with flat top faces, and decorated micropillars. Depending on the specific structure of the superhydrophobic surfaces and the presence and amount of entrapped air, different interactions were observed. Soot-templated surfaces in the Cassie state showed superaerophilic behavior: Once the electrostatic double-layer force and a hydrodynamic repulsion were overcome, bubbles jumped onto the surface and fully merged with the entrapped air. On nanofilaments and micropillar arrays we observed in addition the formation of sessile bubbles with finite contact angles below 90° or the attachment of bubbles, which retained their spherical shape.

Apparent Resistivity and Estimated Interaction Potential of Surface Water and Groundwater along Selected Canals and Streams in the Elkhorn-Loup Model Study Area, North-Central Nebraska, 2006-07

USGS Publications Warehouse

Teeple, Andrew; Vrabel, Joseph; Kress, Wade H.; Cannia, James C.

2009-01-01

In 2005, the State of Nebraska adopted new legislation that in part requires local Natural Resources Districts to include the effect of groundwater use on surface-water systems in their groundwater management plan. In response the U.S. Geological Survey, in cooperation with the Upper Elkhorn, Lower Elkhorn, Upper Loup, Lower Loup, Middle Niobrara, Lower Niobrara, Lewis and Clark, and Lower Platte North Natural Resources Districts, did a study during 2006-07 to investigate the surface-water and groundwater interaction within a 79,800-square-kilometer area in north-central Nebraska. To determine how streambed materials affect surface-water and groundwater interaction, surface geophysical and lithologic data were integrated at four sites to characterize the hydrogeologic conditions within the study area. Frequency-domain electromagnetic and waterborne direct- current resistivity profiles were collected to map the near-surface hydrogeologic conditions along sections of Ainsworth Canal near Ainsworth, Nebraska; Mirdan and Geranium Canals near Ord, Nebraska; North Loup River near Ord, Nebraska; and Middle Loup River near Thedford, Nebraska. Lithologic data were collected from test holes at each site to aid interpretation of the geophysical data. Geostatistical analysis incorporating the spatial variability of resistivity was used to account for the effect of lithologic heterogeneity on effective hydraulic permeability. The geostatistical analysis and lithologic data descriptions were used to make an interpretation of the hydrogeologic system and derive estimates of surface-water/groundwater interaction potential within the canals and streambeds. The estimated interaction potential at the Ainsworth Canal site and the Mirdan and Geranium Canal site is generally low to moderately low. The sediment textures at nearby test holes typically were silt and clay and fine-to-medium sand. The apparent resistivity values for these sites ranged from 2 to 120 ohm-meters. The vertical and horizontal variability of the apparent resistivity data were consistently low. Low resistive variability indicates little lithologic heterogeneity for either canal site. The surface-water/groundwater interaction-potential estimates are in agreement with the narrow frequency distribution of resistivity, low apparent resistivities, low spatial heterogeneity, and test-hole grain-size ranges. The estimated surface-water/groundwater interaction potential at the North Loup and Middle Loup River sites is moderate to moderately high. The sediment textures at nearby test holes were predominantly fine, medium, and coarse sand with some silt and silty to sandy clay. The apparent resistivity values for these sites ranged from 34 to 1,338 ohm-meters. The vertical variability of the resistivity data was moderately high. The horizontal variability at these sites is low to moderately low. The higher resistive variability at these sites indicates generally greater lithologic heterogeneity than at either the Ainsworth Canal site or the Mirdan and Geranium Canal site. The surface-water/groundwater interaction-potential estimates are in agreement with the generally moderate to high apparent resistivity, the greater spatial heterogeneity, and the variable lithologic texture. A higher interaction potential as compared to the canal sites is expected because of the higher subsurface resistivity and greater lithologic heterogeneity.

Experimental and numerical modelling of surface water-groundwater flow and pollution interactions under tidal forcing

NASA Astrophysics Data System (ADS)

Spanoudaki, Katerina; Bockelmann-Evans, Bettina; Schaefer, Florian; Kampanis, Nikolaos; Nanou-Giannarou, Aikaterini; Stamou, Anastasios; Falconer, Roger

2015-04-01

Surface water and groundwater are integral components of the hydrologic continuum and the interaction between them affects both their quantity and quality. However, surface water and groundwater are often considered as two separate systems and are analysed independently. This separation is partly due to the different time scales, which apply in surface water and groundwater flows and partly due to the difficulties in measuring and modelling their interactions (Winter et al., 1998). Coastal areas in particular are a difficult hydrologic environment to represent with a mathematical model due to the large number of contributing hydrologic processes. Accurate prediction of interactions between coastal waters, groundwater and neighbouring wetlands, for example, requires the use of integrated surface water-groundwater models. In the past few decades a large number of mathematical models and field methods have been developed in order to quantify the interaction between groundwater and hydraulically connected surface water bodies. Field studies may provide the best data (Hughes, 1995) but are usually expensive and involve too many parameters. In addition, the interpretation of field measurements and linking with modelling tools often proves to be difficult. In contrast, experimental studies are less expensive and provide controlled data. However, experimental studies of surface water-groundwater interaction are less frequently encountered in the literature than filed studies (e.g. Ebrahimi et al., 2007; Kuan et al., 2012; Sparks et al., 2013). To this end, an experimental model has been constructed at the Hyder Hydraulics Laboratory at Cardiff University to enable measurements to be made of groundwater transport through a sand embankment between a tidal water body such as an estuary and a non-tidal water body such as a wetland. The transport behaviour of a conservative tracer was studied for a constant water level on the wetland side of the embankment, while running a continuous tide on the coastal side. The integrated surface water-groundwater numerical model IRENE (Spanoudaki et al., 2009, Spanoudaki, 2010) was also used in the study, with the numerical model predictions being compared with experimental results, which provide a valuable database for model calibration and validation. IRENE couples the 3D, non-steady state Navier-Stokes equations, after Reynolds averaging and with the assumption of hydrostatic pressure distribution, to the equations describing 3D saturated groundwater flow of constant density. The model uses the finite volume method with a cell-centered structured grid providing thus flexibility and accuracy in simulating irregular boundary geometries. A semi-implicit finite difference scheme is used to solve the surface water flow equations, while a fully implicit finite difference scheme is used for the groundwater equations. Pollution interactions are simulated by coupling the advection-diffusion equation describing the fate and transport of contaminants introduced in a 3D turbulent flow field to the partial differential equation describing the fate and transport of contaminants in 3D transient groundwater flow systems. References Ebrahimi, K., Falconer, R.A. and Lin B. (2007). Flow and solute fluxes in integrated wetland and coastal systems. Environmental Modelling and Software, 22 (9), 1337-1348. Hughes, S.A. (1995). Physical Modelling and Laboratory Techniques in Coastal Engineering. World Scientific Publishing Co. Pte. Ltd., Singapore. Kuan, W.K., Jin, G., Xin, P., Robinson, C. Gibbes, B. and Li. L. (2012). Tidal influence on seawater intrusion in unconfined coastal aquifers. Water Resources Research, 48 (2), doi:10.1029/2011WR010678. Spanoudaki, K., Stamou, A.I. and Nanou-Giannarou, A. (2009). Development and verification of a 3-D integrated surface water-groundwater model. Journal of Hydrology, 375 (3-4), 410-427. Spanoudaki, K. (2010). Integrated numerical modelling of surface water groundwater systems (in Greek). Ph.D. Thesis, National Technical University of Athens, Greece. Sparks, T. D., Bockelmann-Evans, B. N. and Falconer, R. A. (2013). Laboratory Validation of an Integrated Surface Water- Groundwater Model. Journal of Water Resource and Protection, 5, 377-394. Winter, T.C., Harvey, J.W., Franke, O.L. and Alley, W.M., 1998. Groundwater and surface water - A single resource. USGS, Circular 1139.

A hybrid finite-difference and analytic element groundwater model

USGS Publications Warehouse

Haitjema, Henk M.; Feinstein, Daniel T.; Hunt, Randall J.; Gusyev, Maksym

2010-01-01

Regional finite-difference models tend to have large cell sizes, often on the order of 1–2 km on a side. Although the regional flow patterns in deeper formations may be adequately represented by such a model, the intricate surface water and groundwater interactions in the shallower layers are not. Several stream reaches and nearby wells may occur in a single cell, precluding any meaningful modeling of the surface water and groundwater interactions between the individual features. We propose to replace the upper MODFLOW layer or layers, in which the surface water and groundwater interactions occur, by an analytic element model (GFLOW) that does not employ a model grid; instead, it represents wells and surface waters directly by the use of point-sinks and line-sinks. For many practical cases it suffices to provide GFLOW with the vertical leakage rates calculated in the original coarse MODFLOW model in order to obtain a good representation of surface water and groundwater interactions. However, when the combined transmissivities in the deeper (MODFLOW) layers dominate, the accuracy of the GFLOW solution diminishes. For those cases, an iterative coupling procedure, whereby the leakages between the GFLOW and MODFLOW model are updated, appreciably improves the overall solution, albeit at considerable computational cost. The coupled GFLOW–MODFLOW model is applicable to relatively large areas, in many cases to the entire model domain, thus forming an attractive alternative to local grid refinement or inset models.

Molecular dynamics approach to probe PKCβII-ligand interactions and influence of crystal water molecules on these interactions.

PubMed

Grewal, Baljinder K; Bhat, Jyotsna; Sobhia, Masilamani Elizabeth

2015-01-01

PKCβII is a potential target for therapeutic intervention against pandemic diabetic complications. Present study probes the molecular interactions of PKCβII with its clinically important ligands, viz. ruboxistaurin, enzastaurin and co-crystallized ligand, 2-methyl-1H-indol-3-yl-BIM-1. The essentials of PKCβII-ligand interaction, crystal water-induced alterations in these interactions and key interacting flexible residues are analyzed. Computational methodologies, viz. molecular docking and molecular simulation coupled with molecular mechanics-Poisson-Boltzmann surface area and generalized born surface area (MM-PB[GB]SA) are employed. The structural changes in the presence and absence of crystal water molecules in PKCβII ATP binding site residues, and its interaction with bound ligand, are identified. Difference in interaction of selective and nonselective ligand with ATP binding site residues of PKCβII is reported. The study showed that the nonbonding interactions contribute significantly in PKCβII-ligand binding and presence of crystal water molecules affects the interactions. The findings of present work may integrate the new aspects in the drug design process of PKCβII inhibitors.

Energy Landscape of Water and Ethanol on Silica Surfaces

DOE PAGES

Wu, Di; Guo, Xiaofeng; Sun, Hui; ...

2015-06-26

Fundamental understanding of small molecule–silica surface interactions at their interfaces is essential for the scientific, technological, and medical communities. We report direct enthalpy of adsorption (Δh ads) measurements for ethanol and water vapor on porous silica glass (CPG-10), in both hydroxylated and dehydroxylated (hydrophobic) forms. Results suggest a spectrum of energetics as a function of coverage, stepwise for ethanol but continuous for water. The zero-coverage enthalpy of adsorption for hydroxylated silica shows the most exothermic enthalpies for both water (-72.7 ± 3.1 kJ/mol water) and ethanol (-78.0 ± 1.9 kJ/mol ethanol). The water adsorption enthalpy becomes less exothermic gradually untilmore » reaching its only plateau (-20.7 ± 2.2 kJ/mol water) reflecting water clustering on a largely hydrophobic surface, while the enthalpy of ethanol adsorption profile presents two well separated plateaus, corresponding to strong chemisorption of ethanol on adsorbate-free silica surface (-66.4 ± 4.8 kJ/mol ethanol), and weak physisorption of ethanol on ethanol covered silica (-4.0 ± 1.6 kJ/mol ethanol). On the other hand, dehydroxylation leads to missing water–silica interactions, whereas the number of ethanol binding sites is not impacted. The isotherms and partial molar properties of adsorption suggest that water may only bind strongly onto the silanols (which are a minor species on silica glass), whereas ethanol can interact strongly with both silanols and the hydrophobic areas of the silica surface.« less

Development of a classical force field for the oxidized Si surface: application to hydrophilic wafer bonding.

PubMed

Cole, Daniel J; Payne, Mike C; Csányi, Gábor; Spearing, S Mark; Colombi Ciacchi, Lucio

2007-11-28

We have developed a classical two- and three-body interaction potential to simulate the hydroxylated, natively oxidized Si surface in contact with water solutions, based on the combination and extension of the Stillinger-Weber potential and of a potential originally developed to simulate SiO(2) polymorphs. The potential parameters are chosen to reproduce the structure, charge distribution, tensile surface stress, and interactions with single water molecules of a natively oxidized Si surface model previously obtained by means of accurate density functional theory simulations. We have applied the potential to the case of hydrophilic silicon wafer bonding at room temperature, revealing maximum room temperature work of adhesion values for natively oxidized and amorphous silica surfaces of 97 and 90 mJm(2), respectively, at a water adsorption coverage of approximately 1 ML. The difference arises from the stronger interaction of the natively oxidized surface with liquid water, resulting in a higher heat of immersion (203 vs 166 mJm(2)), and may be explained in terms of the more pronounced water structuring close to the surface in alternating layers of larger and smaller densities with respect to the liquid bulk. The computed force-displacement bonding curves may be a useful input for cohesive zone models where both the topographic details of the surfaces and the dependence of the attractive force on the initial surface separation and wetting can be taken into account.

Hydrogeological controls of groundwater - land surface interactions

NASA Astrophysics Data System (ADS)

Bresciani, Etienne; Batelaan, Okke; Goderniaux, Pascal

2017-04-01

Interaction of groundwater with the land surface impacts a wide range of climatic, hydrologic, ecologic and geomorphologic processes. Many site-specific studies have successfully focused on measuring and modelling groundwater-surface water interaction, but upscaling or estimation at catchment or regional scale appears to be challenging. The factors controlling the interaction at regional scale are still poorly understood. In this contribution, a new 2-D (cross-sectional) analytical groundwater flow solution is used to derive a dimensionless criterion that expresses the conditions under which the groundwater outcrops at the land surface (Bresciani et al., 2016). The criterion gives insights into the functional relationships between geology, topography, climate and the locations of groundwater discharge along river systems. This sheds light on the debate about the topographic control of groundwater flow and groundwater-surface water interaction, as effectively the topography only influences the interaction when the groundwater table reaches the land surface. The criterion provides a practical tool to predict locations of groundwater discharge if a limited number of geomorphological and hydrogeological parameters (recharge, hydraulic conductivity and depth to impervious base) are known, and conversely it can provide regional estimates of the ratio of recharge over hydraulic conductivity if locations of groundwater discharge are known. A case study with known groundwater discharge locations located in South-West Brittany, France shows the feasibility of regional estimates of the ratio of recharge over hydraulic conductivity. Bresciani, E., Goderniaux, P. and Batelaan, O., 2016, Hydrogeological controls of water table-land surface interactions. Geophysical Research Letters 43(18): 9653-9661. http://dx.doi.org/10.1002/2016GL070618

Water: a responsive small molecule.

PubMed

Shultz, Mary Jane; Vu, Tuan Hoang; Meyer, Bryce; Bisson, Patrick

2012-01-17

Unique among small molecules, water forms a nearly tetrahedral yet flexible hydrogen-bond network. In addition to its flexibility, this network is dynamic: bonds are formed or broken on a picosecond time scale. These unique features make probing the local structure of water challenging. Despite the challenges, there is intense interest in developing a picture of the local water structure due to water's fundamental importance in many fields of chemistry. Understanding changes in the local network structure of water near solutes likely holds the key to unlock problems from analyzing parameters that determine the three dimensional structure of proteins to modeling the fate of volatile materials released into the atmosphere. Pictures of the local structure of water are heavily influenced by what is known about the structure of ice. In hexagonal I(h) ice, the most stable form of solid water under ordinary conditions, water has an equal number of donor and acceptor bonds; a kind of symmetry. This symmetric tetrahedral coordination is only approximately preserved in the liquid. The most obvious manifestation of this altered tetrahedral bonding is the greater density in the liquid compared with the solid. Formation of an interface or addition of solutes further modifies the local bonding in water. Because the O-H stretching frequency is sensitive to the environment, vibrational spectroscopy provides an excellent probe for the hydrogen-bond structure in water. In this Account, we examine both local interactions between water and small solutes and longer range interactions at the aqueous surface. Locally, the results suggest that water is not a symmetric donor or acceptor, but rather has a propensity to act as an acceptor. In interactions with hydrocarbons, action is centered at the water oxygen. For soluble inorganic salts, interaction is greater with the cation than the anion. The vibrational spectrum of the surface of salt solutions is altered compared with that of neat water. Studies of local salt-water interactions suggest that the picture of the local water structure and the ion distribution at the surface deduced from the surface vibrational spectrum should encompass both ions of the salt.

Molecular dynamics simulation study of the structure of poly(ethylene oxide) brushes on nonpolar surfaces in aqueous solution.

PubMed

Bedrov, Dmitry; Smith, Grant D

2006-07-04

The structure of poly(ethylene oxide) (PEO, M(w) = 526) brushes of various grafting density (sigma) on nonpolar graphite and hydrophobic (oily) surfaces in aqueous solution has been studied using atomistic molecular dynamics simulations. Additionally, the influence of PEO-surface interactions on the brush structure was investigated by systematically reducing the strength of the (dispersion) attraction between PEO and the surfaces. PEO chains were found to adsorb strongly to the graphite surface due primarily to the relative strength of dispersion interactions between PEO and the atomically dense graphite compared to those between water and graphite. For the oily surface, PEO-surface and water-surface dispersion interactions are much weaker, greatly reducing the energetic driving force for PEO adsorption. This reduction is mediated to some extent by a hydrophobic driving force for PEO adsorption on the oily surface. Reduction in the strength of PEO-surface attraction results in reduced adsorption of PEO for both surfaces, with the effect being much greater for the graphite surface where the strong PEO-surface dispersion interactions dominate. At high grafting density (sigma approximately 1/R(g)(2)), the PEO density profiles exhibited classical brush behavior and were largely independent of the strength of the PEO-surface interaction. With decreasing grafting density (sigma < 1/R(g)(2)), coverage of the surface by PEO requires an increasingly large fraction of PEO segments resulting in a strong dependence of the PEO density profile on the nature of the PEO-surface interaction.

Is it the shape of the cavity, or the shape of the water in the cavity?

NASA Astrophysics Data System (ADS)

Snyder, Phillip W.; Lockett, Matthew R.; Moustakas, Demetri T.; Whitesides, George M.

2014-04-01

Historical interpretations of the thermodynamics characterizing biomolecular recognition have marginalized the role of water. An important (even, perhaps, dominant) contribution to molecular recognition in water comes from the "hydrophobic effect," in which non-polar portions of a ligand interact preferentially with non-polar regions of a protein. Water surrounds the ligand, and water fills the binding pocket of the protein: when the protein-ligand complex forms, and hydrophobic surfaces of the binding pocket and the ligand approach one another, the molecules (and hydrogen-bonded networks of molecules) of water associated with both surfaces rearrange and, in part, entirely escape into the bulk solution. It is now clear that neither of the two most commonly cited rationalizations for the hydrophobic effect-an entropy-dominated hydrophobic effect, in which ordered waters at the surface of the ligand, and water at the surface of the protein, are released to the bulk upon binding, and a "lock-and-key" model, in which the surface of a ligand interacts directly with a surface of a protein having a complementary shape-can account for water-mediated interactions between the ligand and the protein, and neither is sufficient to account for the experimental observation of both entropy- andenthalpy-dominated hydrophobic effects. What is now clear is that there is no single hydrophobic effect, with a universally applicable, common, thermodynamic description: different processes (i.e., partitioning between phases of different hydrophobicity, aggregation in water, and binding) with different thermodynamics, depend on the molecular-level details of the structures of the molecules involved, and of the aggregates that form. A "water-centric" description of the hydrophobic effect in biomolecular recognition focuses on the structures of water surrounding the ligand, and of water filling the binding pocket of the protein, both before and after binding. This view attributes the hydrophobic effect to changes in the free energy of the networks of hydrogen bonds that are formed, broken, or re-arranged when two hydrophobic surfaces approach (but do not necessarily contact) one another. The details of the molecular topography (and the polar character) of the mole- cular surfaces play an important role in determining the structure of these networks of hydrogen-bonded waters, and in the thermodynamic description of the hydrophobic effect(s). Theorists have led the formulation of this "water-centric view", although experiments are now supplying support for it. It poses complex problems for would-be "designers" of protein-ligand interactions, and for so-called "rational drug design".

Deriving Scaling Factors Using a Global Hydrological Model to Restore GRACE Total Water Storage Changes for China's Yangtze River Basin

NASA Technical Reports Server (NTRS)

Long, Di; Yang, Yuting; Yoshihide, Wada; Hong, Yang; Liang, Wei; Chen, Yaning; Yong, Bin; Hou, Aizhong; Wei, Jiangfeng; Chen, Lu

2015-01-01

This study used a global hydrological model (GHM), PCR-GLOBWB, which simulates surface water storage changes, natural and human induced groundwater storage changes, and the interactions between surface water and subsurface water, to generate scaling factors by mimicking low-pass filtering of GRACE signals. Signal losses in GRACE data were subsequently restored by the scaling factors from PCR-GLOBWB. Results indicate greater spatial heterogeneity in scaling factor from PCR-GLOBWB and CLM4.0 than that from GLDAS-1 Noah due to comprehensive simulation of surface and subsurface water storage changes for PCR-GLOBWB and CLM4.0. Filtered GRACE total water storage (TWS) changes applied with PCR-GLOBWB scaling factors show closer agreement with water budget estimates of TWS changes than those with scaling factors from other land surface models (LSMs) in China's Yangtze River basin. Results of this study develop a further understanding of the behavior of scaling factors from different LSMs or GHMs over hydrologically complex basins, and could be valuable in providing more accurate TWS changes for hydrological applications (e.g., monitoring drought and groundwater storage depletion) over regions where human-induced interactions between surface water and subsurface water are intensive.

Free energy of adhesion of lipid bilayers on silica surfaces

NASA Astrophysics Data System (ADS)

Schneemilch, M.; Quirke, N.

2018-05-01

The free energy of adhesion per unit area (hereafter referred to as the adhesion strength) of lipid arrays on surfaces is a key parameter that determines the nature of the interaction between materials and biological systems. Here we report classical molecular simulations of water and 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid bilayers at model silica surfaces with a range of silanol densities and structures. We employ a novel technique that enables us to estimate the adhesion strength of supported lipid bilayers in the presence of water. We find that silanols on the silica surface form hydrogen bonds with water molecules and that the water immersion enthalpy for all surfaces varies linearly with the surface density of these hydrogen bonds. The adhesion strength of lipid bilayers is a linear function of the surface density of hydrogen bonds formed between silanols and the lipid molecules on crystalline surfaces. Approximately 20% of isolated silanols form such bonds but more than 99% of mutually interacting geminal silanols do not engage in hydrogen bonding with water. On amorphous silica, the bilayer displays much stronger adhesion than expected from the crystalline surface data. We discuss the implications of these results for nanoparticle toxicity.

Hydrology of Bishop Creek, California: An Isotopic Analysis

Treesearch

Michael L. Space; John W. Hess; Stanley D. Smith

1989-01-01

Five power generation plants along an eleven kilometer stretch divert Bishop Creek water for hydro-electric power. Stream diversion may be adversely affecting the riparian vegetation. Stable isotopic analysis is employed to determine surface water/ground-water interactions along the creek. surface water originates primarily from three headwater lakes. Discharge into...

Thermally decarboxylated sodium bicarbonate: Interactions with water vapour, calorimetric study

PubMed Central

Volkova, Natalia; Hansson, Henri; Ljunggren, Lennart

2012-01-01

Isothermal titration calorimetry (ITC) was used to study interactions between water vapour and the surface of thermally converted sodium bicarbonate (NaHCO3). The decarboxylation degree of the samples was varied from 3% to 35% and the humidity range was 54–100%. The obtained enthalpy values were all exothermic and showed a positive linear correlation with decarboxylation degrees for each humidity studied. The critical humidity, 75% (RHo), was determined as the inflection point on a plot of the mean−ΔH kJ/mole Na2CO3 against RH. Humidities above the critical humidity lead to complete surface dissolution. The water uptake (m) was determined after each calorimetric experiment, complementing the enthalpy data. A mechanism of water vapour interaction with decarboxylated samples, including the formation of trona and Wegscheider’s salt on the bicarbonate surface is proposed for humidities below RHo. PMID:29403816

Light-scattering studies of protein solutions: role of hydration in weak protein-protein interactions.

PubMed

Paliwal, A; Asthagiri, D; Abras, D; Lenhoff, A M; Paulaitis, M E

2005-09-01

We model the hydration contribution to short-range electrostatic/dispersion protein interactions embodied in the osmotic second virial coefficient, B(2), by adopting a quasi-chemical description in which water molecules associated with the protein are identified through explicit molecular dynamics simulations. These water molecules reduce the surface complementarity of highly favorable short-range interactions, and therefore can play an important role in mediating protein-protein interactions. Here we examine this quasi-chemical view of hydration by predicting the interaction part of B(2) and comparing our results with those derived from light-scattering measurements of B(2) for staphylococcal nuclease, lysozyme, and chymotrypsinogen at 25 degrees C as a function of solution pH and ionic strength. We find that short-range protein interactions are influenced by water molecules strongly associated with a relatively small fraction of the protein surface. However, the effect of these strongly associated water molecules on the surface complementarity of short-range protein interactions is significant, and must be taken into account for an accurate description of B(2). We also observe remarkably similar hydration behavior for these proteins despite substantial differences in their three-dimensional structures and spatial charge distributions, suggesting a general characterization of protein hydration.

Investigating How Contact Angle Effects the Interaction between Water and a Hydrophobic Surface

NASA Astrophysics Data System (ADS)

Poynor, Adele; Neidig, Caitlyn

2012-02-01

By definition hydrophobic substances hate water. What happens when water is forced into contact with a hydrophobic surface? One theory is that an ultra-thin low-density region forms near the surface. Contact angle is a measure of how hydrophobic a surface is. We have employed an automated home-built Surface Plasmon Resonance (SPR) apparatus to investigate the effect of varying the contact angle on the depletion layer

Radionuclides as natural tracers of the interaction between groundwater and surface water in the River Andarax, Spain.

PubMed

Navarro-Martinez, Francisco; Salas Garcia, Alejandro; Sánchez-Martos, Francisco; Baeza Espasa, Antonio; Molina Sánchez, Luis; Rodríguez Perulero, Antonio

2017-12-01

The identification of specific aquifers that supply water to river systems is fundamental to understanding the dynamics of the rivers' hydrochemistry, particularly in arid and semiarid environments where river flow may be discontinuous. There are multiple methods to identify the source of river water. In this study of the River Andarax, in the Southeast of Spain, an analysis of natural tracers (physico-chemical parameters, uranium, radium and radon) in surface water and groundwater indicates that chemical parameters and uranium clearly identify the areas where there is groundwater-surface water interaction. The concentration of uranium found in the river defines two areas: the headwaters with U concentrations of 2 μg L -1 and the lower reaches, with U of 6 μg L -1 . Furthermore, variation in the 234 U/ 238 U isotopic ratio allowed us to detect the influence that groundwater from the carbonate aquifer has on surface water in the headwaters of the river, where the saline content is lower and the water has a calcium bicarbonate facies. The concentration of 226 Ra and 222 Rn are low in the surface waters: <1.6 × 10 -6  μg L -1 and <5.1 × 10 -12  μg L -1 , respectively. There is a slight increase in the lower reaches where the water has a permanent flow, greater salinity and a calcium-magnesium-sulphate facies. All this is favoured by the influence of groundwater from the detritic aquifer on the surface waters. The results of this study indicate the utility in the use of physico-chemical and radiological data conjointly as tracers of groundwater-surface water interaction in semiarid areas where the lithology of aquifers is diverse (carbonate and detritic) and where evaporitic rocks are present. Copyright © 2017 Elsevier Ltd. All rights reserved.

Quantifying Spatially Integrated Floodplain and Wetland Systems for the Conterminous US

EPA Science Inventory

Wetlands interact with other waters across a variable connectivity continuum, from permanent to transient, from fast to slow, and from primarily surface water to exclusively groundwater flows. Floodplain wetlands typically experience fast and frequent surface and near-surface gro...

A simulation-optimization model for effective water resources management in the coastal zone

NASA Astrophysics Data System (ADS)

Spanoudaki, Katerina; Kampanis, Nikolaos

2015-04-01

Coastal areas are the most densely-populated areas in the world. Consequently water demand is high, posing great pressure on fresh water resources. Climatic change and its direct impacts on meteorological variables (e.g. precipitation) and indirect impact on sea level rise, as well as anthropogenic pressures (e.g. groundwater abstraction), are strong drivers causing groundwater salinisation and subsequently affecting coastal wetlands salinity with adverse effects on the corresponding ecosystems. Coastal zones are a difficult hydrologic environment to represent with a mathematical model due to the large number of contributing hydrologic processes and variable-density flow conditions. Simulation of sea level rise and tidal effects on aquifer salinisation and accurate prediction of interactions between coastal waters, groundwater and neighbouring wetlands requires the use of integrated surface water-groundwater mathematical models. In the past few decades several computer codes have been developed to simulate coupled surface and groundwater flow. However, most integrated surface water-groundwater models are based on the assumption of constant fluid density and therefore their applicability to coastal regions is questionable. Thus, most of the existing codes are not well-suited to represent surface water-groundwater interactions in coastal areas. To this end, the 3D integrated surface water-groundwater model IRENE (Spanoudaki et al., 2009; Spanoudaki, 2010) has been modified in order to simulate surface water-groundwater flow and salinity interactions in the coastal zone. IRENE, in its original form, couples the 3D shallow water equations to the equations describing 3D saturated groundwater flow of constant density. A semi-implicit finite difference scheme is used to solve the surface water flow equations, while a fully implicit finite difference scheme is used for the groundwater equations. Pollution interactions are simulated by coupling the advection-diffusion equation describing the fate and transport of contaminants introduced in a 3D turbulent flow field to the partial differential equation describing the fate and transport of contaminants in 3D transient groundwater flow systems. The model has been further developed to include the effects of density variations on surface water and groundwater flow, while the already built-in solute transport capabilities are used to simulate salinity interactions. The refined model is based on the finite volume method using a cell-centred structured grid, providing thus flexibility and accuracy in simulating irregular boundary geometries. For addressing water resources management problems, simulation models are usually externally coupled with optimisation-based management models. However this usually requires a very large number of iterations between the optimisation and simulation models in order to obtain the optimal management solution. As an alternative approach, for improved computational efficiency, an Artificial Neural Network (ANN) is trained as an approximate simulator of IRENE. The trained ANN is then linked to a Genetic Algorithm (GA) based optimisation model for managing salinisation problems in the coastal zone. The linked simulation-optimisation model is applied to a hypothetical study area for performance evaluation. Acknowledgement The work presented in this paper has been funded by the Greek State Scholarships Foundation (IKY), Fellowships of Excellence for Postdoctoral Studies (Siemens Program), 'A simulation-optimization model for assessing the best practices for the protection of surface water and groundwater in the coastal zone', (2013 - 2015). References Spanoudaki, K., Stamou, A.I. and Nanou-Giannarou, A. (2009). Development and verification of a 3-D integrated surface water-groundwater model. Journal of Hydrology, 375 (3-4), 410-427. Spanoudaki, K. (2010). Integrated numerical modelling of surface water groundwater systems (in Greek). Ph.D. Thesis, National Technical University of Athens, Greece.

Interlayer Water Regulates the Bio-nano Interface of a β-sheet Protein stacking on Graphene

PubMed Central

Lv, Wenping; Xu, Guiju; Zhang, Hongyan; Li, Xin; Liu, Shengju; Niu, Huan; Xu, Dongsheng; Wu, Ren'an

2015-01-01

Using molecular dynamics simulations, we investigated an integrated bio-nano interface consisting of a β-sheet protein stacked onto graphene. We found that the stacking assembly of the model protein on graphene could be controlled by water molecules. The interlayer water filled within interstices of the bio-nano interface could suppress the molecular vibration of surface groups on protein, and could impair the CH···π interaction driving the attraction of the protein and graphene. The intermolecular coupling of interlayer water would be relaxed by the relative motion of protein upon graphene due to the interaction between water and protein surface. This effect reduced the hindrance of the interlayer water against the assembly of protein on graphene, resulting an appropriate adsorption status of protein on graphene with a deep free energy trap. Thereby, the confinement and the relative sliding between protein and graphene, the coupling of protein and water, and the interaction between graphene and water all have involved in the modulation of behaviors of water molecules within the bio-nano interface, governing the hindrance of interlayer water against the protein assembly on hydrophobic graphene. These results provide a deep insight into the fundamental mechanism of protein adsorption onto graphene surface in water. PMID:25557857

Interlayer water regulates the bio-nano interface of a β-sheet protein stacking on graphene.

PubMed

Lv, Wenping; Xu, Guiju; Zhang, Hongyan; Li, Xin; Liu, Shengju; Niu, Huan; Xu, Dongsheng; Wu, Ren'an

2015-01-05

Using molecular dynamics simulations, we investigated an integrated bio-nano interface consisting of a β-sheet protein stacked onto graphene. We found that the stacking assembly of the model protein on graphene could be controlled by water molecules. The interlayer water filled within interstices of the bio-nano interface could suppress the molecular vibration of surface groups on protein, and could impair the CH···π interaction driving the attraction of the protein and graphene. The intermolecular coupling of interlayer water would be relaxed by the relative motion of protein upon graphene due to the interaction between water and protein surface. This effect reduced the hindrance of the interlayer water against the assembly of protein on graphene, resulting an appropriate adsorption status of protein on graphene with a deep free energy trap. Thereby, the confinement and the relative sliding between protein and graphene, the coupling of protein and water, and the interaction between graphene and water all have involved in the modulation of behaviors of water molecules within the bio-nano interface, governing the hindrance of interlayer water against the protein assembly on hydrophobic graphene. These results provide a deep insight into the fundamental mechanism of protein adsorption onto graphene surface in water.

Interlayer Water Regulates the Bio-nano Interface of a β-sheet Protein stacking on Graphene

NASA Astrophysics Data System (ADS)

Lv, Wenping; Xu, Guiju; Zhang, Hongyan; Li, Xin; Liu, Shengju; Niu, Huan; Xu, Dongsheng; Wu, Ren'an

2015-01-01

Using molecular dynamics simulations, we investigated an integrated bio-nano interface consisting of a β-sheet protein stacked onto graphene. We found that the stacking assembly of the model protein on graphene could be controlled by water molecules. The interlayer water filled within interstices of the bio-nano interface could suppress the molecular vibration of surface groups on protein, and could impair the CH...π interaction driving the attraction of the protein and graphene. The intermolecular coupling of interlayer water would be relaxed by the relative motion of protein upon graphene due to the interaction between water and protein surface. This effect reduced the hindrance of the interlayer water against the assembly of protein on graphene, resulting an appropriate adsorption status of protein on graphene with a deep free energy trap. Thereby, the confinement and the relative sliding between protein and graphene, the coupling of protein and water, and the interaction between graphene and water all have involved in the modulation of behaviors of water molecules within the bio-nano interface, governing the hindrance of interlayer water against the protein assembly on hydrophobic graphene. These results provide a deep insight into the fundamental mechanism of protein adsorption onto graphene surface in water.

Hydrologic indices for nontidal wetlands

USGS Publications Warehouse

Lent, Robert M.; Weiskel, Peter K.; Lyford, Forest P.; Armstrong, David S.

1997-01-01

Two sets of hydrologic indices were developed to characterize the water-budget components of nontidal wetlands. The first set consisted of six water-budget indices for input and output variables, and the second set consisted of two hydrologic interaction indices derived from the water-budget indices. The indices then were applied to 19 wetlands with previously published water-budget data. Two trilinear diagrams for each wetland were constructed, one for the three input indices and another for the three output indices. These two trilinear diagrams then were combined with a central quadrangle to form a Piper-type diagram, with data points from the trilinear diagrams projected onto the quadrangle. The quadrangle then was divided into nine fields that summarized the water-budget information. Two quantitative "interaction indices" were calculated from two of the six water-budget indices (precipitation and evapotranspiration). They also were obtained graphically from the water-budget indices, which were first projected to the central quadrangle of a Piper-type diagram from the flanking trilinear plots. The first interaction index (l) defines the strength of interaction between a wetland and the surrounding ground- and surface-water system. The second interaction index (S) defines the nature of the interaction between the wetland and the surrounding ground- and surface-water system (source versus sink). Evaluation of these indices using published wetland water-budget data illustrates the usefulness of the technique.

Incorporating human-water dynamics in a hyper-resolution land surface model

NASA Astrophysics Data System (ADS)

Vergopolan, N.; Chaney, N.; Wanders, N.; Sheffield, J.; Wood, E. F.

2017-12-01

The increasing demand for water, energy, and food is leading to unsustainable groundwater and surface water exploitation. As a result, the human interactions with the environment, through alteration of land and water resources dynamics, need to be reflected in hydrologic and land surface models (LSMs). Advancements in representing human-water dynamics still leave challenges related to the lack of water use data, water allocation algorithms, and modeling scales. This leads to an over-simplistic representation of human water use in large-scale models; this is in turn leads to an inability to capture extreme events signatures and to provide reliable information at stakeholder-level spatial scales. The emergence of hyper-resolution models allows one to address these challenges by simulating the hydrological processes and interactions with the human impacts at field scales. We integrated human-water dynamics into HydroBlocks - a hyper-resolution, field-scale resolving LSM. HydroBlocks explicitly solves the field-scale spatial heterogeneity of land surface processes through interacting hydrologic response units (HRUs); and its HRU-based model parallelization allows computationally efficient long-term simulations as well as ensemble predictions. The implemented human-water dynamics include groundwater and surface water abstraction to meet agricultural, domestic and industrial water demands. Furthermore, a supply-demand water allocation scheme based on relative costs helps to determine sectoral water use requirements and tradeoffs. A set of HydroBlocks simulations over the Midwest United States (daily, at 30-m spatial resolution for 30 years) are used to quantify the irrigation impacts on water availability. The model captures large reductions in total soil moisture and water table levels, as well as spatiotemporal changes in evapotranspiration and runoff peaks, with their intensity related to the adopted water management strategy. By incorporating human-water dynamics in a hyper-resolution LSM this work allows for progress on hydrological monitoring and predictions, as well as drought preparedness and water impact assessments at relevant decision-making scales.

Evaporation of tiny water aggregation on solid surfaces with different wetting properties.

PubMed

Wang, Shen; Tu, Yusong; Wan, Rongzheng; Fang, Haiping

2012-11-29

The evaporation of a tiny amount of water on the solid surface with different wettabilities has been studied by molecular dynamics simulations. From nonequilibrium MD simulations, we found that, as the surface changed from hydrophobic to hydrophilic, the evaporation speed did not show a monotonic decrease as intuitively expected, but increased first, and then decreased after it reached a maximum value. The analysis of the simulation trajectory and calculation of the surface water interaction illustrate that the competition between the number of water molecules on the water-gas surface from where the water molecules can evaporate and the potential barrier to prevent those water molecules from evaporating results in the unexpected behavior of the evaporation. This finding is helpful in understanding the evaporation on biological surfaces, designing artificial surfaces of ultrafast water evaporating, or preserving water in soil.

Wettability, Polarity, and Water Absorption of Holm Oak Leaves: Effect of Leaf Side and Age1[OPEN

PubMed Central

Fernández, Victoria; Sancho-Knapik, Domingo; Guzmán, Paula; Peguero-Pina, José Javier; Gil, Luis; Karabourniotis, George; Khayet, Mohamed; Fasseas, Costas; Heredia-Guerrero, José Alejandro; Heredia, Antonio; Gil-Pelegrín, Eustaquio

2014-01-01

Plant trichomes play important protective functions and may have a major influence on leaf surface wettability. With the aim of gaining insight into trichome structure, composition, and function in relation to water-plant surface interactions, we analyzed the adaxial and abaxial leaf surface of holm oak (Quercus ilex) as a model. By measuring the leaf water potential 24 h after the deposition of water drops onto abaxial and adaxial surfaces, evidence for water penetration through the upper leaf side was gained in young and mature leaves. The structure and chemical composition of the abaxial (always present) and adaxial (occurring only in young leaves) trichomes were analyzed by various microscopic and analytical procedures. The adaxial surfaces were wettable and had a high degree of water drop adhesion in contrast to the highly unwettable and water-repellent abaxial holm oak leaf sides. The surface free energy and solubility parameter decreased with leaf age, with higher values determined for the adaxial sides. All holm oak leaf trichomes were covered with a cuticle. The abaxial trichomes were composed of 8% soluble waxes, 49% cutin, and 43% polysaccharides. For the adaxial side, it is concluded that trichomes and the scars after trichome shedding contribute to water uptake, while the abaxial leaf side is highly hydrophobic due to its high degree of pubescence and different trichome structure, composition, and density. Results are interpreted in terms of water-plant surface interactions, plant surface physical chemistry, and plant ecophysiology. PMID:24913938

Spatial and Temporal Scales of Surface Water-Groundwater Interactions

NASA Astrophysics Data System (ADS)

Boano, F.

2016-12-01

The interfaces between surface water and groundwater (i.e., river and lake sediments) represent hotspots for nutrient transformation in watersheds. This intense biochemical activity stems from the peculiar physicochemical properties of these interface areas. Here, the exchange of water and nutrients between surface and subsurface environments creates an ecotone region that can support the presence of different microbial species responsible for nutrient transformation. Previous studies have elucidated that water exchange between rivers and aquifers is organized in a complex system of nested flow cells. Each cell entails a range of residence timescales spanning multiple order of magnitudes, providing opportunities for different biochemical reactions to occur. Physically-bases models represent useful tools to deal with the wide range of spatial and temporal scales that characterize surface-subsurface water exchange. This contribution will present insights about how hydrodynamic processes control scale organization for surface water - groundwater interactions. The specific focus will be the influence of exchange processes on microbial activity and nutrient transformation, discussing how groundwater flow at watershed scale controls flow conditions and hence constrain microbial reactions at much smaller scales.

Drug-polymer interactions at water-crystal interfaces and implications for crystallization inhibition: molecular dynamics simulations of amphiphilic block copolymer interactions with tolazamide crystals.

PubMed

Gao, Yi; Olsen, Kenneth W

2015-07-01

A diblock copolymer, poly(ethylene glycol)-block-poly(lactic acid) (PEG-b-PLA), modulates the crystal growth of tolazamide (TLZ), resulting in a crystal morphology change from needles to plates in aqueous media. To understand this crystal surface drug-polymer interaction, we conducted molecular dynamics simulations on crystal surfaces of TLZ in water containing PEG-b-PLA. A 130-ns simulation of the polymer in a large water box was run before initiating 50 ns simulations with each of the crystal surfaces. The simulations demonstrated differentiated drug-polymer interactions that are consistent with experimental studies. Interaction of PEG-b-PLA with the (001) face occurred more rapidly (≤10 ns) and strongly (total interaction energy of -121.1 kJ/mol/monomer) than that with the (010) face (∼35 ns, -85.4 kJ/mol/monomer). There was little interaction with the (100) face. Hydrophobic and van der Waals (VDW) interactions were the dominant forces, accounting for more than 90% of total interaction energies. It suggests that polymers capable of forming strong hydrophobic and VDW interactions might be more effective in inhibiting crystallization of poorly water-soluble and hydrophobic drugs in aqueous media (such as gastrointestinal fluid) than those with hydrogen-bonding capacities. Such in-depth analysis and understanding facilitate the rational selection of polymers in designing supersaturation-based enabling formulations. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Structural and dynamical characterization of water on the Au (100) and graphene surfaces: A molecular dynamics simulation approach

NASA Astrophysics Data System (ADS)

Foroutan, Masumeh; Darvishi, Mehdi; Fatemi, S. Mahmood

2017-09-01

The positioning, adsorption, and movement of water on substrates is dependent upon the chemical nature and arrangement of the atoms of the surface. Therefore the behavior of water molecules on a substrate is a reflection of properties of the surface. Based on this premise, graphene and gold substrates were chosen to study this subject from a molecular perspective. In this work, the structural and dynamical behaviors of a water nanodroplet on Au (100) and the graphene interfaces have been studied by molecular dynamics simulation. The results have shown how the structural and dynamical behaviors of water molecules at the interface reflect the characteristics of these surfaces. The results have demonstrated that residence time and hydrogen bonds' lifetime at the water-Au (100) interface are bigger than at the water-graphene interface. Energy contour map analysis indicates a more uniform surface energy on graphene than on the gold surface. The obtained results illustrate that water clusters on gold and graphene form tetramer and hexamer structures, respectively. Furthermore, the water molecules are more ordered on the gold surface than on graphene. The study of hydrogen bonds showed that the order, stability, and the number of hydrogen bonds is higher on the gold surface. The positioning pattern of water molecules is also similar to the arrangement of gold atoms while no regularity was observed on graphene. The study of dynamical behavior of water molecules revealed that the movement of water on gold is much less than on graphene which is in agreement with the strong water-gold interaction in comparison to the water-graphene interaction.

Molecular interactions in a surfactant-water-polyacrylamide system, according to densimetry, viscometry, conductometry, and spectroscopy data

NASA Astrophysics Data System (ADS)

Harutyunyan, R. S.

2013-08-01

Molecular interactions in a surfactant-polyacrylamide-water system are investigated. It is established that the interactions affect such physicochemical parameters of the system as viscosity, density, surface tension, conductivity, and critical micelle concentration. It is shown that in a polyacrylamide-water system, raising the polyacrylamide concentration to 0.02% causes conformational changes in its macromolecule.

The impact of changing climate on surface and ground water quality in southeast of Ireland

NASA Astrophysics Data System (ADS)

Tribak, Kamal

2015-04-01

In the current changing climate globally, Ireland have been experiencing a yearly recurrent extreme heavy rainfall events in the last decade, with damaging visible effects socially, economically and on the environment. Ireland intensive agriculture production is a major treat to the aquatic environment, Nitrogen and phosphorus losses to the water courses are major causes to eutrophication. The European Water Frame Directive (WFD 2000/60/EC) and Nitrates Directive (91/676/EEC) sets a number of measures to better protect and improve water status. Five years of high temporal resolution river water quality data measurement from two contrasting catchment in the southeast of Ireland were correlated with rain fall and nutrients losses to the ground and surface water, additional to the integrated Southeast River District Basin ground and surface water quality to establish spatiotemporal connection to the agriculture activities, the first well-drained soil catchment had high coefficient correlation with rain fall with higher losses to groundwater, on the other hand higher nutrients losses to surface water were higher with less influence from groundwater recharge of N and P transfer, the poorly clay base soil contributed to higher increased losses to surface water during excessive rain fall. Agriculture activities, hydrology, geology and human interaction can interact according to their site specific setting and the effects will fluctuate dependent on the conditions influencing the impact on water quality, there is a requirement to better distinguish those effects together and identify areas and land uses control and nutrients management to improve the water quality, stakeholders co-operation along with effective polices, long term monitoring, nutrients pathways management and better understanding of the environmental factors interaction on national, regional and catchment scale to enable planning policies and enforcement measures to be more focused on areas of high risk than others.

Animated molecular dynamics simulations of hydrated caesium-smectite interlayers

PubMed Central

Sutton, Rebecca; Sposito, Garrison

2002-01-01

Computer animation of center of mass coordinates obtained from 800 ps molecular dynamics simulations of Cs-smectite hydrates (1/3 and 2/3 water monolayers) provided information concerning the structure and dynamics of the interlayer region that could not be obtained through traditional simulation analysis methods. Cs+ formed inner sphere complexes with the mineral surface, and could be seen to jump from one attracting location near a layer charge site to the next, while water molecules were observed to migrate from the hydration shell of one ion to that of another. Neighboring ions maintained a partial hydration shell by sharing water molecules, such that a single water molecule hydrated two ions simultaneously for hundreds of picoseconds. Cs-montmorillonite hydrates featured the largest extent of this sharing interaction, because interlayer ions were able to inhabit positions near surface cavities as well as at their edges, close to oxygen triads. The greater positional freedom of Cs+ within the montmorillonite interlayer, a result of structural hydroxyl orientation and low tetrahedral charge, promoted the optimization of distances between cations and water molecules required for water sharing. Preference of Cs+ for locations near oxygen triads was observed within interlayer beidellite and hectorite. Water molecules also could be seen to interact directly with the mineral surface, entering its surface cavities to approach attracting charge sites and structural hydroxyls. With increasing water content, water molecules exhibited increased frequency and duration of both cavity habitation and water sharing interactions. Competition between Cs+ and water molecules for surface sites was evident. These important cooperative and competitive features of interlayer molecular behavior were uniquely revealed by animation of an otherwise highly complex simulation output.

Linking hyporheic flow and nitrogen cycling near the Willamette River - A large river in Oregon, USA

USGS Publications Warehouse

Hinkle, S.R.; Duff, J.H.; Triska, F.J.; Laenen, A.; Gates, E.B.; Bencala, K.E.; Wentz, D.A.; Silva, S.R.

2001-01-01

Several approaches were used to characterize ground water/surface water interactions near the Willamette River - A large (ninth order) river in Oregon, USA. A series of potentiometric surface maps demonstrated the presence of highly dynamic hydraulic gradients between rivers and the adjacent aquifer. Hyporheic zone gradients extended on the order of hundreds of meters. River gains and losses at the river stretch scale (tens of kilometers) were consistent with fluxes implied by the potentiometric surface maps, and apparently reflect regional ground water/surface water interactions. Gains and losses of up to 5-10% of streamflow were observed at this scale. On the river reach scale (1-2 km), gains and losses on the order of 5% of streamflow were interpreted as representing primarily local hyporheic exchange. Isotopic and chemical data collected from shallow hyporheic zone wells demonstrated interaction between regional ground water and river water. The origin of sampled hyporheic zone water ranged from a mixture dominated by regional ground water to water containing 100% river water. The common assumption that ground and river water mix primarily in the river channel is not applicable in this system. Isotopic and chemical data also indicated that significant (nearly complete) vegetative nitrate uptake and/or nitrate reduction occurred in water from 4 of 12 hyporheic zone sites. In these cases, it was primarily nitrate transported to the hyporheic zone in regional ground water that was removed from solution. Isotopes of water and nitrate indicated that hyporheic zone water sampled at two sites was composed of water originating as river water and demonstrated that significant vegetative nitrate uptake and nitrate reduction occurred along these hyporheic zone flowpaths. Thus, the hyporheic zone may, in some instances, serve to remove nitrate from river water. Additional investigations with chemical tools and microbial enzyme assays were conducted at one hyporheic site. A strong vertical redox gradient was observed, with nitrate-limited denitrification potential in deeper sediment and both nitrification and denitrification potential in shallower sediment. Since nitrogen cycling is strongly affected by redox conditions, nitrogen cycling in the hyporheic zone of this large-river system likely is affected by dynamics of ground water/surface water interactions that control fluxes of nitrogen and other redox species to hyporheic zone sediment.

Simulations of ecosystem hydrological processes using a unified multi-scale model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Xiaofan; Liu, Chongxuan; Fang, Yilin

2015-01-01

This paper presents a unified multi-scale model (UMSM) that we developed to simulate hydrological processes in an ecosystem containing both surface water and groundwater. The UMSM approach modifies the Navier–Stokes equation by adding a Darcy force term to formulate a single set of equations to describe fluid momentum and uses a generalized equation to describe fluid mass balance. The advantage of the approach is that the single set of the equations can describe hydrological processes in both surface water and groundwater where different models are traditionally required to simulate fluid flow. This feature of the UMSM significantly facilitates modelling ofmore » hydrological processes in ecosystems, especially at locations where soil/sediment may be frequently inundated and drained in response to precipitation, regional hydrological and climate changes. In this paper, the UMSM was benchmarked using WASH123D, a model commonly used for simulating coupled surface water and groundwater flow. Disney Wilderness Preserve (DWP) site at the Kissimmee, Florida, where active field monitoring and measurements are ongoing to understand hydrological and biogeochemical processes, was then used as an example to illustrate the UMSM modelling approach. The simulations results demonstrated that the DWP site is subject to the frequent changes in soil saturation, the geometry and volume of surface water bodies, and groundwater and surface water exchange. All the hydrological phenomena in surface water and groundwater components including inundation and draining, river bank flow, groundwater table change, soil saturation, hydrological interactions between groundwater and surface water, and the migration of surface water and groundwater interfaces can be simultaneously simulated using the UMSM. Overall, the UMSM offers a cross-scale approach that is particularly suitable to simulate coupled surface and ground water flow in ecosystems with strong surface water and groundwater interactions.« less

Interaction between ground water and surface water in the northern Everglades and relation to water budget and mercury cycling; study methods and appendixes

USGS Publications Warehouse

Harvey, Judson W.; Krupa, S.L.; Gefvert, C.J.; Choi, Jungyill; Mooney, R.H.; Giddings, J.B.

2000-01-01

The data presented in this report are products of an investigation that quantified interactions between ground water and surface water at several study sites in the northern Everglades. Goals included identifying the major geologic controls and human alterations that affect interactions between ground water and surface water, and determining how those interactions affect mercury contamination. The primary study area was the 3,815-acre Everglades Nutrient Removal (ENR), a wetland constructed in the early 1990s as a prototype Stormwater Treatment Area (STA), to determine the effectiveness in removing excess nutrients from agricultural drainage. In order to ensure that results from ENR are broadly informative, work was also conducted in Water Conservation Area-2A (WCA-2A), a 105,000-acre basin surrounded by levees. In the past 50 years, WCA-2A has experienced extensive re- engineering of water flow, alterations in the pattern of water-level fluctuations and timing of fire frequency, as well as substantial ecological changes. The most visible ecological alteration is the change in dominance over the past 30 years from a sawgrass wetland to cattail wetland in the northeastern part of WCA-2A. The drastic change in vegetation in WCA-2A resulted at least in part from inputs of excess phosphorus from agricultural drainage. Substantial data collection programs were already in progress in both ENR and WCA- 2A when the present work began. The South Florida Water Management District (SFWMD) constructed the ENR project in 1994 to determine the effectiveness of constructed wetlands for water treatment. Measurements of surface water flow and water quality were made frequently in ENR between 1994 and 1998. Fewer ground water data were collected at ENR, and almost all of it was collected from shallow wells emplaced on perimeter levees. In contrast to the short-term nature of data collection in ENR, hydrologic and chemical data were collected over a much longer period in WCA-2A (since at least the mid- 1970s), but the number of sites and data- collection frequency is much less. Very little prior ground water data were available in WCA-2A. Given the availability of prior information, the present study emphasized the collection of ground water field data, particularly in the interior wetland areas of ENR and WCA- 2A. New wells were emplaced to permit the geologic, hydraulic, and chemical sampling that was needed to characterize interactions between surface water and ground water. In particular, lithology and hydraulic properties of the Surficial aquifer were determined, ground water flow paths and velocities were delineated, hydrologic fluxes between surface water and ground water were measured, and water budgets and surface- subsurface fluxes of mercury were determined. The purpose of this report is to compile under one cover all of the data collected in this investigation. In addition, the report contains a detailed description of the study methods and information about study sites, borehole drilling, well construction, seepage meter installation, and hydraulic and geochemical chemical sampling. Data interpretations are the subject of a companion report.

Free-Surface Fluid-Object Interaction for the Large-Scale Computation of Ship Hydrodynamics Phenomena

DTIC Science & Technology

2014-05-21

simulating air-water free -surface flow, fluid-object interaction (FOI), and fluid-structure interaction (FSI) phenomena for complex geometries, and...with no limitations on the motion of the free surface, and with particular emphasis on ship hydrodynamics. The following specific research objectives...were identified for this project: 1) Development of a theoretical framework for free -surface flow, FOI and FSI that is a suitable starting point

Cation specific binding with protein surface charges

PubMed Central

Hess, Berk; van der Vegt, Nico F. A.

2009-01-01

Biological organization depends on a sensitive balance of noncovalent interactions, in particular also those involving interactions between ions. Ion-pairing is qualitatively described by the law of “matching water affinities.” This law predicts that cations and anions (with equal valence) form stable contact ion pairs if their sizes match. We show that this simple physical model fails to describe the interaction of cations with (molecular) anions of weak carboxylic acids, which are present on the surfaces of many intra- and extracellular proteins. We performed molecular simulations with quantitatively accurate models and observed that the order K+ < Na+ < Li+ of increasing binding affinity with carboxylate ions is caused by a stronger preference for forming weak solvent-shared ion pairs. The relative insignificance of contact pair interactions with protein surfaces indicates that thermodynamic stability and interactions between proteins in alkali salt solutions is governed by interactions mediated through hydration water molecules. PMID:19666545

Use of hydrologic budgets and hydrochemistry to determine ground-water and surface-water interactions for Rapid Creek, Western South Dakota

USGS Publications Warehouse

Anderson, Mark T.

1995-01-01

The study of ground-water and surface-water interactions often employs streamflow-gaging records and hydrologic budgets to determine ground-water seepage. Because ground-water seepage usually is computed as a residual in the hydrologic budget approach, all uncertainty of measurement and estimation of budget components is associated with the ground-water seepage. This uncertainty can exceed the estimate, especially when streamflow and its associated error of measurement, is large relative to other budget components. In a study of Rapid Creek in western South Dakota, the hydrologic budget approach with hydrochemistry was combined to determine ground-water seepage. The City of Rapid City obtains most of its municipal water from three infiltration galleries (Jackson Springs, Meadowbrook, and Girl Scout) constructed in the near-stream alluvium along Rapid Creek. The reach of Rapid Creek between Pactola Reservoir and Rapid City and, in particular the two subreaches containing the galleries, were studied intensively to identify the sources of water to each gallery. Jackson Springs Gallery was found to pump predominantly ground water with a minor component of surface water. Meadowbrook and Girl Scout Galleries induce infiltration of surface water from Rapid Creek but also have a significant component of ground water.

A Study on the Surface and Subsurface Water Interaction Based on the Groundwater Recession Curve

NASA Astrophysics Data System (ADS)

Wang, S. T.; Chen, Y. W.; Chang, L. C.; Chiang, C. J.; Wang, Y. S.

2017-12-01

The interaction of surface to subsurface water is an important issue for groundwater resources assessment and management. The influences of surface water to groundwater are mainly through the rainfall recharge, river recharge and discharge and other boundary sources. During a drought period, the interaction of river and groundwater may be one of the main sources of groundwater level recession. Therefore, this study explores the interaction of surface water to groundwater via the groundwater recession. During drought periods, the pumping and river interaction together are the main mechanisms causing the recession of groundwater level. In principle, larger gradient of the recession curve indicates more groundwater discharge and it is an important characteristic of the groundwater system. In this study, to avoid time-consuming manual analysis, the Python programming language is used to develop a statistical analysis model for exploring the groundwater recession information. First, the slopes of the groundwater level hydrograph at every time step were computed for each well. Then, for each well, the represented slope to each groundwater level was defined as the slope with 90% exceedance probability. The relationship between the recession slope and the groundwater level can then be obtained. The developed model is applied to Choushui River Alluvial Fan. In most wells, the results show strong positive correlations between the groundwater levels and the absolute values of the recession slopes.

Chemical modeling constraints on Martian surface mineralogies formed in an early, warm, wet climate, and speculations on the occurrence of phosphate minerals in the Martian regolith

NASA Technical Reports Server (NTRS)

Plumlee, Geoffrey S.; Ridley, W. Ian; Debraal, Jeffrey D.

1992-01-01

This is one in a series of reports summarizing our chemical modeling studies of water-rock-gas interactions at the martian surface through time. The purpose of these studies is to place constraints on possible mineralogies formed at the martian surface and to model the geochemical implications of martian surficial processes proposed by previous researchers. Plumlee and Ridley summarize geochemical processes that may have occurred as a result of inferred volcano- and impact-driven hydrothermal activity on Mars. DeBraal et al. model the geochemical aspects of water-rock interactions and water evaporation near 0 C, as a prelude to future calculations that will model sub-0 C brine-rock-clathrate interactions under the current martian climate. In this report, we discuss reaction path calculations that model chemical processes that may have occurred at the martian surface in a postulated early, warm, wet climate. We assume a temperature of 25 C in all our calculations. Processes we model here include (1) the reaction of rainwater under various ambient CO2 and O2 pressures with basaltic rocks at the martian surface, (2) the formation of acid rain by volcanic gases such as HCl and SO2, (3) the reactions of acid rain with basaltic surficial materials, and (4) evaporation of waters resulting from rainwater-basalt interactions.

Fiber lubrication: A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Liu, Hongyi

Molecular and mesoscopic level description of friction and lubrication remains a challenge because of difficulties in the phenomenological understanding of to the behaviors of solid-liquid interfaces during sliding. Fortunately, there is the computational simulation approach opens an opportunity to predict and analyze interfacial phenomena, which were studied with molecular dynamics (MD) and mesoscopic dynamics (MesoDyn) simulations. Polypropylene (PP) and cellulose are two of most common polymers in textile fibers. Confined amorphous surface layers of PP and cellulose were built successfully with xenon crystals which were used to compact the polymers. The physical and surface properties of the PP and cellulose surface layers were investigated by MD simulations, including the density, cohesive energy, volumetric thermal expansion, and contact angle with water. The topology method was employed to predict the properties of poly(alkylene glycol) (PAG) diblock copolymers and Pluronic triblock copolymers used as lubricants on surfaces. Density, zero shear viscosity, shear module, cohesive energy and solubility parameter were predicted with each block copolymer. Molecular dynamics simulations were used to study the interaction energy per unit contact area of block copolymer melts with PP and cellulose surfaces. The interaction energy is defined as the ratio of interfacial interaction energy to the contact area. Both poly(proplene oxide) (PPO) and poly(ethylene oxide) (PEO) segments provided a lipophilic character to both PP and cellulose surfaces. The PPO/PEO ratio and the molecular weight were found to impact the interaction energy on both PP and cellulose surfaces. In aqueous solutions, the interaction energy is complicated due to the presence of water and the cross interactions between the multiple molecular components. The polymer-water-surface (PWS) calculation method was proposed to calculate such complex systems. In a contrast with a vacuum condition, the presence of water increases the attractive interaction energy of the diblock copolymer on the cellulose surface, compared with that on the PP surface. Water decreases the interaction energy of the triblock copolymer on the cellulose surface, compared with that on the PP surface. MesoDyn was adopted to investigate the self-assembled morphology of the triblock copolymer, in aqueous solution, confined and sheared at solid-liquid interfaces. In a bulk aqueous solution, when the polymer concentration reached 10% v/v, micelles were observed with PPO blocks in the core and PEO blocks in the shell of the micelles. At the concentrations of 25% and 50%, worm-like micelles and irregular cylinders were observed in solutions, respectively. The micelles were formed faster in aqueous solutions confined by cellulose surfaces than that in the bulk. The formed micelles were broken under shearing, which led to a depletion of polymers at the interfaces. During the shearing on the PP surfaces, the polymers were adsorbed on the surfaces protecting the PP surfaces. This simulation study in the fiber lubrication was in good agreement with the experimental results and so provided an approach to visualize the polymer configuration at the liquid-solid interface, predict the lubricant-surface systems, and theoretically guide the experiments of designing new/efficient lubricants for fibers.

Modelling surface water-groundwater interaction with a conceptual approach: model development and application in New Zealand

NASA Astrophysics Data System (ADS)

Yang, J.; Zammit, C.; McMillan, H. K.

2016-12-01

As in most countries worldwide, water management in lowland areas is a big concern for New Zealand due to its economic importance for water related human activities. As a result, the estimation of available water resources in these areas (e.g., for irrigation and water supply purpose) is crucial and often requires an understanding of complex hydrological processes, which are often characterized by strong interactions between surface water and groundwater (usually expressed as losing and gaining rivers). These processes are often represented and simulated using integrated physically based hydrological models. However models with physically based groundwater modules typically require large amount of non-readily available geologic and aquifer information and are computationally intensive. Instead, this paper presents a conceptual groundwater model that is fully integrated into New Zealand's national hydrological model TopNet based on TopModel concepts (Beven, 1992). Within this conceptual framework, the integrated model can simulate not only surface processes, but also groundwater processes and surface water-groundwater interaction processes (including groundwater flow, river-groundwater interaction, and groundwater interaction with external watersheds). The developed model was applied to two New Zealand catchments with different hydro-geological and climate characteristics (Pareora catchment in the Canterbury Plains and Grey catchment on the West Coast). Previous studies have documented strong interactions between the river and groundwater, based on the analysis of a large number of concurrent flow measurements and associated information along the river main stem. Application of the integrated hydrological model indicates flow simulation (compared to the original hydrological model conceptualisation) during low flow conditions are significantly improved and further insights on local river dynamics are gained. Due to its conceptual characteristics and low level of data requirement, the integrated model could be used at local and national scales to improve the simulation of hydrological processes in non-topographically driven areas (where groundwater processes are important), and to assess impact of climate change on the integrated hydrological cycle in these areas.

Ground-Water System in the Chimacum Creek Basin and Surface Water/Ground Water Interaction in Chimacum and Tarboo Creeks and the Big and Little Quilcene Rivers, Eastern Jefferson County, Washington

USGS Publications Warehouse

Simonds, F. William; Longpre, Claire I.; Justin, Greg B.

2004-01-01

A detailed study of the ground-water system in the unconsolidated glacial deposits in the Chimacum Creek Basin and the interactions between surface water and ground water in four main drainage basins was conducted in eastern Jefferson County, Washington. The study will assist local watershed planners in assessing the status of the water resources and the potential effects of ground-water development on surface-water systems. A new surficial geologic map of the Chimacum Creek Basin and a series of hydrogeologic sections were developed by incorporating LIDAR imagery, existing map sources, and drillers' logs from 110 inventoried wells. The hydrogeologic framework outlined in the study will help characterize the occurrence of ground water in the unconsolidated glacial deposits and how it interacts with the surface-water system. Water levels measured throughout the study show that the altitude of the water table parallels the surface topography and ranges from 0 to 400 feet above the North American Vertical Datum of 1988 across the basin, and seasonal variations in precipitation due to natural cycles generally are on the order of 2 to 3 feet. Synoptic stream-discharge measurements and instream mini-piezometers and piezometers with nested temperature sensors provided additional data to refine the positions of gaining and losing reaches and delineate seasonal variations. Chimacum Creek generally gains water from the shallow ground-water system, except near the community of Chimacum where localized losses occur. In the lower portions of Chimacum Creek, gaining conditions dominate in the summer when creek stages are low and ground-water levels are high, and losing conditions dominate in the winter when creek stages are high relative to ground-water levels. In the Quilcene Bay area, three drainage basins were studied specifically to assess surface water/ground water interactions. The upper reaches of Tarboo Creek generally gain water from the shallow ground-water system throughout most of the year and the lower reaches have little or no gains. The Big Quilcene River generally gains water from the shallow ground-water system after it emerges from a bedrock canyon and loses water from the town of Quilcene to the mouth of the river in Quilcene Bay. The Little Quilcene River generally loses water to the shallow ground-water system, although two localized areas were found to have gaining conditions. The Big Quilcene and Little Quilcene Rivers incur significant losses on the alluvial plain at the head of Quilcene Bay. Each of the creeks examined had a unique pattern of gaining and losing reaches, owing to the hydraulic conductivity of the streambed material and the relative altitude of the surrounding water table. Although the magnitudes of gains and losses varied seasonally, the spatial distribution did not vary greatly, suggesting that patterns of gains and losses in surface-water systems depend greatly on the geology underlying the streambed.

Measurement of surface energy balance components in dryland wheat/fallow and limited-irrigation corn

USDA-ARS?s Scientific Manuscript database

Water evaporation from soil and plant surfaces and plant transpiration comprise land surface/canopy evapotranspiration (ET), which is essential to estimate for land-atmosphere interaction and crop water use. There are no direct measurements of ET, and the most direct methods (e.g., weighing lysimet...

Blueprint for a coupled model of sedimentology, hydrology, and hydrogeology in streambeds

NASA Astrophysics Data System (ADS)

Partington, Daniel; Therrien, Rene; Simmons, Craig T.; Brunner, Philip

2017-06-01

The streambed constitutes the physical interface between the surface and the subsurface of a stream. Across all spatial scales, the physical properties of the streambed control surface water-groundwater interactions. Continuous alteration of streambed properties such as topography or hydraulic conductivity occurs through erosion and sedimentation processes. Recent studies from the fields of ecology, hydrogeology, and sedimentology provide field evidence that sedimentological processes themselves can be heavily influenced by surface water-groundwater interactions, giving rise to complex feedback mechanisms between sedimentology, hydrology, and hydrogeology. More explicitly, surface water-groundwater exchanges play a significant role in the deposition of fine sediments, which in turn modify the hydraulic properties of the streambed. We explore these feedback mechanisms and critically review the extent of current interaction between the different disciplines. We identify opportunities to improve current modeling practices. For example, hydrogeological models treat the streambed as a static rather than a dynamic entity, while sedimentological models do not account for critical catchment processes such as surface water-groundwater exchange. We propose a blueprint for a new modeling framework that bridges the conceptual gaps between sedimentology, hydrogeology, and hydrology. Specifically, this blueprint (1) fully integrates surface-subsurface flows with erosion, transport, and deposition of sediments and (2) accounts for the dynamic changes in surface elevation and hydraulic conductivity of the streambed. Finally, we discuss the opportunities for new research within the coupled framework.

A quantum mechanical study of water adsorption on the (110) surfaces of rutile SnO₂ and TiO₂: investigating the effects of intermolecular interactions using hybrid-exchange density functional theory.

PubMed

Patel, M; Sanches, F F; Mallia, G; Harrison, N M

2014-10-21

Periodic hybrid-exchange density functional theory calculations are used to explore the first layer of water at model oxide surfaces, which is an important step for understanding the photocatalytic reactions involved in solar water splitting. By comparing the structure and properties of SnO2(110) and TiO2(110) surfaces in contact with water, the effects of structural and electronic differences on the water chemistry are examined. The dissociative adsorption mode at low coverage (1/7 ML) up to monolayer coverage (1 ML) on both SnO2 and TiO2(110) surfaces is analysed. To investigate further the intermolecular interactions between adjacent adsorbates, monolayer adsorption on each surface is explored in terms of binding energies and bond lengths. Analysis of the water adsorption geometry and energetics shows that the relative stability of water adsorption on SnO2(110) is governed largely by the strength of the chemisorption and hydrogen bonds at the surface of the adsorbate-substrate system. However on TiO2(110), a more complicated scenario of the first layer of water on its surface arises in which there is an interplay between chemisorption, hydrogen bonding and adsorbate-induced atomic displacements in the surface. Furthermore the projected density of states of each surface in contact with a mixture of adsorbed water molecules and adsorbed hydroxyls is presented and sheds some light on the nature of the crystalline chemical bonds as well as on why adsorbed water has often been reported to be unstable on rutile SnO2(110).

Simulation of the Regional Ground-Water-Flow System and Ground-Water/Surface-Water Interaction in the Rock River Basin, Wisconsin

USGS Publications Warehouse

Juckem, Paul F.

2009-01-01

A regional, two-dimensional, areal ground-water-flow model was developed to simulate the ground-water-flow system and ground-water/surface-water interaction in the Rock River Basin. The model was developed by the U.S. Geological Survey (USGS), in cooperation with the Rock River Coalition. The objectives of the regional model were to improve understanding of the ground-water-flow system and to develop a tool suitable for evaluating the effects of potential regional water-management programs. The computer code GFLOW was used because of the ease with which the model can simulate ground-water/surface-water interactions, provide a framework for simulating regional ground-water-flow systems, and be refined in a stepwise fashion to incorporate new data and simulate ground-water-flow patterns at multiple scales. The ground-water-flow model described in this report simulates the major hydrogeologic features of the modeled area, including bedrock and surficial aquifers, ground-water/surface-water interactions, and ground-water withdrawals from high-capacity wells. The steady-state model treats the ground-water-flow system as a single layer with hydraulic conductivity and base elevation zones that reflect the distribution of lithologic groups above the Precambrian bedrock and a regionally significant confining unit, the Maquoketa Formation. In the eastern part of the Basin where the shale-rich Maquoketa Formation is present, deep ground-water flow in the sandstone aquifer below the Maquoketa Formation was not simulated directly, but flow into this aquifer was incorporated into the GFLOW model from previous work in southeastern Wisconsin. Recharge was constrained primarily by stream base-flow estimates and was applied uniformly within zones guided by regional infiltration estimates for soils. The model includes average ground-water withdrawals from 1997 to 2006 for municipal wells and from 1997 to 2005 for high-capacity irrigation, industrial, and commercial wells. In addition, the model routes tributary base flow through the river network to the Rock River. The parameter-estimation code PEST was linked to the GFLOW model to select the combination of parameter values best able to match more than 8,000 water-level measurements and base-flow estimates at 9 streamgages. Results from the calibrated GFLOW model show simulated (1) ground-water-flow directions, (2) ground-water/surface-water interactions, as depicted in a map of gaining and losing river and lake sections, (3) ground-water contributing areas for selected tributary rivers, and (4) areas of relatively local ground water captured by rivers. Ground-water flow patterns are controlled primarily by river geometries, with most river sections gaining water from the ground-water-flow system; losing sections are most common on the downgradient shore of lakes and reservoirs or near major pumping centers. Ground-water contributing areas to tributary rivers generally coincide with surface watersheds; however the locations of ground-water divides are controlled by the water table, whereas surface-water divides are controlled by surface topography. Finally, areas of relatively local ground water captured by rivers generally extend upgradient from rivers but are modified by the regional flow pattern, such that these areas tend to shift toward regional ground-water divides for relatively small rivers. It is important to recognize the limitations of this regional-scale model. Heterogeneities in subsurface properties and in recharge rates are considered only at a very broad scale (miles to tens of miles). No account is taken of vertical variations in properties or pumping rates, and no provision is made to account for stacked ground-water-flow systems that have different flow patterns at different depths. Small-scale flow systems (hundreds to thousands of feet) associated with minor water bodies are not considered; as a result, the model is not currently designed for simulating site-specifi

Wettability, polarity, and water absorption of holm oak leaves: effect of leaf side and age.

PubMed

Fernández, Victoria; Sancho-Knapik, Domingo; Guzmán, Paula; Peguero-Pina, José Javier; Gil, Luis; Karabourniotis, George; Khayet, Mohamed; Fasseas, Costas; Heredia-Guerrero, José Alejandro; Heredia, Antonio; Gil-Pelegrín, Eustaquio

2014-09-01

Plant trichomes play important protective functions and may have a major influence on leaf surface wettability. With the aim of gaining insight into trichome structure, composition, and function in relation to water-plant surface interactions, we analyzed the adaxial and abaxial leaf surface of holm oak (Quercus ilex) as a model. By measuring the leaf water potential 24 h after the deposition of water drops onto abaxial and adaxial surfaces, evidence for water penetration through the upper leaf side was gained in young and mature leaves. The structure and chemical composition of the abaxial (always present) and adaxial (occurring only in young leaves) trichomes were analyzed by various microscopic and analytical procedures. The adaxial surfaces were wettable and had a high degree of water drop adhesion in contrast to the highly unwettable and water-repellent abaxial holm oak leaf sides. The surface free energy and solubility parameter decreased with leaf age, with higher values determined for the adaxial sides. All holm oak leaf trichomes were covered with a cuticle. The abaxial trichomes were composed of 8% soluble waxes, 49% cutin, and 43% polysaccharides. For the adaxial side, it is concluded that trichomes and the scars after trichome shedding contribute to water uptake, while the abaxial leaf side is highly hydrophobic due to its high degree of pubescence and different trichome structure, composition, and density. Results are interpreted in terms of water-plant surface interactions, plant surface physical chemistry, and plant ecophysiology. © 2014 American Society of Plant Biologists. All Rights Reserved.

A nested observation and model approach to non linear groundwater surface water interactions.

NASA Astrophysics Data System (ADS)

van der Velde, Y.; Rozemeijer, J. C.; de Rooij, G. H.

2009-04-01

Surface water quality measurements in The Netherlands are scattered in time and space. Therefore, water quality status and its variations and trends are difficult to determine. In order to reach the water quality goals according to the European Water Framework Directive, we need to improve our understanding of the dynamics of surface water quality and the processes that affect it. In heavily drained lowland catchment groundwater influences the discharge towards the surface water network in many complex ways. Especially a strong seasonal contracting and expanding system of discharging ditches and streams affects discharge and solute transport. At a tube drained field site the tube drain flux and the combined flux of all other flow routes toward a stretch of 45 m of surface water have been measured for a year. Also the groundwater levels at various locations in the field and the discharge at two nested catchment scales have been monitored. The unique reaction of individual flow routes on rainfall events at the field site allowed us to separate the discharge at a 4 ha catchment and at a 6 km2 into flow route contributions. The results of this nested experimental setup combined with the results of a distributed hydrological model has lead to the formulation of a process model approach that focuses on the spatial variability of discharge generation driven by temporal and spatial variations in groundwater levels. The main idea of this approach is that discharge is not generated by catchment average storages or groundwater heads, but is mainly generated by points scale extremes i.e. extreme low permeability, extreme high groundwater heads or extreme low surface elevations, all leading to catchment discharge. We focused on describing the spatial extremes in point scale storages and this led to a simple and measurable expression that governs the non-linear groundwater surface water interaction. We will present the analysis of the field site data to demonstrate the potential of nested-scale, high frequency observations. The distributed hydrological model results will be used to show transient catchment scale relations between groundwater levels and discharges. These analyses lead to a simple expression that can describe catchment scale groundwater surface water interactions.

Determining temperature and thermal properties for heat-based studies of surface-water ground-water interactions: Appendix A of Heat as a tool for studying the movement of ground water near streams (Cir1260)

USGS Publications Warehouse

Stonestrom, David A.; Blasch, Kyle W.; Stonestrom, David A.; Constantz, Jim

2003-01-01

Advances in electronics leading to improved sensor technologies, large-scale circuit integration, and attendant miniaturization have created new opportunities to use heat as a tracer of subsurface flow. Because nature provides abundant thermal forcing at the land surface, heat is particularly useful in studying stream-groundwater interactions. This appendix describes methods for obtaining the thermal data needed in heat-based investigations of shallow subsurface flow.

Adsorption of aromatic hydrocarbons and ozone at environmental aqueous surfaces.

PubMed

Vácha, Robert; Cwiklik, Lukasz; Rezác, Jan; Hobza, Pavel; Jungwirth, Pavel; Valsaraj, Kalliat; Bahr, Stephan; Kempter, Volker

2008-06-05

Adsorption of environmentally important aromatic molecules on a water surface is studied by means of classical and ab initio molecular dynamics simulations and by reflection-absorption infrared spectroscopy. Both techniques show strong activity and orientational preference of these molecules at the surface. Benzene and naphthalene, which bind weakly to water surface with a significant contribution of dispersion interactions, prefer to lie flat on water but retain a large degree of orientational flexibility. Pyridine is more rigid at the surface. It is tilted with the nitrogen end having strong hydrogen bonding interactions with water molecules. The degree of adsorption and orientation of aromatic molecules on aqueous droplets has atmospheric implications for heterogeneous ozonolysis, for which the Langmuir-Hinshelwood kinetics mechanism is discussed. At higher coverages of aromatic molecules the incoming ozone almost does not come into contact with the underlying aqueous phase. This may rationalize the experimental insensitivity of the ozonolysis on the chemical nature of the substrate on which the aromatic molecules adsorb.

Site Competition During Coadsorption of Acetone with Methanol and Water on TiO2(110)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shen, Mingmin; Henderson, Michael A.

2011-08-02

The competitive interaction between acetone and two solvent molecules (methanol and water) for surface sites on rutile TiO2(110) was studied using temperature programmed desorption (TPD). On a vacuum reduced TiO2(110) surface, which possessed ~5% oxygen vacancy sites, excess methanol displaced preadsorbed acetone molecules to weakly bound and physisorbed desorption states below 200 K, whereas acetone was stabilized to 250 K against displacement by methanol on an oxidized surface through formation of an acetone-diolate species. These behaviors of acetone differ from the competitive interactions between acetone and water in that acetone is less susceptible to displacement by water. Examination of acetone+methanolmore » and acetone+water multilayer combinations shows that acetone is more compatible in water-ice films than in methanol-ice films, presumably because water has greater potential as a hydrogen-bond donor than does methanol. Acetone molecules displaced from the TiO2(110) surface by water are more likely to be retained in the near-surface region, having a greater opportunity to revisit the surface, than when methanol is used as a coadsorbate. 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.« less

Progression towards optimization of viscosity of highly concentrated carbonaceous solid-water slurries by incorporating and modifying surface chemistry parameters with and without additives

NASA Astrophysics Data System (ADS)

Mukherjee, Amrita

Carbonaceous solid-water slurries (CSWS) are concentrated suspensions of coal, petcoke bitumen, pitch etc. in water which are used as feedstock for gasifiers. The high solid loading (60-75 wt.%) in the slurry increases CSWS viscosity. For easier handling and pumping of these highly loaded mixtures, low viscosities are desirable. Depending on the nature of the carbonaceous solid, solids loading in the slurry and the particle size distribution, viscosity of a slurry can vary significantly. Ability to accurately predict the viscosity of a slurry will provide a better control over the design of slurry transport system and for viscosity optimization. The existing viscosity prediction models were originally developed for hard-sphere suspensions and therefore do not take into account surface chemistry. As a result, the viscosity predictions using these models for CSWS are not very accurate. Additives are commonly added to decrease viscosity of the CSWS by altering the surface chemistry. Since additives are specific to CSWS, selection of appropriate additives is crucial. The goal of this research was to aid in optimization of CSWS viscosity through improved prediction and selection of appropriate additive. To incorporate effect of surface chemistry in the models predicting suspension viscosity, the effect of the different interfacial interactions caused by different surface chemistries has to be accounted for. Slurries of five carbonaceous solids with varying O/C ratio (to represent different surface chemistry parameters) were used for the study. To determine the interparticle interactions of the carbonaceous solids in water, interfacial energies were calculated on the basis of surface chemistries, characterized by contact angles and zeta potential measurements. The carbonaceous solid particles in the slurries were assumed to be spherical. Polar interaction energy (hydrophobic/hydrophilic interaction energy), which was observed to be 5-6 orders of magnitude higher than the electrostatic interaction energy, and the van der Waals interaction energy, was clearly the dominant interaction energy for such a system. Hydrophobic interactions lead to the formation of aggregation networks of solids in the suspensions, entrapping a part of the bulk water, whereas hydrophilic interactions result in the formation of hydration layers around carbonaceous solids. Both of these phenomena cause a loss of bulk water from the slurry and increase the effective solid volume fraction, resulting in an increase in slurry viscosity. The water in the bulk of the slurry, responsible for the fluidity of the slurry is called free water. The amount of free water was determined using thermogravimetric analysis and was observed to increase with an increase in the O/C ratio of a carbonaceous solid (up to ˜20%). The free water to total water ratio was observed to be constant for the slurry of a particular carbonaceous solid for various loadings of solids (44 wt.% to 67 wt.%). The increase in the effective solid volume fractions of slurries was determined using viscosity measurements. A relationship between the effective solid volume fraction and the O/C ratio of the carbonaceous solid was developed. This correlation was then incorporated into the existing equation for viscosity prediction (developed based on particle size distribution and solid volume fraction), to account for the surface chemistry of the carbonaceous solid and hence improve the predictive capabilities. This modified equation was validated using three concentrated carbonaceous slurries with different particle size distributions and was observed to significantly improve accuracy of prediction (deviation of predicted results decreased from up to 96% to 25%). The validation was performed with a lignite, bituminous coal and a petcoke-all with low ash yield. Additives modify the surface chemistry of the carbonaceous solids, thereby affecting the interfacial interactions. Through this research, the effects of additives on the interfacial interactions and hence on slurry viscosity were determined. Since the additives used are specific to the surface chemistry of the solids in the slurry, this knowledge aids in the selection of the appropriate additive. The study was conducted using three carbonaceous solids with different O/C ratios and an anionic and a non-ionic additive. The adsorption of the additives on the carbonaceous solids, the change in the zeta potential and hydrophobicity/hydrophilicity of the solids and the change in the free water content of the slurries were determined. The adsorption of the additives increased with an increase in the mineral matter content of the carbonaceous solids. There was also an increase in the zeta potential of the carbonaceous solids in water upon the addition of the anionic additive (up to ˜30%). However, the calculated resultant electrostatic repulsion energy upon the addition of the anionic additive was 5-6 orders of magnitude lower than the polar interaction energy of the carbonaceous solids in water. Contact angle measurements indicated that both additives changed the hydrophobicity/hydrophilicity of the solid surface (by up to 70°). This resulted in the release of bound water into the bulk slurries (up to 6%), resulting in greater fluidity. The increase in free water content of the slurries with additives was confirmed by thermogravimetric analysis (TGA). A correlation predicting the slurry viscosity on the basis of the weight fraction of free water in the slurries with additives was also developed.

Hydrochemical and environmental isotope analysis of groundwater and surface water in a dry mountain region in Northern Chile.

PubMed

Zang, Carina; Dame, Juliane; Nüsser, Marcus

2018-05-08

This case study examines the geological imprint and land use practices on water quality in the arid Huasco Valley against the backdrop of ongoing water conflicts surrounding competing demands for agriculture and mining. The study is based on a detailed analysis of spatial and temporal variations of monthly surface and bi-monthly groundwater quality samples measured during the Chilean summer of 2015/16. Additional information on source regions and river-groundwater interactions were collected using stable water isotopes. Regarding the geological impact on water quality, high concentrations of Ca 2+ , SO 4 2- and HCO 3 - indicate a strong influence of magmatic rocks, which constitute this high mountain basin, on the hydrochemistry. Piper and Gibbs-diagrams revealed that all samples show a homogenous distribution dominated by rock-water interactions. Measured NO 3 - concentrations in surface water are generally low. However, groundwater aquifers exhibit higher concentrations. Mn is the only heavy metal with elevated concentrations in surface water, which are possibly related to mining activities. The results illustrate that both surface and groundwater can be classified as suitable for irrigation. In addition, groundwater has been found to be suitable as drinking water. High similarities in isotopic signatures indicate a strong connection between surface and groundwater. Isotopic analyses suggest a strong influence of evaporation. This combined approach of hydrogeochemical and isotopic analysis proved to be a helpful tool in characterizing the catchment and can serve as a basis for future sustainable water management.

Surface-groundwater interactions in hard rocks in Sardon Catchment of western Spain: An integrated modeling approach

NASA Astrophysics Data System (ADS)

Hassan, S. M. Tanvir; Lubczynski, Maciek W.; Niswonger, Richard G.; Su, Zhongbo

2014-09-01

The structural and hydrological complexity of hard rock systems (HRSs) affects dynamics of surface-groundwater interactions. These complexities are not well described or understood by hydrogeologists because simplified analyses typically are used to study HRSs. A transient, integrated hydrologic model (IHM) GSFLOW (Groundwater and Surface water FLOW) was calibrated and post-audited using 18 years of daily groundwater head and stream discharge data to evaluate the surface-groundwater interactions in semi-arid, ∼80 km2 granitic Sardon hilly catchment in Spain characterized by shallow water table conditions, relatively low storage, dense drainage networks and frequent, high intensity rainfall. The following hydrological observations for the Sardon Catchment, and more generally for HRSs were made: (i) significant bi-directional vertical flows occur between surface water and groundwater throughout the HRSs; (ii) relatively large groundwater recharge represents 16% of precipitation (P, 562 mm.y-1) and large groundwater exfiltration (∼11% of P) results in short groundwater flow paths due to a dense network of streams, low permeability and hilly topographic relief; deep, long groundwater flow paths constitute a smaller component of the water budget (∼1% of P); quite high groundwater evapotranspiration (∼5% of P and ∼7% of total evapotranspiration); low permeability and shallow soils are the main reasons for relatively large components of Hortonian flow and interflow (15% and 11% of P, respectively); (iii) the majority of drainage from the catchment leaves as surface water; (iv) declining 18 years trend (4.44 mm.y-1) of groundwater storage; and (v) large spatio-temporal variability of water fluxes. This IHM study of HRSs provides greater understanding of these relatively unknown hydrologic systems that are widespread throughout the world and are important for water resources in many regions.

Surface-water Interface Induces Conformational Changes Critical for Protein Adsorption: Implications for Monolayer Formation of EAS Hydrophobin

PubMed Central

Ley, Kamron; Christofferson, Andrew; Penna, Matthew; Winkler, Dave; Maclaughlin, Shane; Yarovsky, Irene

2015-01-01

The class I hydrophobin EAS is part of a family of small, amphiphilic fungal proteins best known for their ability to self-assemble into stable monolayers that modify the hydrophobicity of a surface to facilitate further microbial growth. These proteins have attracted increasing attention for industrial and biomedical applications, with the aim of designing surfaces that have the potential to maintain their clean state by resisting non-specific protein binding. To gain a better understanding of this process, we have employed all-atom molecular dynamics to study initial stages of the spontaneous adsorption of monomeric EAS hydrophobin on fully hydroxylated silica, a commonly used industrial and biomedical substrate. Particular interest has been paid to the Cys3-Cys4 loop, which has been shown to exhibit disruptive behavior in solution, and the Cys7-Cys8 loop, which is believed to be involved in the aggregation of EAS hydrophobin at interfaces. Specific and water mediated interactions with the surface were also analyzed. We have identified two possible binding motifs, one which allows unfolding of the Cys7-Cys8 loop due to the surfactant-like behavior of the Cys3-Cys4 loop, and another which has limited unfolding due to the Cys3-Cys4 loop remaining disordered in solution. We have also identified intermittent interactions with water which mediate the protein adsorption to the surface, as well as longer lasting interactions which control the diffusion of water around the adsorption site. These results have shown that EAS behaves in a similar way at the air-water and surface-water interfaces, and have also highlighted the need for hydrophilic ligand functionalization of the silica surface in order to prevent the adsorption of EAS hydrophobin. PMID:26636091

Surface-water Interface Induces Conformational Changes Critical for Protein Adsorption: Implications for Monolayer Formation of EAS Hydrophobin.

PubMed

Ley, Kamron; Christofferson, Andrew; Penna, Matthew; Winkler, Dave; Maclaughlin, Shane; Yarovsky, Irene

2015-01-01

The class I hydrophobin EAS is part of a family of small, amphiphilic fungal proteins best known for their ability to self-assemble into stable monolayers that modify the hydrophobicity of a surface to facilitate further microbial growth. These proteins have attracted increasing attention for industrial and biomedical applications, with the aim of designing surfaces that have the potential to maintain their clean state by resisting non-specific protein binding. To gain a better understanding of this process, we have employed all-atom molecular dynamics to study initial stages of the spontaneous adsorption of monomeric EAS hydrophobin on fully hydroxylated silica, a commonly used industrial and biomedical substrate. Particular interest has been paid to the Cys3-Cys4 loop, which has been shown to exhibit disruptive behavior in solution, and the Cys7-Cys8 loop, which is believed to be involved in the aggregation of EAS hydrophobin at interfaces. Specific and water mediated interactions with the surface were also analyzed. We have identified two possible binding motifs, one which allows unfolding of the Cys7-Cys8 loop due to the surfactant-like behavior of the Cys3-Cys4 loop, and another which has limited unfolding due to the Cys3-Cys4 loop remaining disordered in solution. We have also identified intermittent interactions with water which mediate the protein adsorption to the surface, as well as longer lasting interactions which control the diffusion of water around the adsorption site. These results have shown that EAS behaves in a similar way at the air-water and surface-water interfaces, and have also highlighted the need for hydrophilic ligand functionalization of the silica surface in order to prevent the adsorption of EAS hydrophobin.

Groundwater-Surface Water Interaction: A Case Study of Embankment Dam Safety Assessment in Sweden.

NASA Astrophysics Data System (ADS)

Ferdos, F.; Dargahi, B.

2015-12-01

Seepage, when excessive and unimpeded, can cause embankment dam failure. Such failures are often initiated by internal erosion and piping. Modelling these phenomena in embankment dams, accounting for the groundwater-surface water interactions, is crucial when performing dam safety assessments. The aim of this study was to evaluate the applicability of modelling seepage flows in multi-region dams using a finite element based multi-physics model. The model was applied to the Trängslet dam, the largest dam in Sweden. The objectives were to analyze the characteristics of both the flow and the surface-ground water interactions occurring in the dam, including: i) the saturated and unsaturated laminar flow regimes within the dam body, ii) the non-linear through-flow in the dam shoulders' coarse material, iii) the influence of the surface waves in the reservoir on the seepage flow by coupling the physics to a hydrodynamic interface, and iv) the influence of a conceptual "erosion tunnel" on the seepage flow and its interaction with the surface water flow by coupling the physics to a CFD interface. The focus of the study was on the influence of the transient water head boundary condition, surface waves and the internal erosion tunnel on the location of the phreatic line and the seepage flow rate. The simulated seepage flow of the dam in its original condition tallied with the monitoring measurements (40-70 l/s). The main feature found was the relatively high position of the phreatic line, which could compromise the stability of the dam. The combination of the seepage model with the reservoir hydrodynamics indicated a negligible influence of the surface waves on seepage flow. Results from the combination of the seepage model with fluid dynamics indicated that a conceptual "erosion tunnel" placed within the dam, even as high as in the unsaturated zone, significantly affects the phreatic line's position. This also causes the seepage flow to increase by several orders of magnitude, resulting in non-linear turbulent flow regimes in the downstream shoulder of the dam and, ultimately, dam failure. While the modelling was limited by a lack of reliable geometrical and geotechnical data, the results of the study do highlight the importance of including groundwater-surface water interactions in dam safety assessments.

Surfing with capillary waves: a survival strategy for trapped bees

NASA Astrophysics Data System (ADS)

Roh, Chris; Gharib, Morteza

2017-11-01

Honeybees are able to propel themselves at the water surface. A rapid vibration (30-220 Hz) of wings at the air-water interface results in a locomotion speed of 3-4 cm/s. A mechanism for generating thrust required for achieving and maintaining such speed must be different from their mechanism of flight inasmuch as they are in a different fluid environment. In this study, we present the thrust generating mechanism of the honeybee at the air-water interface. A close observation of the wing's interaction with the water surface showed that the wing does not penetrate nor detach from the water surface. Moreover, the stroke speed of the wing exceeds the minimum capillary wave speed, which signifies that the wing constantly generates the capillary wave by pulling on the surface with its wetted underside. Observation of such interaction suggests that honeybee's locomotion at the water surface resembles surfing on the self-generated capillary wave. A further evidence of described mechanism is explored by constructing a similarly sized mechanical model. This material is based upon work supported by the National Science Foundation under Grant No. CBET-1511414; additional support by the National Science Foundation Graduate Research Fellowship under Grant No. DGE-1144469.

Altered Landscapes and Groundwater Sustainability — Exploring Impacts with Induced Polarization, DC Resistivity, and Thermal Tracing

NASA Astrophysics Data System (ADS)

Eddy-Miller, C.; Caldwell, R.; Wheeler, J.; McCarthy, P.; Binley, A. M.; Constantz, J. E.; Stonestrom, D. A.

2009-12-01

Anthropogenically impacted landscapes constitute rising proportions of the Earth’s surface that are characterized by generally elevated nutrient and sediment loadings concurrent with increased consumptive water withdrawals. In recent years a growing number of hydraulically engineered riparian habitat restoration projects have attempted to ameliorate negative impacts of land use on groundwater-surface water systems resulting, e.g., from agricultural practices and urban development. Often the nature of groundwater-surface water interactions in pre- and minimally altered systems is poorly known, making it difficult to assess the impacts of land use and restoration projects on groundwater sustainability. Traditional assessments of surface water parameters (flow, temperature, dissolved oxygen, biotic composition, etc.) can be complemented by hydraulic and thermal measurements to better understand the important role played by groundwater-surface water interactions. Hydraulic and thermal measurements are usually limited to point samples, however, making non-invasive and spatially extensive geophysical characterizations an attractive additional tool. Groundwater-surface water interactions along the Smith River, a tributary to the Missouri River in Montana, and Fish Creek and Flat Creek, tributaries to the Snake River in Wyoming, are being examined using a combination of hydraulic measurements, thermal tracing, and electrical-property imaging. Ninety-two direct-current (DC) resistivity and induced polarization cross sections were obtained at stream transects covering a wide variety of hydrogeologic settings ranging from shallow bedrock to thick alluvial sequences, nature of groundwater-surface water interactions (always gaining, always losing, or seasonally varying) and anthropogenic impacts (minimal low-intensity agriculture to major landscape engineering, including channel reconstruction). DC resistivity and induced polarization delineated mutually distinct features related to hydraulic architecture. For example, induced polarization imaging resolved channel-edge muck deposits that are presumed to be sites of low hydraulic conductivity, chemical reduction, and metal accumulation. DC resistivity delineated bedrock-alluvium contacts and showed potential for tracking changes in salinization. While electrical properties cannot substitute for hydraulic and thermal data, the addition of relatively rapidly acquired, spatially extensive resistivity and induced polarization imaging offers synergistic opportunities for interpretive hydrologic investigations.

Interaction of hydrogen chloride with alumina. [atmospheric effluent concentrations and interaction of solid rocket propellants used in space shuttle

NASA Technical Reports Server (NTRS)

Bailey, R. R.; Wightman, J. P.

1978-01-01

The influence of temperature, pressure, and outgas conditions on the absorption of hydrogen chloride and water vapor on both alpha and gamma alumina was studied. Characterization of the adsorbents was performed using X-ray powder diffraction, scanning electron microscopy (SEM), low temperature nitrogen adsorption desorption measurements, BET nitrogen surface area measurements and electron spectroscopy for chemical analysis (ESCA). Water vapor adsorption isotherms at 30, 40, and 50 C were measured on alpha and gamma alumina after outgassing at 80, 200, and 400 C. Both outgas temperature and adsorption temperature influenced the adsorption of water vapor on the aluminas. The water vapor adsorption was completely reversible. Alpha alumina absorbed more water per unit area than gamma alumina. Differences in the adsorption capacity for water vapor of the two aluminas were explained on the basis of ideal surface models of alpha and gamma alumina. Isosteric heats of adsorption for water vapor on the aluminas were determined over a limited range of surface coverage.

Chloride concentrations and stable isotopes of hydrogen and oxygen in surface water and groundwater in and near Fish Creek, Teton County, Wyoming, 2005-06

USGS Publications Warehouse

Eddy-Miller, Cheryl A.; Wheeler, Jerrod D.

2010-01-01

Fish Creek, an approximately 25-kilometer long tributary to the Snake River, is located in Teton County in western Wyoming near the town of Wilson. The U.S. Geological Survey, in cooperation with the Teton Conservation District, conducted a study to determine the interaction of local surface water and groundwater in and near Fish Creek. In conjunction with the surface water and groundwater interaction study, samples were collected for analysis of chloride and stable isotopes of hydrogen and oxygen in water. Chloride concentrations ranged from 2.9 to 26.4 milligrams per liter (mg/L) near Teton Village, 1.2 to 4.9 mg/L near Resor's Bridge, and 1.8 to 5.0 mg/L near Wilson. Stable isotope data for hydrogen and oxygen in water samples collected in and near the three cross sections on Fish Creek are shown in relation to the Global Meteoric Water Line and the Local Meteoric Water Line.

Insights into structural and dynamical features of water at halloysite interfaces probed by DFT and classical molecular dynamics simulations.

PubMed

Presti, Davide; Pedone, Alfonso; Mancini, Giordano; Duce, Celia; Tiné, Maria Rosaria; Barone, Vincenzo

2016-01-21

Density functional theory calculations and classical molecular dynamics simulations have been used to investigate the structure and dynamics of water molecules on kaolinite surfaces and confined in the interlayer of a halloysite model of nanometric dimension. The first technique allowed us to accurately describe the structure of the tetrahedral-octahedral slab of kaolinite in vacuum and in interaction with water molecules and to assess the performance of two widely employed empirical force fields to model water/clay interfaces. Classical molecular dynamics simulations were used to study the hydrogen bond network structure and dynamics of water adsorbed on kaolinite surfaces and confined in the halloysite interlayer. The results are in nice agreement with the few experimental data available in the literature, showing a pronounced ordering and reduced mobility of water molecules at the hydrophilic octahedral surfaces of kaolinite and confined in the halloysite interlayer, with respect to water interacting with the hydrophobic tetrahedral surfaces and in the bulk. Finally, this investigation provides new atomistic insights into the structural and dynamical properties of water-clay interfaces, which are of fundamental importance for both natural processes and industrial applications.

From watershed- to stream-reach-scale: the influence of multiple spatial scales on surface water-groundwater exchange

NASA Astrophysics Data System (ADS)

Caruso, Alice; Boano, Fulvio; Ridolfi, Luca

2015-04-01

Surface water bodies continuously interact with the subsurface and it is by now widely known that the hyporheic zone plays a key role in the mixing of river water with shallow groundwater. Hyporheic exchange occurs over a very wide range of spatial and temporal scales and the exchange processes at different scales interact and determine a complex system of nested flow cells. This intricacy results from the multiplicity of spatial scale that characterize landscape and river morphology. In the last years, many processes that regulate the surface-groundwater interactions have been elucidated and a more holistic view of groundwater and surface water has been adopted. However, despite several insights on the mechanisms of hyporheic exchange have been achieved, many important aspects remain to be clarified, i.e. how surface-groundwater interactions influence solute transport, microbial activity and biogeochemical transformations at the scale of entire watersheds. To date a deep knowledge of small-scale processes has been developed but what is lacking is a unifying overview of the role of surface water-groundwater exchange for the health of the whole water system at larger scales, i.e. the scale of the entire basin. In order to better understand the complex multiscale nature of spatial patterns of surface-subsurface exchange, we aim to assess the importance of the individual scales included in the range between watershed scale to stream reach scale. Hence, we study the large-scale subsurface flow field taking into account the surface-groundwater interactions induced by landscape topography from the basin scale to smaller scales ranging from tens of kilometers to tens of meters. The aim of this research is to analyze how individual topographic scales affect the flow field and to understand which ones are the most important and should be focused on. To study the impact of various scales of landscape topography we apply an analytical model that provides an exact solution of the underlying three dimensional groundwater flow and a numerical particle tracking routine that allows to obtain streamlines and residence time distributions from the flow field. Therefore, starting from a previously published mathematical tool we set the goal of investigating the interaction between the scales and clarifying their role. We consider real basin examples and describe subsurface flow at the landscape scale, identifying inflow patterns of groundwater to the river network, in order to obtain, in the near future, results to be used for conserving, managing and restoring of a riverine ecosystem.

Ground water and surface water: the linkage tightens, but challenges remain

USGS Publications Warehouse

Winter, Thomas C.

2001-01-01

Hydrologists have recognized for more than a century that groundwater and surface water are closely linked, but for most of that timestudies of their interaction were carried out largely by single disci-plines. This is slowly changing, however, as the need for integratedstudies involving many disciplines is becoming more evident.

ECO Update / Groundwater Foum Issue Paper: Evaluating Ground-Water/Surface-Water Transition Zones in Ecological Risk Assessments

EPA Pesticide Factsheets

This ECO Update builds on the standard approach to ERA (U.S. EPA 1997), by providing a framework for incorporating groundwater/surface-water (GW/SW) interactions into existing ERAs (see U.S. EPA 1997 and 2001a for an introduction to ecological risk....

Flux Meter Assesses the Effects of Groundwater, Surface Water, and Contaminated Sediment Interactions on Ecosystems

EPA Science Inventory

The slow flow of water between groundwater (GW) and surface water (SW) is often referred to as seepage, or in scientific terms, advective flux. This slow flow at the GW/SW interface presents measurement difficulties. This project was conducted to develop a durable advective flux ...

Interactions on External MOF Surfaces: Desorption of Water and Ethanol from CuBDC Nanosheets.

PubMed

Elder, Alexander C; Aleksandrov, Alexandr B; Nair, Sankar; Orlando, Thomas M

2017-10-03

The external surfaces of metal-organic framework (MOF) materials are difficult to experimentally isolate due to the high porosities of these materials. MOF surface surrogates in the form of copper benzenedicarboxylate (CuBDC) nanosheets were synthesized using a bottom-up approach, and the surface interactions of water and ethanol were investigated by temperature-programmed desorption (TPD). A method of analysis of diffusion-influenced TPD was developed to measure the desorption properties of these porous materials. This approach also allows the extraction of diffusion coefficients from TPD data. The transmission Fourier transform infrared spectra, powder X-ray diffraction patterns, and TPD data indicate that water desorbs from CuBDC nanosheets with activation energies of 44 ± 2 kJ/mol at edge sites and 58 ± 1 kJ/mol at external surface and internal and pore sites. Ethanol desorbs with activation energies of 58 ± 1 kJ/mol at internal pore sites and 66 ± 0.4 kJ/mol at external surface sites. Co-adsorption of water and ethanol was also investigated. The presence of ethanol was found to inhibit the desorption of water, resulting in a water desorption process with an activation energy of 68 ± 0.7 kJ/mol.

Natural attenuation of chlorinated-hydrocarbon contamination at Fort Wainwright, Alaska; a hydrogeochemical and microbiological investigation workplan

USGS Publications Warehouse

McCarthy, Kathleen A.; Lilly, Michael R.; Braddock, Joan F.; Hinzman, Larry D.

1998-01-01

Natural attenuation processes include biological degradation, by which microorganisms break down contaminants into simpler product compounds; adsorption of contaminants to soil particles, which decreases the mass of contaminants dissolved in ground water; and dispersion, which decreases dissolved contaminant concentrations through dilution. The primary objectives of this study are to (1) assess the degree to which such natural processes are attenuating chlorinated-hydrocarbon contamination in ground water, and (2) evaluate the effects of ground-water/surface-water interactions on natural-attenuation processes in the area of the former East and West Quartermasters Fueling Systems for Fort Wainwright, Alaska. The study will include investigations of the hydrologic, geochemical, and microbiological processes occurring at this site that influence the transport and fate of chlorinated hydrocarbons in ground water. To accomplish these objectives, a data-collection program has been initiated that includes measurements of water-table elevations and the stage of the Chena River; measurements of vertical temperature profiles within the subsurface; characterization of moisture distribution and movement in the unsaturated zone; collection of ground-water samples for determination of both organic and inorganic chemical constituents; and collection of ground-water samples for enumeration of microorganisms and determination of their potential to mineralize contaminants. We will use results from the data-collection program described above to refine our conceptual model of hydrology and contaminant attenuation at this site. Measurements of water-table elevations and river stage will help us to understand the magnitude and direction of ground-water flow and how changes in the stage of the Chena River affect ground-water flow. Because ambient ground water and surface water typically have different temperature characteristics, temperature monitoring will likely provide further insight into ground-water/surface-water interactions in the subsurface. Characterization of the unsaturated zone will improve our understanding of interactions among ground water, the unsaturated zone, and the atmosphere. The interactions likely of importance to this study include the migration of water, dissolved contaminants, nutrients, and gases (oxygen, carbon dioxide, and methane) between the saturated and unsaturated zones. We will use the results of ground-water chemical analyses to determine the spatial and temporal distribution of (1) chlorinated-hydrocarbon contaminants and their degradation products, (2) oxidation-reduction indicators, (3) nutrients, and (4) major ground-water ions. These water-quality data will provide insight into ground-water flow directions, interactions between ground water and surface water, attenuation of contaminant concentrations caused by dispersion, and intrinsic microbiological processes. Microbiological analyses will indicate whether microorganisms at the site are capable of degrading the contaminants of interest, and will allow us to estimate their potential to attenuate existing contamination. Physical and chemical data interpreted as part of the analysis of ground water and surface water mixing will improve our understanding of the relationship between water quality and contaminant source mixing.

Interaction of gases with lunar materials. [analysis of lunar samples from Apollo 17 flight

NASA Technical Reports Server (NTRS)

Holmes, H. F.; Fuller, E. L., Jr.; Gammage, R. B.

1974-01-01

The surface chemistry of Apollo 17 lunar fines samples 74220 (the orange soil) and 74241 (the gray control soil) has been studied by measuring the adsorption of nitrogen, argon, and oxygen (all at 77 K) and also water vapor (at 20 or 22 C). In agreement with results for samples from other missions, both samples had low initial specific surface areas, consisted of nonporous particles, and were attacked by water vapor at high relative pressure to give an increased specific surface area and create a pore system which gave rise to a capillary condensation hysteresis loop in the adsorption isotherms. In contrast to previous samples, both of the Apollo 17 soils were partially hydrophobic in their initial interaction with water vapor (both samples were completely hydrophilic after the reaction with water). The results are consistent with formation at high temperatures without subsequent exposure to significant amounts of water.

Phase transitions of a water overlayer on charged graphene: from electromelting to electrofreezing.

PubMed

Zhu, Xueyan; Yuan, Quanzi; Zhao, Ya-Pu

2014-05-21

We show by using molecular dynamics simulations that a water overlayer on charged graphene experiences first-order ice-to-liquid (electromelting), and then liquid-to-ice (electrofreezing) phase transitions with the increase of the charge value. Corresponding to the ice-liquid-ice transition, the variations of the order parameters indicate an order-disorder-order transition. The key to this novel phenomenon is the surface charge induced change of the orientations of water dipoles, which leads to the change of the water-water interactions from being attractive to repulsive at a critical charge value qc. To further uncover how the orientations of water dipoles influence the interaction strength between water molecules, a theoretical model considering both the Coulomb and van der Waals interactions is established. The results show that with the increase of the charge value, the interaction strength between water molecules decreases below qc, then increases above qc. These two inverse processes lead to electromelting and electrofreezing, respectively. Combining this model with the Eyring equation, the diffusion coefficient is obtained, the variation of which is in qualitative agreement with the simulation results. Our findings not only expand our knowledge of the graphene-water interface, but related analyses could also help recognize the controversial role of the surface charge or electric field in promoting phase transitions of water.

A molecular model for ice nucleation and growth, attachment 1

NASA Technical Reports Server (NTRS)

Plummer, P. L. M.

1981-01-01

The quantum mechanical technique is used to study ionic, configurational, and impurity defects in the ice surface. In addition to static calculations of the energetics of the water monomer-ice surface interactions, molecular dynamics studies were initiated. The calculations of the monomer-ice surface interaction, molecular dynamics studies were initiated. The calculations of monomer-ice surface interactions indicate that many adsorption sites exist on the ice surfaces and that the barriers between bonding sites are relatively low. Bonding on the prism face of ice is preferentially above lattice sites.

Technical note: Examining ozone deposition over seawater

EPA Science Inventory

Surface layer resistance plays an important role in determining ozone deposition velocity over sea-water and can be influenced by chemical interactions at the air-water interface. Here, we examine the effect of chemical interactions of iodide, dimethylsulfide, dissolved organic c...

Effect of collector molecular structure on the wettability of gold for froth flotation

NASA Astrophysics Data System (ADS)

Moncayo-Riascos, Ivan; Hoyos, Bibian A.

2017-10-01

Molecular dynamics simulations were conducted to evaluate the alteration of the hydrophilic state of gold surfaces caused by the adsorption of collectors with different molecular structures, using the contact angle of water droplets as an evaluation parameter. Four collectors were evaluated: SDS (with twelve hydrogenated carbon atoms), PAX (with five hydrogenated carbon atoms), DTP (with two branched aliphatic chains) and MBT (with an aromatic ring). The contact angle was evaluated for coatings of a monolayer (ML) and for surface densities of 2.89 μmol/m2 for each collector. For a ML, the hydrophobic effect generated by the aromatic ring of the MBT collector is comparable with the effect of the non-polar short chain of the PAX collector. The increase in hydrophobicity for the gold surfaces achieved by collectors with aliphatic chains is because the water-collector interaction energy is significantly higher (repulsive) than the water-gold interactions (attractive). The lowest increase in hydrophobicity was achieved with the MBT collector, since the carbon-water interaction energy of the aromatic ring is stronger than the interaction with the carbon atoms in the aliphatic chains. The calculated contact angles of the water droplets deviated less than 4% with respect to the experimental values.

Separation of oil from bilge water I. Bilge water characteristics and the interaction of bilge water with chemically modified surfaces. Interim report, October 1994-September 1995

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chang, E.L.; Calvert, J.M.; Koloski, T.

1997-02-01

We report on the results of a project using surface characterization and novel surface-modification techniques to address the issues of developing a minimally fouling ceramic membrane filter. We have studied the physical characteristics of a synthetic bilge water mixture, examined the surfaces of the ceramic filters for evidence of fouling, and identified several surface modifications that, under laboratory conditions, work well in prevention of foulants. These surfaces include hydrophobic as well as polar coatings. For the bilge water, it was discovered that detergent, at certain concentrations, may be useful in separating and coalescing oil droplets from the bilge water. Basedmore » on the results of the studies, several strategies for optimizing the removal of oil from water are suggested.« less

An in situ XPS study of L-cysteine co-adsorbed with water on polycrystalline copper and gold

NASA Astrophysics Data System (ADS)

Jürgensen, Astrid; Raschke, Hannes; Esser, Norbert; Hergenröder, Roland

2018-03-01

The interactions of biomolecules with metal surfaces are important because an adsorbed layer of such molecules introduces complex reactive functionality to the substrate. However, studying these interactions is challenging: they usually take place in an aqueous environment, and the structure of the first few monolayers on the surface is of particular interest, as these layers determine most interfacial properties. Ideally, this requires surface sensitive analysis methods that are operated under ambient conditions, for example ambient pressure x-ray photoelectron spectroscopy (AP-XPS). This paper focuses on an AP-XPS study of the interaction of water vapour and l-Cysteine on polycrystalline copper and gold surfaces. Thin films of l-Cysteine were characterized with XPS in UHV and in a water vapour atmosphere (P ≤ 1 mbar): the structure of the adsorbed l-Cysteine layer depended on substrate material and deposition method, and exposure of the surface to water vapour led to the formation of hydrogen bonds between H2O molecules and the COO- and NH2 groups of adsorbed l-Cysteine zwitterions and neutral molecules, respectively. This study also proved that it is possible to investigate monolayers of biomolecules in a gas atmosphere with AP-XPS using a conventional laboratory Al-Kα x-ray source.

Characterization of the interaction between AFM tips and surface nanobubbles.

PubMed

Walczyk, Wiktoria; Schönherr, Holger

2014-06-24

While the presence of gaseous enclosures observed at various solid-water interfaces, the so-called "surface nanobubles", has been confirmed by many groups in recent years, their formation, properties, and stability have not been convincingly and exhaustively explained. Here we report on an atomic force microscopy (AFM) study of argon nanobubbles on highly oriented pyrolitic graphite (HOPG) in water to elucidate the properties of nanobubble surfaces and the mechanism of AFM tip-nanobubble interaction. In particular, the deformation of the nanobubble-water interface by the AFM tip and the question whether the AFM tip penetrates the nanobubble during scanning were addressed by this combined intermittent contact (tapping) mode and force volume AFM study. We found that the stiffness of nanobubbles was smaller than the cantilever spring constant and comparable with the surface tension of water. The interaction with the AFM tip resulted in severe quasi-linear deformation of the bubbles; however, in the case of tip-bubble attraction, the interface deformed toward the tip. We tested two models of tip-bubble interaction, namely, the capillary force and the dynamic interaction model, and found, depending on the tip properties, good agreement with experimental data. The results showed that the tip-bubble interaction strength and the magnitude of the bubble deformation depend strongly on tip and bubble geometry and on tip and substrate material, and are very sensitive to the presence of contaminations that alter the interfacial tension. In particular, nanobubbles interacted differently with hydrophilic and hydrophobic AFM tips, which resulted in qualitatively and quantitatively different force curves measured on the bubbles in the experiments. To minimize bubble deformation and obtain reliable AFM results, nanobubbles must be measured with a sharp hydrophilic tip and with a cantilever having a very low spring constant in a contamination-free system.

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. Copyright © 2015 Elsevier Inc. All rights reserved.

Incorporating water-release and lateral protein interactions in modeling equilibrium adsorption for ion-exchange chromatography.

PubMed

Thrash, Marvin E; Pinto, Neville G

2006-09-08

The equilibrium adsorption of two albumin proteins on a commercial ion exchanger has been studied using a colloidal model. The model accounts for electrostatic and van der Waals forces between proteins and the ion exchanger surface, the energy of interaction between adsorbed proteins, and the contribution of entropy from water-release accompanying protein adsorption. Protein-surface interactions were calculated using methods previously reported in the literature. Lateral interactions between adsorbed proteins were experimentally measured with microcalorimetry. Water-release was estimated by applying the preferential interaction approach to chromatographic retention data. The adsorption of ovalbumin and bovine serum albumin on an anion exchanger at solution pH>pI of protein was measured. The experimental isotherms have been modeled from the linear region to saturation, and the influence of three modulating alkali chlorides on capacity has been evaluated. The heat of adsorption is endothermic for all cases studied, despite the fact that the net charge on the protein is opposite that of the adsorbing surface. Strong repulsive forces between adsorbed proteins underlie the endothermic heat of adsorption, and these forces intensify with protein loading. It was found that the driving force for adsorption is the entropy increase due to the release of water from the protein and adsorbent surfaces. It is shown that the colloidal model predicts protein adsorption capacity in both the linear and non-linear isotherm regions, and can account for the effects of modulating salt.

Chemical effect on ozone deposition over seawater

EPA Science Inventory

Surface layer resistance plays an important role in determining ozone deposition velocity over seawater. Recent studies suggest that surface layer resistance over sea-water is influenced by wind-speed and chemical interaction at the air-water interface. Here, we investigate the e...

River-spring connectivity and hydrogeochemical interactions in a shallow fractured rock formation. The case study of Fuensanta river valley (Southern Spain)

NASA Astrophysics Data System (ADS)

Barberá, J. A.; Andreo, B.

2017-04-01

In upland catchments, the hydrology and hydrochemistry of streams are largely influenced by groundwater inflows, at both regional and local scale. However, reverse conditions (groundwater dynamics conditioned by surface water interferences), although less described, may also occur. In this research, the local river-spring connectivity and induced hydrogeochemical interactions in intensely folded, fractured and layered Cretaceous marls and marly-limestones (Fuensanta river valley, S Spain) are discussed based on field observations, tracer tests and hydrodynamic and hydrochemical data. The differential flow measurements and tracing experiments performed in the Fuensanta river permitted us to quantify the surface water losses and to verify its direct hydraulic connection with the Fuensanta spring. The numerical simulations of tracer breakthrough curves suggest the existence of a groundwater flow system through well-connected master and tributary fractures, with fast and multi-source flow components. Furthermore, the multivariate statistical analysis conducted using chemical data from the sampled waters, the geochemical study of water-rock interactions and the proposed water mixing approach allowed the spatial characterization of the chemistry of the springs and river/stream waters draining low permeable Cretaceous formations. Results corroborated that the mixing of surface waters, as well as calcite dissolution and CO2 dissolution/exsolution, are the main geochemical processes constraining Fuensanta spring hydrochemistry. The estimated contribution of the tributary surface waters to the spring flow during the research period was approximately 26-53% (Fuensanta river) and 47-74% (Convento stream), being predominant the first component during high flow and the second one during the dry season. The identification of secondary geochemical processes (dolomite and gypsum dissolution and dedolomitization) in Fuensanta spring waters evidences the induced hydrogeochemical changes resulting from the allogenic recharge. This research highlights the usefulness of an integrated approach based on river and spring flow examination, dye tracing interpretation and regression and multivariate statistical analysis using hydrochemical data for surface water-groundwater interaction assessment in fractured complex environments worldwide, whose implementation becomes critical for an appropriate groundwater policy.

Molecular dynamics simulations of the adsorption of bone morphogenetic protein-2 on surfaces with medical relevance.

PubMed

Utesch, Tillmann; Daminelli, Grazia; Mroginski, Maria Andrea

2011-11-01

Bone morphogenetic protein-2 (BMP-2) plays a crucial role in osteoblast differentiation and proliferation. Its effective therapeutic use for ectopic bone and cartilage regeneration depends, among other factors, on the interaction with the carrier at the implant site. In this study, we used classical molecular dynamics (MD) and a hybrid approach of steered molecular dynamics (SMD) combined with MD simulations to investigate the initial stages of the adsorption of BMP-2 when approaching two implant surfaces, hydrophobic graphite and hydrophilic titanium dioxide rutile. Surface adsorption was evaluated for six different orientations of the protein, two end-on and four side-on, in explicit water environment. On graphite, we observed a weak but stable adsorption. Depending on the initial orientation, hydrophobic patches as well as flexible loops of the protein were involved in the interaction with graphite. On the contrary, BMP-2 adsorbed only loosely to hydrophilic titanium dioxide. Despite a favorable interaction energy between protein and the TiO(2) surface, the rapid formation of a two-layer water structure prevented the direct interaction between protein and titanium dioxide. The first water adlayer had a strong repulsive effect on the protein, while the second attracted the protein toward the surface. For both surfaces, hydrophobic graphite and hydrophilic titanium dioxide, denaturation of BMP-2 induced by adsorption was not observed on the nanosecond time scale.

Water interaction with hydrophobic and hydrophilic soot particles.

PubMed

Popovicheva, Olga; Persiantseva, Natalia M; Shonija, Natalia K; DeMott, Paul; Koehler, Kirsten; Petters, Markus; Kreidenweis, Sonia; Tishkova, Victoria; Demirdjian, Benjamin; Suzanne, Jean

2008-05-07

The interaction of water with laboratory soots possessing a range of properties relevant for atmospheric studies is examined by two complementary methods: gravimetrical measurement of water uptake coupled with chemical composition and porosity analysis and HTDMA (humidified tandem differential mobility analyzer) inference of water uptake accompanied by separate TEM (transmission electron microscopy) analysis of single particles. The first method clarifies the mechanism of water uptake for bulk soot and allows the classification of soot with respect to its hygroscopicity. The second method highlights the dependence of the soot aerosol growth factor on relative humidity (RH) for quasi-monodisperse particles. Hydrophobic and hydrophilic soot are qualitatively defined by their water uptake and surface polarity: laboratory soot particles are thus classified from very hydrophobic to very hydrophilic. Thermal soot particles produced from natural gas combustion are classified as hydrophobic with a surface of low polarity since water is found to cover only half of the surface. Graphitized thermal soot particles are proposed for comparison as extremely hydrophobic and of very low surface polarity. Soot particles produced from laboratory flame of TC1 aviation kerosene are less hydrophobic, with their entire surface being available for statistical monolayer water coverage at RH approximately 10%. Porosity measurements suggest that, initially, much of this surface water resides within micropores. Consequently, the growth factor increase of these particles to 1.07 at RH > 80% is attributed to irreversible swelling that accompanies water uptake. Hysteresis of adsorption/desorption cycles strongly supports this conclusion. In contrast, aircraft engine soot, produced from burning TC1 kerosene in a gas turbine engine combustor, has an extremely hydrophilic surface of high polarity. Due to the presence of water soluble organic and inorganic material it can be covered by many water layers even below water saturation conditions. This soot demonstrates a gradual diameter growth factor (D(wet)/D(dry)) increase up to 1.22 at 93% relative humidity, most likely due to the presence of single particles with water soluble material heterogeneously distributed over their surface.

Effect of rapidly changing river stage on uranium flux through the hyporheic zone.

PubMed

Fritz, Brad G; Arntzen, Evan V

2007-01-01

Measurement of ground water/surface water interaction within the hyporheic zone is increasingly recognized as an important aspect of subsurface contaminant fate and transport. Understanding the interaction between ground water and surface water is critical in developing a complete conceptual model of contaminant transport through the hyporheic zone. At the Hanford Site near Richland, Washington, ground water contaminated with uranium discharges to the Columbia River through the hyporheic zone. Ground water flux varies according to changes in hydraulic gradient caused by fluctuating river stage, which changes in response to operation of dams on the Columbia River. Piezometers and continuous water quality monitoring probes were installed in the hyporheic zone to provide long-term, high-frequency measurement of hydraulic gradient and estimated uranium concentrations. Subsequently, the flux of water and uranium was calculated for each half-hour time period over a 15-month study period. In addition, measurement of water levels in the near-shore unconfined aquifer enhanced the understanding of the relationship between river stage, aquifer elevation, and uranium flux. Changing river stage resulted in fluctuating hydraulic gradient within the hyporheic zone. Further, influx of river water caused lower uranium concentrations as a result of dilution. The methods employed in this study provide a better understanding of the interaction between surface and ground water in a situation with a dynamically varying vertical hydraulic gradient and illustrate how the combination of relatively standard methods can be used to derive an accurate estimation of water and contaminant flux through the hyporheic zone.

Hydrogen Isotopic Constraints on the Evolution of Surface and Subsurface Water on Mars

NASA Technical Reports Server (NTRS)

Usui, T.; Kurokawa, H.; Wang, J.; Alexander, C. M. O’D.; Simon, J. I.; Jones, J. H.

2017-01-01

The geology and geomorphology of Mars provide clear evidence for the presence of liquid water on its surface during the Noachian and Hesperien eras (i.e., >3 Ga). In contrast to the ancient watery environment, today the surface of Mars is relatively dry. The current desert-like surface conditions, however, do not necessarily indicate a lack of surface or near-surface water/ice. In fact, massive deposits of ground ice and/or icy sediments have been proposed based on subsurface radar sounder observations. Hence, accurate knowledge of both the evolution of the distribution of water and of the global water inventory is crucial to our understanding of the evolution of the climate and near-surface environments and the potential habitability of Mars. This study presents insights from hydrogen isotopes for the interactive evolution of Martian water reservoirs. In particular, based on our new measurement of the D/H ratio of 4 Ga-old Noachian water, we constrain the atmospheric loss and possible exchange of surface and subsurface water through time.

Surface-water/ground-water interaction along reaches of the Snake River and Henrys Fork, Idaho

USGS Publications Warehouse

Hortness, Jon E.; Vidmar, Peter

2005-01-01

Declining water levels in the eastern Snake River Plain aquifer and decreases in spring discharges from the aquifer to the Snake River have spurred studies to improve understanding of the surface-water/ground-water interaction on the plain. This study was done to estimate streamflow gains and losses along specific reaches of the Snake River and Henrys Fork and to compare changes in gain and loss estimates to changes in ground-water levels over time. Data collected during this study will be used to enhance the conceptual model of the hydrologic system and to refine computer models of ground-water flow and surface-water/ground-water interactions. Estimates of streamflow gains and losses along specific subreaches of the Snake River and Henrys Fork, based on the results of five seepage studies completed during 2001?02, varied greatly across the study area, ranging from a loss estimate of 606 ft3/s in a subreach of the upper Snake River near Heise to a gain estimate of 3,450 ft3/s in a subreach of the Snake River that includes Thousand Springs. Some variations over time also were apparent in specific subreaches. Surface spring flow accounted for much of the inflow to subreaches having large gain estimates. Several subreaches alternately gained and lost streamflow during the study. Changes in estimates of streamflow gains and losses along some of the subreaches were compared with changes in water levels, measured at three different times during 2001?02, in adjacent wells. In some instances, a strong relation between changes in estimates of gains or losses and changes in ground-water levels was apparent.

Forming chemical composition of surface waters in the Arctic as "water - rock" interaction. Case study of lake Inari and river Paz

NASA Astrophysics Data System (ADS)

Mazukhina, Svetlana; Sandimirov, Sergey; Pozhilenko, Vladimir; Ivanov, Stanislav; Maksimova, Viktoriia

2017-04-01

Due to the depletion of fresh water supplies and the deterioration of their quality as a result of anthropogenic impact on the Arctic ecosystems, the research questions of forming surface and ground waters, their interactions with the rocks, development of the foundations for their rational use and protection are of great fundamental and practical importance. The aim of the work is to evaluate the influence of the chemical composition of rocks of the northern part of the Fennoscandian (Baltic) shield on forming surface waters chemical composition (Lake Inari, river Paz) using physical-chemical modeling (Chudnenko, 2010, Selector software package). River Paz (Paatsjoki) is the largest river in North Fennoscandia and flows through the territory of three countries - Finland, Russia and Norway. It originates from Lake Inari, which a large number of streams and rivers flow into, coming from the mountain range of the northern Finland (Maanselkä hill). Within the catchment of inflows feeding the lake Inari and river Paz in its upper flow there are mainly diverse early Precambrian metamorphic and intrusive rocks of the Lapland granulite belt and its framing, and to a lesser extent - various gneisses and migmatites with relicts of amphibolites, granitic gneisses, plagioclase and plagio- and plagiomicrocline granites, and quartz diorites of Inari terrane (Meriläinen, 1976, fig 1; Hörmann et al, 1980, fig 1; Geologicalmap, 2001). Basing on the techniques developed earlier (Mazukhina, 2012), and the data of monitoring of the chemical composition of surface waters and investigation of the chemical composition of the rocks, physical-chemical modeling (FCM) (Selector software package) was carried out. FCM includes 34 independent components (Al-B-Br-Ar-He-Ne-C-Ca-Cl-F-Fe-K-Mg-Mn-N-Na-P-S-Si-Sr-Cu-Zn-Ni-Pb-V-Ba-Co-Cr-Hg-As-Cd-H-O-e), 996 dependent components, of them 369 in aqueous solution, 76 in the gas phase, 111 liquid hydrocarbons, and 440 solid phases, organic and mineral substances. A set of solid phases of the multisystem is formed with the mineral composition of the crystalline rocks of the Fennoscandian (Baltic) shield taken into account. The processes of forming the surface waters in the "water - rock - atmosphere" system depending on the degree of interaction (ξ) of rocks with aqueous solutions under open conditions (100 kg of atmosphere, 1000 kg of water, T-5oC, P-1 bar and rock (100 g) - the rock average composition: 1) Inari terrane rocks, 2) granulites of the Lapland granulite belt were investigated. Clarke concentrations of S, C, F, Zn, Ni, Pb, Cu (Vinogradov, 1962) were taken into account in order to determine their influence on forming the chemical composition of water solutions, and water migration coefficients (Perelman, 1989). Comparison of the modeling results with the monitoring results of the source of river Paz shows that the chemical composition of waters of lake Inari as well as the upper flow of river Paz is formed by interactions of surface waters, ground waters, and fissure waters with granulites of the Lapland granulite belt, as well as gneisses, diorites and granitoids of Inari terrane of the northern Fennoscandia. Thermodynamic modeling determined that the chemical composition of surface waters is formed as a result of interaction of atmospheric precipitation with intrusive and sedimentary rocks of the northern Fennoscandia, containing clarke concentrations of S, C, F, Zn, Ni, Pb, Cu. The obtained model solutions indicate that surface waters are formed within the considered system as a result of "water-rock-atmosphere" interaction.

Implementation and use of direct-flow connections in a coupled ground-water and surface-water model

USGS Publications Warehouse

Swain, Eric D.

1994-01-01

The U.S. Geological Survey's MODFLOW finite-difference ground-water flow model has been coupled with three surface-water packages - the MODBRANCH, River, and Stream packages - to simulate surface water and its interaction with ground water. Prior to the development of the coupling packages, the only interaction between these modeling packages was that leakage values could be passed between MODFLOW and the three surface-water packages. To facilitate wider and more flexible uses of the models, a computer program was developed and added to MODFLOW to allow direct flows or stages to be passed between any of the packages and MODFLOW. The flows or stages calculated in one package can be set as boundary discharges or stages to be used in another package. Several modeling packages can be used in the same simulation depending upon the level of sophistication needed in the various reaches being modeled. This computer program is especially useful when any of the River, Stream, or MODBRANCH packages are used to model a river flowing directly into or out of wetlands in direct connection with the aquifer and represented in the model as an aquifer block. A field case study is shown to illustrate an application.

Surface force and vibrational spectroscopic analyses of interfacial water molecules in the vicinity of methoxy-tri(ethylene glycol)-terminated monolayers: mechanisms underlying the effect of lateral packing density on bioinertness.

PubMed

Sekine, Taito; Asatyas, Syifa; Sato, Chikako; Morita, Shigeaki; Tanaka, Masaru; Hayashi, Tomohiro

Unequivocal dependence of bioinertness of self-assembled monolayers of methoxy-tri(ethylene glycol)-terminated alkanethiol (EG3-OMe SAMs) on their packing density has been a mystery for more than two decades. We tackled this long-standing question by performing surface force and surface-enhanced infrared absorption (SEIRA) spectroscopic measurements. Our surface force measurements revealed a physical barrier of interfacial water in the vicinity of the Au-supported EG3-OMe SAM (low packing density), whereas the Ag-supported one (high packing density) did not possess such interfacial water. In addition, the results of SEIRA measurements clearly exhibited that hydrogen bonding states of the interfacial water differ depending on the substrates. We also characterized the bioinertness of these SAMs by protein adsorption tests and adhesion assays of platelet and human umbilical vein endothelial cells. The hydrogen bonding states of the interfacial water and water-induced interaction clearly correlated with the bioinertness of the SAMs, suggesting that the interfacial water plays an important role determining the interaction of the SAMs with biomolecules and cells.

On the Interaction between Marine Boundary Layer Cellular Cloudiness and Surface Heat Fluxes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kazil, J.; Feingold, G.; Wang, Hailong

2014-01-02

The interaction between marine boundary layer cellular cloudiness and surface uxes of sensible and latent heat is investigated. The investigation focuses on the non-precipitating closed-cell state and the precipitating open-cell state at low geostrophic wind speed. The Advanced Research WRF model is used to conduct cloud-system-resolving simulations with interactive surface fluxes of sensible heat, latent heat, and of sea salt aerosol, and with a detailed representation of the interaction between aerosol particles and clouds. The mechanisms responsible for the temporal evolution and spatial distribution of the surface heat fluxes in the closed- and open-cell state are investigated and explained. Itmore » is found that the horizontal spatial structure of the closed-cell state determines, by entrainment of dry free tropospheric air, the spatial distribution of surface air temperature and water vapor, and, to a lesser degree, of the surface sensible and latent heat flux. The synchronized dynamics of the the open-cell state drives oscillations in surface air temperature, water vapor, and in the surface fluxes of sensible and latent heat, and of sea salt aerosol. Open-cell cloud formation, cloud optical depth and liquid water path, and cloud and rain water path are identified as good predictors of the spatial distribution of surface air temperature and sensible heat flux, but not of surface water vapor and latent heat flux. It is shown that by enhancing the surface sensible heat flux, the open-cell state creates conditions by which it is maintained. While the open-cell state under consideration is not depleted in aerosol, and is insensitive to variations in sea-salt fluxes, it also enhances the sea-salt flux relative to the closed-cell state. In aerosol-depleted conditions, this enhancement may replenish the aerosol needed for cloud formation, and hence contribute to the perpetuation of the open-cell state as well. Spatial homogenization of the surface fluxes is found to have only a small effect on cloud properties in the investigated cases. This indicates that sub-grid scale spatial variability in the surface flux of sensible and latent heat and of sea salt aerosol may not be required in large scale and global models to describe marine boundary layer cellular cloudiness.« less

Modification of land-atmosphere interactions by CO2 effects: Implications for summer dryness and heat wave amplitude

NASA Astrophysics Data System (ADS)

Lemordant, Léo.; Gentine, Pierre; Stéfanon, Marc; Drobinski, Philippe; Fatichi, Simone

2016-10-01

Plant stomata couple the energy, water, and carbon cycles. We use the framework of Regional Climate Modeling to simulate the 2003 European heat wave and assess how higher levels of surface CO2 may affect such an extreme event through land-atmosphere interactions. Increased CO2 modifies the seasonality of the water cycle through stomatal regulation and increased leaf area. As a result, the water saved during the growing season through higher water use efficiency mitigates summer dryness and the heat wave impact. Land-atmosphere interactions and CO2 fertilization together synergistically contribute to increased summer transpiration. This, in turn, alters the surface energy budget and decreases sensible heat flux, mitigating air temperature rise. Accurate representation of the response to higher CO2 levels and of the coupling between the carbon and water cycles is therefore critical to forecasting seasonal climate, water cycle dynamics, and to enhance the accuracy of extreme event prediction under future climate.

Desktop Techniques for Analyzing Surface-Ground Water Interactions. The Reelfoot Lake Case Study

DTIC Science & Technology

1988-05-01

Reelfoot Lake Case Study DTlCSELECTE JUN 13 M Research Document No. 28 May 1988 Approved for Public Release. Distribution Unlimited. 86 , l~ g DESKTOP...TECHNIQUES FOR ANALYZING SURFACE-GROUND WATER INTERACTIONS The Reelfoot Lake Case Study Prepared by Dennis B. McLaughlin ’ Ia Prepared for The...Engineers became involved in a study of Reelfoot Lake , a large natural lake in northwestern Tennessee. Although modeling studies of the lake and its

DOE Office of Scientific and Technical Information (OSTI.GOV)

Farmer, R.W.; Dussert, B.W.; Kovacic, S.L.

Laboratory studies have identified the cause of the pH rise, which occurs during water treatment with activated carbon, as an interaction between the naturally occurring anions and protons in the water and the carbon surface. The interaction can be described as an ion exchange type of phenomenon, in which the carbon surface sorbs the anions and corresponding hydronium ions from the water. These studies have shown that the anion sorption and resulting pH increase is independent of the raw material used for the activated carbon production, e.g. bituminous or subbituminous coal, peat, wood or coconut. Also, the pH excursions occurmore » with virgin, reactivated, and acid washed granular carbons. Current pH control technologies focus on adjustment of the wastewater pH prior to discharge or recycle of the initial effluent water until the pH increase abates. However, improved water pH control options have been realized by altering the carbon surface through controlled oxidation rather than the water chemistry or extended preprocessing at the treatment site.« less

Surface rearrangement of water-immersed hydrophobic solids by gaseous nanobubbles.

PubMed

Tarábková, Hana; Bastl, Zdeněk; Janda, Pavel

2014-12-09

Interactions of gaseous (ambient) nanobubbles (10-100 nm diameter) with different hydrophobic materials-Teflon, polystyrene, paraffin, and basal plane highly ordered pyrolytic graphite (HOPG)-are studied by AFM in situ and ex situ. Exactly identical surface locations are examined before and after exposure to ambient gas nanobubbles in deionized water and compared for nanomorphological changes. While freely flooded/immersed surfaces, regularly occupied by nanobubbles, do not exhibit resolvable alterations, significant surface rearrangement is found on whole flooded area after mild pressure drop (10 kPa) applied on the solid-liquid interface. Nanopattern and its characteristic dimension appear to be material specific and solely reflect surface-nanobubble interaction. Mild, nonswelling, noncorrosive conditions (20 °C, deionized water) prevent intervention of chemical reaction and high-energy-demanding processes. Experimental results, in accordance with the presented model, indicate that the mild pressure drop triggers expansion of pinned nanobubbles, imposing local tensile stress on the solid surface. Consequently, nanobubbles should be considered as large-area nanoscale patterning elements.

Modeling Water Waves with Smoothed Particle Hydrodynamics

DTIC Science & Technology

2013-09-30

SPH Model for Water Waves and Other Free Surface Flows ...Lagrangian nature of SPH allows the modeling of wave breaking, surf zones, ship waves, and wave-structure interaction, where the free surface becomes...proving to be a competent modeling scheme for free surface flows in three dimensions including the complex flows of the surf zone. As the GPU

Characterization of protein hydration by solution NMR spectroscopy

NASA Astrophysics Data System (ADS)

Wand, Joshua

A comprehensive understanding of the interactions between protein molecules and hydration water remains elusive. Solution nuclear magnetic resonance (NMR) spectroscopy has been proposed as a means to characterize these interactions but is plagued with artifacts when employed in bulk aqueous solution. Encapsulation of proteins in reverse micelles prepared in short chain alkane solvents can overcome these technical limitations. Application of this approach has revealed that the interaction of water with the surface of protein molecules is quite heterogeneous with some regions of the protein having long-lived interactions while other regions show relatively transient hydration. Results from several proteins will be presented including ubiquitin, staphylococcal nuclease, interleukin 1beta, hen egg white lysozyme (HEWL) and T4 lysozyme. Ubiquitin and interleukin 1beta are signaling proteins and interact with other proteins through formation of dry protein-protein interfaces. Interestingly, the protein surfaces of the free proteins show relatively slowed (restricted) motion at the surface, which is indicative of low residual entropy. Other regions of the protein surface have relatively high mobility water. These results are consistent with the idea that proteins have evolved to maximize the hydrophobic effect in optimization of binding with protein partners. As predicted by simulation and theory, we find that hydration of internal hydrophobic cavities of interleukin 1beta and T4 lysozyme is highly disfavored. In contrast, the hydrophilic polar cavity of HEWL is occupied by water. Initial structural correlations suggest that hydration of alpha helical structure is characterized by relatively mobile water while those of beta strands and loops are more ordered and slowed. These and other results from this set of proteins reveals that the dynamical and structural character of hydration of proteins is heterogeneous and complex. Supported by the National Science Foundation.

Groundwater-surface water interactions and their effects on ecosystem metabolism in a coastal wetland: example from the Florida Everglades

NASA Astrophysics Data System (ADS)

Price, R. M.; Zapata, X.; Koch, G. R.

2013-05-01

Groundwater typically has higher concentrations of salts and nutrients as compared to surface waters in coastal wetlands affected by saltwater intrusion. Discharge of the nutrient-laden brackish groundwater is expected to influence ecosystem function in the overlying surface water. In the coastal Everglades, elevated concentrations of phosphorus have been observed in the underlying groundwater due to water-rock interactions occurring as seawater intrudes into the coastal carbonate aquifer. The objective of this research was to determine the timing and amount of brackish groundwater discharge to the coastal wetlands of the Everglades and to evaluate the effects of the groundwater discharge on the surface water chemistry and ecosystem metabolism. The timing of groundwater discharge was determined by four techniques including a water balance, hydraulic gradient, temperature, and geochemical tracers. Groundwater discharge rates were quantified from well data using Darcy's Law. Ecosystem metabolism was estimated as daily rates of gross primary production (GPP), ecosystem respiration (R) and net ecosystem production (NEP) from free-water, diel changes in dissolved oxygen. Over 2 years, all four groundwater discharge techniques converged as to the timing of groundwater discharge which was greatest between May and July. Surface water chemistry was fresh from September through February, but became brackish to hypersaline between March and July, concurrent with the times of highest brackish groundwater discharge. Phosphorus concentrations as well as GPP and R were observed to spike in the surface water during the times of greatest groundwater discharge. The results of this research support the conclusions that brackish groundwater discharge effects surface water chemistry and ecosystem function in the coastal Everglades.

Water clusters contributed to molecular interactions of ionizable organic pollutants with aromatized biochar via π-PAHB: Sorption experiments and DFT calculations.

PubMed

Zhang, Kun; Chen, Baoliang; Mao, Jiefei; Zhu, Lizhong; Xing, Baoshan

2018-05-08

Molecular interactions between biochars and ionizable organic pollutants (IOPs) are of great concern in natural environments, however the role of water clusters on the biochar surface remain unclear. The pH-dependent adsorption of aniline, phenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 4-methylphenol and 4-nitrophenol onto bamboo wood derived biochar (BW700) as a model was conducted to identify conventional and novel interaction mechanisms between aromatized surface and IOPs. The dissociation constant (pK a,surface ) of surface functional groups of BW700 was characterized by acid-base titration and Zeta potential measurements. The pH-dependent adsorption behavior depended on the pK a,IOP of IOPs and also related to the pK a,surface of biochar surface. An obvious peak of adsorption coefficients (K d ) in the range of solution pH was shaped at pH peak  = (pK a,IOP  + pK a,surface )/2, which cannot be well explained by the conventional mechanisms such as hydrophobic effects, π-π interaction, electrostatic attractions, and hydrogen-binding. The contribution of ice-like adlayer (water clusters) on aromatic surface as H-acceptors is proposed for the first time to the adsorption peak of IOP as H-donors at pH peak . Density functional theory (DFT) calculations provided a possible structure of the complex combined with ice-like adlayer and aromatic substrate of BW700, and indicated that the adsorbing peak resulted from the multiple π-bond and polarization assisted H-bond (π-PAHB) interactions. Three distinct properties of π-PAHB were given, based on multiple π-bond, hydrophobicity-dependence and pH sensitivity. This novel mechanism extends the definition of H-bonds for better understanding the molecular interactions of IOP with carbonaceous materials and their environmental fate. Copyright © 2018 Elsevier Ltd. All rights reserved.

SELMA mission: revealing the origin of lunar water

NASA Astrophysics Data System (ADS)

Barabash, Stas; Selma Team

2013-04-01

We propose a very low cost lunar mission to cover a poorly investigated inter-disciplinary area in the lunar science. The mission SELMA (Surface, Environment, and Lunar Magnetic Anomalies) investigates the interaction of the neutral and plasma environment with the lunar surface and the impact of this interaction on the surface composition, in the first hand, on the presence of water. The mission focuses on the fundamental question: What is the origin of the water in the lunar soil? The mission also addresses the questions: What are the lunar exosphere content and composition and how does the exosphere interact with the surface? How do the lunar magnetic anomalies interact with the solar wind and affect the surface? SELMA investigates the origin of the water in the lunar soil via simultaneous measurements of the OH/H2O abundance in the soil, the proton flux deposited to the surface, and transient changes in the exospheric gas content and composition. The water content in the surface is mapped via measurements of the 2700 - 3300 nm OH/H2O/ice absorption lines. The proton flux at the surface is measured remotely via backscattered hydrogen flux (energetic neutral atoms, ENAs). The exospheric gas content and composition and possible transient changes due to micrometeoroid influx or outgassing are monitored by a neutral gas mass spectrometer. Little is known about the tenuous lunar exosphere, its composition, structure, and relation to the plasma environment. The reasons for the present poor knowledge of the lunar exosphere is the difficulty of observations due to the low number densities, and the complexity of models due to the multiplicity of the mechanisms responsible for the input and loss of exospheric species. To investigate the lunar exosphere SELMA is equipped with state-of-the-art time-of-flight neutral gas mass spectrometer with unprecedented sensitivity and mass resolution. The Moon does not have a global magnetic field but possesses local magnetizations. The magnetizations interact with the solar wind plasma creating highly variable mini-magnetospheres affecting, through an as yet unknown mechanism, the surface visible albedo. The electrodynamical interaction is very complex being one of the fundamental solar wind interactions in the solar system. SELMA studies how the magnetic anomaly interact with the solar wind and surface via simultaneous measurements of 3D ion and electron distribution functions, the local magnetic field, solar wind flux variations on the surface through ENA imaging of the backscattered hydrogen flux, imaging in the visible range, and measuring the surface IR spectrum. The SELMA results will be of critical importance for the interpretation of data from Mercury to be collected by the ESA BepiColombo mission in 2020 - 2022. To address its scientific objectives SELMA carries a highly focused suite of instruments including an IR spectrometer, an ENA telescope, an ion and electron spectrometer, a neutral gas mass spectrometer, a magnetometer, and a visible camera. SELMA is a spinning platform to be inserted on a low maintenance quasi-frozen polar orbit of 30 km x 216 km by a dedicated launch and a solid state fuel kick stage. SELMA was proposed to ESA as a candidate for the S-class mission.

Diaminoethane adsorption and water substitution on hydrated TiO2: a thermochemical study based on first-principles calculations.

PubMed

Hémeryck, Anne; Motta, Alessandro; Swiatowska, Jolanta; Pereira-Nabais, Catarina; Marcus, Philippe; Costa, Dominique

2013-07-14

Epoxy-amines are used as structural adhesives deposited on Ti. The amine adhesion to a Ti surface depends highly on the surface state (oxidation, hydroxylation). Amines may adsorb above preadsorbed water molecules or substitute them to bind directly to surface Ti(4+) Lewis acid sites. The adsorption of a model amine molecule, diaminoethane (DAE), on a model surface, hydrated TiO2-anatase (101) surface, is investigated using Density Functional Theory including Dispersive forces (DFT-D) calculations. DAE adsorption and water substitution by DAE are exothermic processes and turn nearly isoenergetic at high coverage with adsorption-substitution energies around -0.3 eV (including dispersion forces and ZPE). Complementary ab initio molecular dynamics studies also suggest that the formation of an amine-water interaction induces water desorption from the surface at room temperature, a preliminary step towards the amine-Ti bond formation. An atomistic thermodynamic approach is developed to evaluate the interfacial free energy balance of both processes (adsorption and substitution). The main contributions to the energetic balance are dispersive interactions between molecules and the surface on the exergonic side, translational and rotational entropic contributions on the endergonic one. The substitution process is stabilized by 0.55 eV versus the adsorption one when free solvation, rotational and vibrational energies are considered. The main contribution to this free energy gain is due to water solvation. The calculations suggest that in toluene solvent with a water concentration of 10(-4) M or less, a full DAE layer replaces a preadsorbed water layer for a threshold concentration of DAE ≥ 0.1 M.

Evidence for Interactions between Surface Water and Periphyton Biofilms in Artificial Streams

EPA Science Inventory

Studies suggest that periphyton in streambeds can harbor fecal indicator bacteria (FIB) and, under certain circumstances, can be transferred from the periphyton biofilm into the surface water. An indoor mesocosm study was conducted at the U.S. Environmental Protection Agency Expe...

Hydrophilization and hydrophobic recovery in polymers obtained by casting of polymer solutions on water surface.

PubMed

Bormashenko, Edward; Chaniel, Gilad; Gendelman, Oleg

2014-12-01

We demonstrate the possibility of hydrophilization of polymer films in situ under the process of their preparation. The polymer surface is hydrophilized when the polymer solution is spread on the water surface and the solvent is evaporated. Essential hydrophilization of the polymer surface is achieved under this process. We relate the observed hydrophilization of polymer films to the dipole-dipole interaction of the polar moieties of polymer chains with highly polar water molecules. The dipole-dipole interaction between water molecules and polar groups of polymer chains, orienting the polar groups of a polymer, may prevail over the London dispersion forces. The process, reported in the paper, allows to manufacture the films in which the hydrophilic moieties of the polymer molecule are oriented toward the polymer/air interface. It is demonstrated that even such traditionally extremely hydrophobic polymers as polydimethylsiloxane can be markedly hydrophilized. This hydrophilization, however, does not persist forever. After removal from the water surface, hydrophobic recovery was observed, i.e. polymer films restored their hydrophobicity with time. The characteristic time of the hydrophobic recovery is on the order of magnitude of hours. Copyright © 2014 Elsevier Inc. All rights reserved.

Wetting and evaporation of salt-water nanodroplets: A molecular dynamics investigation.

PubMed

Zhang, Jun; Borg, Matthew K; Sefiane, Khellil; Reese, Jason M

2015-11-01

We employ molecular dynamics simulations to study the wetting and evaporation of salt-water nanodroplets on platinum surfaces. Our results show that the contact angle of the droplets increases with the salt concentration. To verify this, a second simulation system of a thin salt-water film on a platinum surface is used to calculate the various surface tensions. We find that both the solid-liquid and liquid-vapor surface tensions increase with salt concentration and as a result these cause an increase in the contact angle. However, the evaporation rate of salt-water droplets decreases as the salt concentration increases, due to the hydration of salt ions. When the water molecules have all evaporated from the droplet, two forms of salt crystals are deposited, clump and ringlike, depending on the solid-liquid interaction strength and the evaporation rate. To form salt crystals in a ring, it is crucial that there is a pinned stage in the evaporation process, during which salt ions can move from the center to the rim of the droplets. With a stronger solid-liquid interaction strength, a slower evaporation rate, and a higher salt concentration, a complete salt crystal ring can be deposited on the surface.

Modelling of deformation of underground tunnel lining, interacting with water-saturated soil

NASA Astrophysics Data System (ADS)

Berezhnoi, D. V.; Balafendieva, I. S.; Sachenkov, A. A.; Sekaeva, L. R.

2016-11-01

Built finite element method of calculating the deformation of underground tunnel lining, interacting with dry and water-saturated soils. To simulate the interaction between the lining and soils environments, including physical and non-linear, a special "contact" finite element, which allows to consider all cases of interaction between the contacting surfaces. It solved a number of problems of deformation with the ground subway tunnel lining rings.

On the molecular origins of biomass recalcitrance: the interaction network and solvation structures of cellulose microfibrils.

PubMed

Gross, Adam S; Chu, Jhih-Wei

2010-10-28

Biomass recalcitrance is a fundamental bottleneck to producing fuels from renewable sources. To understand its molecular origin, we characterize the interaction network and solvation structures of cellulose microfibrils via all-atom molecular dynamics simulations. The network is divided into three components: intrachain, interchain, and intersheet interactions. Analysis of their spatial dependence and interaction energetics indicate that intersheet interactions are the most robust and strongest component and do not display a noticeable dependence on solvent exposure. Conversely, the strength of surface-exposed intrachain and interchain hydrogen bonds is significantly reduced. Comparing the interaction networks of I(β) and I(α) cellulose also shows that the number of intersheet interactions is a clear descriptor that distinguishes the two allomorphs and is consistent with the observation that I(β) is the more stable form. These results highlight the dominant role of the often-overlooked intersheet interactions in giving rise to biomass recalcitrance. We also analyze the solvation structures around the surfaces of microfibrils and show that the structural and chemical features at cellulose surfaces constrict water molecules into specific density profiles and pair correlation functions. Calculations of water density and compressibility in the hydration shell show noticeable but not drastic differences. Therefore, specific solvation structures are more prominent signatures of different surfaces.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Jian; Guo, Pan; University of Chinese Academy of Sciences, Beijing 100049

Using molecular dynamics simulations, we show a fine linear relationship between surface energies and microscopic Lennard-Jones parameters of super-hydrophilic surfaces. The linear slope of the super-hydrophilic surfaces is consistent with the linear slope of the super-hydrophobic, hydrophobic, and hydrophilic surfaces where stable water droplets can stand, indicating that there is a universal linear behavior of the surface energies with the water-surface van der Waals interaction that extends from the super-hydrophobic to super-hydrophilic surfaces. Moreover, we find that the linear relationship exists for various substrate types, and the linear slopes of these different types of substrates are dependent on the surfacemore » atom density, i.e., higher surface atom densities correspond to larger linear slopes. These results enrich our understanding of water behavior on solid surfaces, especially the water wetting behaviors on uncharged super-hydrophilic metal surfaces.« less

Statistical robustness of machine-learning estimates for characterizing a groundwater-surface water system, Southland, New Zealand

NASA Astrophysics Data System (ADS)

Friedel, M. J.; Daughney, C.

2016-12-01

The development of a successful surface-groundwater management strategy depends on the quality of data provided for analysis. This study evaluates the statistical robustness when using a modified self-organizing map (MSOM) technique to estimate missing values for three hypersurface models: synoptic groundwater-surface water hydrochemistry, time-series of groundwater-surface water hydrochemistry, and mixed-survey (combination of groundwater-surface water hydrochemistry and lithologies) hydrostratigraphic unit data. These models of increasing complexity are developed and validated based on observations from the Southland region of New Zealand. In each case, the estimation method is sufficiently robust to cope with groundwater-surface water hydrochemistry vagaries due to sample size and extreme data insufficiency, even when >80% of the data are missing. The estimation of surface water hydrochemistry time series values enabled the evaluation of seasonal variation, and the imputation of lithologies facilitated the evaluation of hydrostratigraphic controls on groundwater-surface water interaction. The robust statistical results for groundwater-surface water models of increasing data complexity provide justification to apply the MSOM technique in other regions of New Zealand and abroad.

From hydration repulsion to dry adhesion between asymmetric hydrophilic and hydrophobic surfaces

PubMed Central

Kanduč, Matej; Netz, Roland R.

2015-01-01

Using all-atom molecular dynamics (MD) simulations at constant water chemical potential in combination with basic theoretical arguments, we study hydration-induced interactions between two overall charge-neutral yet polar planar surfaces with different wetting properties. Whether the water film between the two surfaces becomes unstable below a threshold separation and cavitation gives rise to long-range attraction, depends on the sum of the two individual surface contact angles. Consequently, cavitation-induced attraction also occurs for a mildly hydrophilic surface interacting with a very hydrophobic surface. If both surfaces are very hydrophilic, hydration repulsion dominates at small separations and direct attractive force contribution can—if strong enough—give rise to wet adhesion in this case. In between the regimes of cavitation-induced attraction and hydration repulsion we find a narrow range of contact angle combinations where the surfaces adhere at contact in the absence of cavitation. This dry adhesion regime is driven by direct surface–surface interactions. We derive simple laws for the cavitation transition as well as for the transition between hydration repulsion and dry adhesion, which favorably compare with simulation results in a generic adhesion state diagram as a function of the two surface contact angles. PMID:26392526

Fluorescent Water Soluble Polymers for Isozyme-Selective Interactions with Matrix Metalloproteinase-9

PubMed Central

Dutta, Rinku; Scott, Michael D.; Haldar, Manas K.; Ganguly, Bratati; Srivastava, D. K.; Friesner, Daniel L.; Mallik, Sanku

2011-01-01

Matrix metalloproteinases (MMPs) are overexpressed in various pathological conditions, including various cancers. Although these isozymes have similar active sites, the patterns of exposed amino acids on their surfaces are different. Herein, we report the synthesis and molecular interactions of two water-soluble, fluorescent polymers which demonstrate selective interactions with MMP-9 compared to MMP-7 and -10. PMID:21367603

Contributions of nanoscale roughness to anomalous colloid retention and stability behavior

USDA-ARS?s Scientific Manuscript database

All natural surfaces exhibit nanoscale roughness (NR) and chemical heterogeneity (CH) to some extent. Expressions were developed to determine the mean interaction energy between a colloid and a solid-water interface (SWI), as well as for colloid-colloid interactions, when both surfaces contain binar...

Modulating surface rheology by electrostatic protein/polysaccharide interactions.

PubMed

Ganzevles, Renate A; Zinoviadou, Kyriaki; van Vliet, Ton; Cohen, Martien A; de Jongh, Harmen H

2006-11-21

There is a large interest in mixed protein/polysaccharide layers at air-water and oil-water interfaces because of their ability to stabilize foams and emulsions. Mixed protein/polysaccharide adsorbed layers at air-water interfaces can be prepared either by adsorption of soluble protein/polysaccharide complexes or by sequential adsorption of complexes or polysaccharides to a previously formed protein layer. Even though the final protein and polysaccharide bulk concentrations are the same, the behavior of the adsorbed layers can be very different, depending on the method of preparation. The surface shear modulus of a sequentially formed beta-lactoglobulin/pectin layer can be up to a factor of 6 higher than that of a layer made by simultaneous adsorption. Furthermore, the surface dilatational modulus and surface shear modulus strongly (up to factors of 2 and 7, respectively) depend on the bulk -lactoglobulin/pectin mixing ratio. On the basis of the surface rheological behavior, a mechanistic understanding of how the structure of the adsorbed layers depends on the protein/polysaccharide interaction in bulk solution, mixing ratio, ionic strength, and order of adsorption to the interface (simultaneous or sequential) is derived. Insight into the effect of protein/polysaccharide interactions on the properties of adsorbed layers provides a solid basis to modulate surface rheological behavior.

On the representation of many-body interactions in water

DOE PAGES

Medders, Gregory R.; Gotz, Andreas W.; Morales, Miguel A.; ...

2015-09-09

Our recent work has shown that the many-body expansion of the interactionenergy can be used to develop analytical representations of global potential energy surfaces (PESs) for water. In this study, the role of short- and long-range interactions at different orders is investigated by analyzing water potentials that treat the leading terms of the many-body expansion through implicit (i.e., TTM3-F and TTM4-F PESs) and explicit (i.e., WHBB and MB-pol PESs) representations. Moreover, it is found that explicit short-range representations of 2-body and 3-body interactions along with a physically correct incorporation of short- and long-range contributions are necessary for an accurate representationmore » of the waterinteractions from the gas to the condensed phase. Likewise, a complete many-body representation of the dipole moment surface is found to be crucial to reproducing the correct intensities of the infrared spectrum of liquid water.« less

Interactions in the aqueous phase and adsorption at the air-water interface of caseinoglycomacropeptide (GMP) and beta-lactoglobulin mixed systems.

PubMed

Martinez, María J; Sánchez, Cecilio Carrera; Patino, Juan M Rodríguez; Pilosof, Ana M R

2009-01-01

The aim of this work was to study the interactions and adsorption of caseinoglycomacropeptide (GMP) and GMP:beta-lactoglobulin (beta-lg) mixed system in the aqueous phase and at the air-water interface. The existence of associative interactions between GMP and beta-lg in the aqueous phase was investigated by dynamic light scattering, differential scanning calorimetry (DSC), fluorometry and native PAGE-electrophoresis. The surface pressure isotherm and the static and dynamic surface pressure were determined by tensiometry and surface dilatational properties. The results showed that GMP presented higher surface activity than beta-lg at a concentration of 4%wt but beta-lg showed higher film forming ability. In the mixed systems beta-lg dominated the static and dynamic surface pressure and the rheological properties of interfacial films suggesting that beta-lg hinders GMP adsorption because, in simple competition, GMP should dominate because of its higher surface activity. The surface predominance of beta-lg can be attributed to binding of GMP to beta-lg in the aqueous phase that prevents GMP adsorption on its own.

Quantifying why urea is a protein denaturant, whereas glycine betaine is a protein stabilizer

PubMed Central

Guinn, Emily J.; Pegram, Laurel M.; Capp, Michael W.; Pollock, Michelle N.; Record, M. Thomas

2011-01-01

To explain the large, opposite effects of urea and glycine betaine (GB) on stability of folded proteins and protein complexes, we quantify and interpret preferential interactions of urea with 45 model compounds displaying protein functional groups and compare with a previous analysis of GB. This information is needed to use urea as a probe of coupled folding in protein processes and to tune molecular dynamics force fields. Preferential interactions between urea and model compounds relative to their interactions with water are determined by osmometry or solubility and dissected using a unique coarse-grained analysis to obtain interaction potentials quantifying the interaction of urea with each significant type of protein surface (aliphatic, aromatic hydrocarbon (C); polar and charged N and O). Microscopic local-bulk partition coefficients Kp for the accumulation or exclusion of urea in the water of hydration of these surfaces relative to bulk water are obtained. Kp values reveal that urea accumulates moderately at amide O and weakly at aliphatic C, whereas GB is excluded from both. These results provide both thermodynamic and molecular explanations for the opposite effects of urea and glycine betaine on protein stability, as well as deductions about strengths of amide NH—amide O and amide NH—amide N hydrogen bonds relative to hydrogen bonds to water. Interestingly, urea, like GB, is moderately accumulated at aromatic C surface. Urea m-values for protein folding and other protein processes are quantitatively interpreted and predicted using these urea interaction potentials or Kp values. PMID:21930943

Quantifying why urea is a protein denaturant, whereas glycine betaine is a protein stabilizer.

PubMed

Guinn, Emily J; Pegram, Laurel M; Capp, Michael W; Pollock, Michelle N; Record, M Thomas

2011-10-11

To explain the large, opposite effects of urea and glycine betaine (GB) on stability of folded proteins and protein complexes, we quantify and interpret preferential interactions of urea with 45 model compounds displaying protein functional groups and compare with a previous analysis of GB. This information is needed to use urea as a probe of coupled folding in protein processes and to tune molecular dynamics force fields. Preferential interactions between urea and model compounds relative to their interactions with water are determined by osmometry or solubility and dissected using a unique coarse-grained analysis to obtain interaction potentials quantifying the interaction of urea with each significant type of protein surface (aliphatic, aromatic hydrocarbon (C); polar and charged N and O). Microscopic local-bulk partition coefficients K(p) for the accumulation or exclusion of urea in the water of hydration of these surfaces relative to bulk water are obtained. K(p) values reveal that urea accumulates moderately at amide O and weakly at aliphatic C, whereas GB is excluded from both. These results provide both thermodynamic and molecular explanations for the opposite effects of urea and glycine betaine on protein stability, as well as deductions about strengths of amide NH--amide O and amide NH--amide N hydrogen bonds relative to hydrogen bonds to water. Interestingly, urea, like GB, is moderately accumulated at aromatic C surface. Urea m-values for protein folding and other protein processes are quantitatively interpreted and predicted using these urea interaction potentials or K(p) values.

Insight into Chemistry on Cloud/Aerosol Water Surfaces.

PubMed

Zhong, Jie; Kumar, Manoj; Francisco, Joseph S; Zeng, Xiao Cheng

2018-05-15

Cloud/aerosol water surfaces exert significant influence over atmospheric chemical processes. Atmospheric processes at the water surface are observed to follow mechanisms that are quite different from those in the gas phase. This Account summarizes our recent findings of new reaction pathways on the water surface. We have studied these surface reactions using Born-Oppenheimer molecular dynamics simulations. These studies provide useful information on the reaction time scale, the underlying mechanism of surface reactions, and the dynamic behavior of the product formed on the aqueous surface. According to these studies, the aerosol water surfaces confine the atmospheric species into a specific orientation depending on the hydrophilicity of atmospheric species or the hydrogen-bonding interactions between atmospheric species and interfacial water. As a result, atmospheric species are activated toward a particular reaction on the aerosol water surface. For example, the simplest Criegee intermediate (CH 2 OO) exhibits high reactivity toward the interfacial water and hydrogen sulfide, with the reaction times being a few picoseconds, 2-3 orders of magnitude faster than that in the gas phase. The presence of interfacial water molecules induces proton-transfer-based stepwise pathways for these reactions, which are not possible in the gas phase. The strong hydrophobicity of methyl substituents in larger Criegee intermediates (>C1), such as CH 3 CHOO and (CH 3 ) 2 COO, blocks the formation of the necessary prereaction complexes for the Criegee-water reaction to occur at the water droplet surface, which lowers their proton-transfer ability and hampers the reaction. The aerosol water surface provides a solvent medium for acids (e.g., HNO 3 and HCOOH) to participate in reactions via mechanisms that are different from those in the gas and bulk aqueous phases. For example, the anti-CH 3 CHOO-HNO 3 reaction in the gas phase follows a direct reaction between anti-CH 3 CHOO and HNO 3 , whereas on a water surface, the HNO 3 -mediated stepwise hydration of anti-CH 3 CHOO is dominantly observed. The high surface/volume ratio of interfacial water molecules at the aerosol water surface can significantly lower the energy barriers for the proton transfer reactions in the atmosphere. Such catalysis by the aerosol water surface is shown to cause the barrier-less formation of ammonium bisulfate from hydrated NH 3 and SO 3 molecules rather than from the reaction of H 2 SO 4 with NH 3 . Finally, an aerosol water droplet is a polar solvent, which would favorably interact with high polarity substrates. This can accelerate interconversion of different conformers (e.g., anti and syn) of atmospheric species, such as glyoxal, depending on their polarity. The results discussed here enable an improved understanding of atmospheric processes on the aerosol water surface.

Complete Soil-Structure Interaction (SSI) Analyses of I-walls Embedded in Level Ground During Flood Loading

DTIC Science & Technology

2012-09-01

at the ground surface el 0 ft versus water elevation...sheet pile at the ground surface . ................ 62  Figure 3.24. Total displacements for a water elevation of 16.5 ft and a gap tip elevation of -11...103  Figure 4.19. Relative horizontal displacements of the sheet pile at the ground surface

Seasonal variation and partitioning of endocrine disrupting chemicals in waters and sediments of the Pearl River system, South China.

PubMed

Gong, Jian; Duan, Dandan; Yang, Yu; Ran, Yong; Chen, Diyun

2016-12-01

Endocrine disrupting chemicals (EDCs) were seasonally investigated in surface water, suspended particulate matter, and sediments of the Pearl River Delta (PRD), South China. EDC concentrations in the surface water were generally higher in the summer than in winter. The surface water in the investigated rivers was heavily contaminated by the phenolic xenoestrogens. Moreover, the in-situ log K soc and log K poc values and their regression with log K ow in the field experiments suggest that binding mechanisms other than hydrophobic interaction are present for the sedimentary organic carbon and particulate organic carbon (SOC/POC). The logK soc -logK ow and logK poc -logK ow regression analyses imply that higher complexity of nonhydrophobic interactions with EDCs is present on the SOC samples comparing with the POC samples, which is related to their different sources. Copyright © 2016 Elsevier Ltd. All rights reserved.

Molecular dynamics simulations of the surface tension and structure of salt solutions and clusters.

PubMed

Sun, Lu; Li, Xin; Hede, Thomas; Tu, Yaoquan; Leck, Caroline; Ågren, Hans

2012-03-15

Sodium halides, which are abundant in sea salt aerosols, affect the optical properties of aerosols and are active in heterogeneous reactions that cause ozone depletion and acid rain problems. Interfacial properties, including surface tension and halide anion distributions, are crucial issues in the study of the aerosols. We present results from molecular dynamics simulations of water solutions and clusters containing sodium halides with the interatomic interactions described by a conventional force field. The simulations reproduce experimental observations that sodium halides increase the surface tension with respect to pure water and that iodide anions reach the outermost layer of water clusters or solutions. It is found that the van der Waals interactions have an impact on the distribution of the halide anions and that a conventional force field with optimized parameters can model the surface tension of the salt solutions with reasonable accuracy. © 2012 American Chemical Society

Influence of the Hyporheic Zone on Supersaturated Gas Exposure to Incubating Chum Salmon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arntzen, Evan V.; Geist, David R.; Murray, Katherine J.

2009-12-01

Supersaturated total dissolved gas (TDG) is elevated seasonally in the lower Columbia River, with surface water concentrations approaching 120% saturation of TDG. Chum salmon (Oncorhynchus keta) embryos incubating in nearby spawning areas could be affected if depth-compensated TDG concentrations within the hyporheic zone exceed 103% TDG. The objective of this study was to determine if TDG of the hyporheic zone in two chum salmon spawning areas -- one in a side channel near Ives Island, Washington, and another on the mainstem Columbia River near Multnomah Falls, Oregon -- was affected by the elevated TDG of the surface water. Depth-compensated hyporheicmore » TDG did not exceed 103% at the Multnomah Falls site. However, in the Ives Island area, chum salmon redds were exposed to TDG greater than 103% for more than 600 hours. In response to river depth fluctuations, TDG varied significantly in the Ives Island area, suggesting increased interaction between the hyporheic zone and surface water at that site. We conclude from this study that the interaction between surface water and the hyporheic zone affects the concentration of TDG within the hyporheic zone directly via physical mixing as well as indirectly by altering water chemistry and thus dissolved gas solubility. These interactions are important considerations when estimating TDG exposure within egg pocket environments, facilitating improved exposure estimates, and enabling managers to optimize recovery strategies.« less

Groundwater and surface water interaction in a basin surrounded by steep mountains, central Japan

NASA Astrophysics Data System (ADS)

Ikeda, Koichi; Tsujimura, Maki; Kaeriyama, Toshiaki; Nakano, Takanori

2015-04-01

Mountainous headwaters and lower stream alluvial plains are important as water recharge and discharge areas from the view point of groundwater flow system. Especially, groundwater and surface water interaction is one of the most important processes to understand the total groundwater flow system from the mountain to the alluvial plain. We performed tracer approach and hydrometric investigations in a basin with an area 948 square km surrounded by steep mountains with an altitude from 250m to 2060m, collected 258 groundwater samples and 112 surface water samples along four streams flowing in the basin. Also, Stable isotopes ratios of oxygen-18 (18O) and deuterium (D) and strontium (Sr) were determined on all water samples. The 18O and D show distinctive values for each sub-basin affected by different average recharge altitudes among four sub-basins. Also, Sr isotope ratio shows the same trend as 18O and D affected by different geological covers in the recharge areas among four sub-basins. The 18O, D and Sr isotope values of groundwater along some rivers in the middle stream region of the basin show close values as the rivers, and suggesting that direct recharge from the river to the shallow groundwater is predominant in that region. Also, a decreasing trend of discharge rate of the stream along the flow supports this idea of the groundwater and surface water interaction in the basin.

Water levels and groundwater and surface-water exchanges in lakes of the northeast Twin Cities Metropolitan Area, Minnesota, 2002 through 2015

USGS Publications Warehouse

Jones, Perry M.; Trost, Jared J.; Erickson, Melinda L.

2016-10-19

OverviewThis study assessed lake-water levels and regional and local groundwater and surface-water exchanges near northeast Twin Cities Metropolitan Area lakes applying three approaches: statistical analysis, field study, and groundwater-flow modeling.  Statistical analyses of lake levels were completed to assess the effect of physical setting and climate on lake-level fluctuations of selected lakes. A field study of groundwater and surface-water interactions in selected lakes was completed to (1) estimate potential percentages of surface-water contributions to well water across the northeast Twin Cities Metropolitan Area, (2) estimate general ages for waters extracted from the wells, and (3) assess groundwater inflow to lakes and lake-water outflow to aquifers downgradient from White Bear Lake.  Groundwater flow was simulated using a steady-state, groundwater-flow model to assess regional groundwater and surface-water exchanges and the effects of groundwater withdrawals, climate, and other factors on water levels of northeast Twin Cities Metropolitan Area lakes.

Quantifying time-varying ground-water discharge and recharge in wetlands of the northern Florida Everglades

USGS Publications Warehouse

Choi, J.; Harvey, J.W.

2000-01-01

Developing a more thorough understanding of water and chemical budgets in wetlands depends in part on our ability to quantify time-varying interactions between ground water and surface water. We used a combined water and solute mass balance approach to estimate time-varying ground-water discharge and recharge in the Everglades Nutrient Removal project (ENR), a relatively large constructed wetland (1544 hectare) built for removing nutrients from agricultural drainage in the norther Everglades in South Florida, USA. Over a 4-year period (1994 through 1998), ground-water recharge averaged 13.4 hectare-meter per day (ha-m/day) or 0.9 cm/day, which is approximately 31% of surface water pumped into the ENR for treatment. In contrast, ground-water discharge was much smaller (1.4 ha-m/day, or 0.09 cm/day, or 2.8% of water input to ENR for treatment). Using a water-balance approach alone only allowed net ground-water exchange (discharge - recharge) to be estimated (-12 ?? 2.4 ha-ma/day). Disharge and recharge were individually determined by combining a chloride mass balance with the water balance. For a variety of reasons, the ground-water discharge estimated by the combined mass balance approach was not reliable (1.4 ?? 37 ha-m/day). As a result, ground-water interactions could only be reliably estimated by comparing the mass-balance results with other independent approaches, including direct seepage-meter measurements and previous estimates using ground-water modeling. All three independent approaches provided similar estimates of average ground-water recharge, ranging from 13 to 14 ha-m/day. There was also relatively good agreement between ground-water discharge estimates for the mass balance and seepage meter methods, 1.4 and 0.9 ha-m/day, respectively. However, ground-water-flow modeling provided an average discharge estimate that was approximately a factor of four higher (5.4 ha-m/day) than the other two methods. Our study developed an initial understanding of how the design and operation of the ENR increases interactions between ground water and surface water. A considerable portion of recharged ground water (73%) was collected and returned to the ENR by a seepage canal. Additional recharge that was not captured by the seepage canal only occurred when pumped inflow rates to ENR (and ENR water levels) were relatively high. Management of surface water in the northern Everglades therefore clearly has the potential to increase interactions with ground water.

Perspective: A controversial benchmark system for water-oxide interfaces: H2O/TiO2(110)

NASA Astrophysics Data System (ADS)

Diebold, Ulrike

2017-07-01

The interaction of water with the single-crystalline rutile TiO2(110) surface has been the object of intense investigations with both experimental and computational methods. Not only is TiO2(110) widely considered the prototypical oxide surface, its interaction with water is also important in many applications where this material is used. At first, experimental measurements were hampered by the fact that preparation recipes for well-controlled surfaces had yet to be developed, but clear experimental evidence that water dissociation at defects including oxygen vacancies and steps emerged. For a perfect TiO2(110) surface, however, an intense debate has evolved whether or not water adsorbs as an intact molecule or if it dissociates by donating a proton to a so-called bridge-bonded surface oxygen atom. Computational studies agree that the energy difference between these two states is very small and thus depends sensitively on the computational setup and on the approximations used in density functional theory (DFT). While a recent molecular beam/STM experiment [Z.-T. Wang et al., Proc. Natl. Acad. Sci. U. S. A. 114(8), 1801-1805 (2017)] gives conclusive evidence for a slight preference (0.035 eV) for molecular water and a small activation energy of (0.36 eV) for dissociation, understanding the interface between liquid water and TiO2(110) arises as the next controversial frontier.

Partial molar volume of proteins studied by the three-dimensional reference interaction site model theory.

PubMed

Imai, Takashi; Kovalenko, Andriy; Hirata, Fumio

2005-04-14

The three-dimensional reference interaction site model (3D-RISM) theory is applied to the analysis of hydration effects on the partial molar volume of proteins. For the native structure of some proteins, the partial molar volume is decomposed into geometric and hydration contributions using the 3D-RISM theory combined with the geometric volume calculation. The hydration contributions are correlated with the surface properties of the protein. The thermal volume, which is the volume of voids around the protein induced by the thermal fluctuation of water molecules, is directly proportional to the accessible surface area of the protein. The interaction volume, which is the contribution of electrostatic interactions between the protein and water molecules, is apparently governed by the charged atomic groups on the protein surface. The polar atomic groups do not make any contribution to the interaction volume. The volume differences between low- and high-pressure structures of lysozyme are also analyzed by the present method.

Interaction of acoustic levitation field with liquid reflecting surface

NASA Astrophysics Data System (ADS)

Hong, Z. Y.; Xie, W. J.; Wei, B.

2010-01-01

Single-axis acoustic levitation of substances, such as foam, water, polymer, and aluminum, is achieved by employing various liquids as the sound reflectors. The interaction of acoustic levitation field with liquid reflecting surface is investigated theoretically by considering the deformation of the liquid surface under acoustic radiation pressure. Numerical calculations indicate that the deformation degree of the reflecting surface shows a direct proportion to the acoustic radiation power. Appropriate deformation is beneficial whereas excessive deformation is unfavorable to enhance the levitation capability. Typically, the levitation capability with water reflector is smaller than that with the concave rigid reflector but slightly larger than that with the planar rigid reflector at low emitter vibration intensity. Liquid reflectors with larger surface tension and higher density behave more closely to the planar rigid reflector.

Shock wave-droplet interaction

NASA Astrophysics Data System (ADS)

Habibi Khoshmehr, Hamed; Krechetnikov, Rouslan

2016-11-01

Disintegration of a liquid droplet under the action of a shock wave is experimentally investigated. The shock wave-pulse is electromagnetically generated by discharging a high voltage capacitor into a flat spiral coil, above which an isolated circular metal membrane is placed in a close proximity. The Lorentz force arising due to the eddy current induced in the membrane abruptly accelerates it away from the spiral coil thus generating a shock wave. The liquid droplet placed at the center of the membrane, where the maximum deflection occurs, is disintegrated in the process of interaction with the shock wave. The effects of droplet viscosity and surface tension on the droplet destruction are studied with high-speed photography. Water-glycerol solution at different concentrations is used for investigating the effect of viscosity and various concentrations of water-sugar and water-ethanol solution are used for studying the effect of surface tension. Here we report on how the metamorphoses, which a liquid drop undergoes in the process of interaction with a shock wave, are affected by varied viscosity and surface tension.

Mapping hydration dynamics and coupled water-protein fluctuations around a protein surface

NASA Astrophysics Data System (ADS)

Zhang, Luyuan; Wang, Lijuan; Kao, Ya-Ting; Qiu, Weihong; Yang, Yi; Okobiah, Oghaghare; Zhong, Dongping

2009-03-01

Elucidation of the molecular mechanism of water-protein interactions is critical to understanding many fundamental aspects of protein science, such as protein folding and misfolding and enzyme catalysis. We recently carried out a global mapping of protein-surface hydration dynamics around a globular α-helical protein apomyoglobin. The intrinsic optical probe tryptophan was employed to scan the protein surface one at a time by site-specific mutagenesis. With femtosecond resolution, we mapped out the dynamics of water-protein interactions with more than 20 mutants and for two states, native and molten globular. A robust bimodal distribution of time scales was observed, representing two types of water motions: local relaxation and protein-coupled fluctuations. The time scales show a strong correlation with the local protein structural rigidity and chemical identity. We also resolved two distinct contributions to the overall Stokes-shifts from the two time scales. These results are significant to understanding the role of hydration water on protein structural stability, dynamics and function.

Fluid Surface Deformation by Objects in the Cheerios Effect

NASA Astrophysics Data System (ADS)

Nguyen, Khoi; Miller, Michael; Mandre, Shreyas; Mandre Lab Team

2012-11-01

Small objects floating on a fluid/air interface deform of the surface depending on material surface properties, density, and geometry. These objects attract each other through capillary interactions, a phenomenon dubbed the ``cheerios effect.'' The attractive force and torque exerted on these objects by the interface can be estimated if the meniscus deformation is known. In addition, the floating objects can also rotate due to such an interaction. We present a series of experiments focused on visualizing the the motions of the floating objects and the deformation of the interface. The experiments involve thin laser-cut acrylic pieces attracting each other on water in a large glass petri dish and a camera set-up to capture the process. Furthermore, optical distortion of a grid pattern is used to visualize the water surface deformation near the edge of the objects. This study of the deformation of the water surface around a floating object, of the attractive/repulsive forces, and of post-contact rotational dynamics are potentially instrumental in the study of colloidal self-assembly.

Water Adsorption on Clean and Defective Anatase TiO2 (001) Nanotube Surfaces: A Surface Science Approach.

PubMed

Kenmoe, Stephane; Lisovski, Oleg; Piskunov, Sergei; Bocharov, Dmitry; Zhukovskii, Yuri F; Spohr, Eckhard

2018-05-31

We use ab initio molecular dynamics simulations to study the adsorption of thin water films with 1 and 2 ML coverage on anatase TiO 2 (001) nanotubes. The nanotubes are modeled as 2D slabs, which consist of partially constrained and partially relaxed structural motifs from nanotubes. The effect of anion doping on the adsorption is investigated by substituting O atoms with N and S impurities on the nanotube slab surface. Due to strain-induced curvature effects, water adsorbs molecularly on defect-free surfaces via weak bonds on Ti sites and H bonds to surface oxygens. While the introduction of an S atom weakens the interaction of the surface with water, which adsorbs molecularly, the presence of an N impurity renders the surface more reactive to water, with a proton transfer from the water film and the formation of an NH group at the N site. At 2 ML coverage, a further surface-assisted proton transfer takes place in the water film, resulting in the formation of an OH - group and an NH 2 + cationic site on the surface.

Reactive molecular dynamics of the initial oxidation stages of Ni111 in pure water: effect of an applied electric field.

PubMed

Assowe, O; Politano, O; Vignal, V; Arnoux, P; Diawara, B; Verners, O; van Duin, A C T

2012-12-06

Corrosion processes occurring in aqueous solutions are critically dependent upon the interaction between the metal electrode and the solvent. In this work, the interaction of a nickel substrate with water molecules has been investigated using reactive force field (ReaxFF) molecular dynamics simulations. This approach was originally developed by van Duin and co-workers to study hydrocarbon chemistry and the catalytic properties of organic compounds. To our knowledge, this method has not previously been used to study the corrosion of nickel. In this work, we studied the interaction of 480 molecules of water (ρ = 0.99 g·cm(-3)) with Ni(111) surfaces at 300 K. The results showed that a water "bilayer" was adsorbed on the nickel surface. In the absence of an applied electric field, no dissociation of water was observed. However, the nickel atoms at the surface were charged positively, whereas the first water layer was charged negatively, indicating the formation of an electric double layer. To study the corrosion of nickel in pure water, we introduced an external electric field between the metal and the solution. The electric field intensity varied between 10 and 20 MeV/cm. The presence of this electric field led to oxidation of the metal surface. The structural and morphological differences associated with the growth of this oxide film in the presence of the electric field were evaluated. The simulated atomic trajectories were used to analyze the atomic displacement during the reactive process. The growth of the oxide scale on the nickel surface was primarily due to the movement of anions toward the interior of the metal substrate and the migration of nickel toward the free surface. We found that increasing the electric field intensity sped up the corrosion of nickel. The results also showed that the oxide film thickness increased linearly with increasing electric field intensity.

Hydrophobic interaction and charge accumulation at the diamond-electrolyte interface.

PubMed

Dankerl, M; Lippert, A; Birner, S; Stützel, E U; Stutzmann, M; Garrido, J A

2011-05-13

The hydrophobic interaction of surfaces with water is a well-known phenomenon, but experimental evidence of its influence on biosensor devices has been lacking. In this work we investigate diamond field-effect devices, reporting on Hall effect experiments and complementary simulations of the interfacial potential at the hydrogen-terminated diamond/aqueous electrolyte interface. The interfacial capacitance, derived from the gate-dependent Hall carrier concentration, can be modeled only when considering the hydrophobic nature of this surface and its influence on the structure of interfacial water. Our work demonstrates how profoundly the performance of potentiometric biosensor devices can be affected by their surfaces' hydrophobicity.

Modulators of heterogeneous protein surface water dynamics

NASA Astrophysics Data System (ADS)

Han, Songi

The hydration water that solvates proteins is a major factor in driving or enabling biological events, including protein-protein and protein-ligand interactions. We investigate the role of the protein surface in modulating the hydration water fluctuations on both the picosecond and nanosecond timescale with an emerging experimental NMR technique known as Overhauser Dynamic Nuclear Polarization (ODNP). We carry out site-specific ODNP measurements of the hydration water fluctuations along the surface of Chemotaxis Y (CheY), and correlate the measured fluctuations to hydropathic and topological properties of the CheY surface as derived from molecular dynamics (MD) simulation. Furthermore, we compare hydration water fluctuations measured on the CheY surface to that of other globular proteins, as well as intrinsically disordered proteins, peptides, and liposome surfaces to systematically test characteristic effects of the biomolecular surface on the hydration water dynamics. Our results suggest that the labile (ps) hydration water fluctuations are modulated by the chemical nature of the surface, while the bound (ns) water fluctuations are present on surfaces that feature a rough topology and chemical heterogeneity such as the surface of a folded and structured protein. In collaboration with: Ryan Barnes, Dept of Chemistry and Biochemistry, University of California Santa Barbara

The influence of data characteristics on detecting wetland/stream surface-water connections in the Delmarva Peninsula, Maryland and Delaware

USGS Publications Warehouse

Vanderhoof, Melanie; Distler, Hayley; Lang, Megan W.; Alexander, Laurie C.

2018-01-01

The dependence of downstream waters on upstream ecosystems necessitates an improved understanding of watershed-scale hydrological interactions including connections between wetlands and streams. An evaluation of such connections is challenging when, (1) accurate and complete datasets of wetland and stream locations are often not available and (2) natural variability in surface-water extent influences the frequency and duration of wetland/stream connectivity. The Upper Choptank River watershed on the Delmarva Peninsula in eastern Maryland and Delaware is dominated by a high density of small, forested wetlands. In this analysis, wetland/stream surface water connections were quantified using multiple wetland and stream datasets, including headwater streams and depressions mapped from a lidar-derived digital elevation model. Surface-water extent was mapped across the watershed for spring 2015 using Landsat-8, Radarsat-2 and Worldview-3 imagery. The frequency of wetland/stream connections increased as a more complete and accurate stream dataset was used and surface-water extent was included, in particular when the spatial resolution of the imagery was finer (i.e., <10 m). Depending on the datasets used, 12–60% of wetlands by count (21–93% of wetlands by area) experienced surface-water interactions with streams during spring 2015. This translated into a range of 50–94% of the watershed contributing direct surface water runoff to streamflow. This finding suggests that our interpretation of the frequency and duration of wetland/stream connections will be influenced not only by the spatial and temporal characteristics of wetlands, streams and potential flowpaths, but also by the completeness, accuracy and resolution of input datasets.

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 interface. PMID:8534807

PERCHLORATE CROP INTERACTIONS VIA CONTAMINATED IRRIGATION WATER

EPA Science Inventory

Perchlorate has contaminated water and sods at several locations in the United States. Perchlorate is water soluble, exceedingly mobile in aqueous systems, and can persist for many decades under typical ground- and surface water conditions. Perchlorate is of concern because of un...

Measuring groundwater-surface water interaction and its effect on wetland stream benthic productivity, Trout Lake watershed, northern Wisconsin, USA

USGS Publications Warehouse

Hunt, R.J.; Strand, M.; Walker, J.F.

2006-01-01

Measurements of groundwater-surface water exchange at three wetland stream sites were related to patterns in benthic productivity as part of the US Geological Survey's Northern Temperate Lakes-Water, Energy and Biogeochemical Budgets (NTL-WEBB) project. The three sites included one high groundwater discharge (HGD) site, one weak groundwater discharge (WGD) site, and one groundwater recharge (GR) site. Large upward vertical gradients at the HGD site were associated with smallest variation in head below the stream and fewest gradient reversals between the stream and the groundwater beneath the stream, and the stream and the adjacent streambank. The WGD site had the highest number of gradient reversals reflecting the average condition being closest to zero vertical gradient. The duration of groundwater discharge events was related to the amount of discharge, where the HGD site had the longest strong-gradient durations for both horizontal and vertical groundwater flow. Strong groundwater discharge also controlled transient temperature and chemical hyporheic conditions by limiting the infiltration of surface water. Groundwater-surface water interactions were related to highly significant patterns in benthic invertebrate abundance, taxonomic richness, and periphyton respiration. The HGD site abundance was 35% greater than in the WGD site and 53% greater than the GR site; richness and periphyton respiration were also significantly greater (p???0.001, 31 and 44%, respectively) in the HGD site than in the GR site. The WGD site had greater abundance (27%), richness (19%) and periphyton respiration (39%) than the GR site. This work suggests groundwater-surface water interactions can strongly influence benthic productivity, thus emphasizing the importance of quantitative hydrology for management of wetland-stream ecosystems in the northern temperate regions. ?? 2005 Elsevier B.V. All rights reserved.

Molecular modeling studies of interactions between sodium polyacrylate polymer and calcite surface

NASA Astrophysics Data System (ADS)

Ylikantola, A.; Linnanto, J.; Knuutinen, J.; Oravilahti, A.; Toivakka, M.

2013-07-01

The interactions between calcite pigment and sodium polyacrylate dispersing agent, widely used in papermaking as paper coating components, were investigated using classical force field and quantum chemical approaches. The objective was to understand interactions between the calcite surface and sodium polyacrylate polymer at 300 K using molecular dynamics simulations. A quantum mechanical ab initio Hartree-Fock method was also used to obtain detailed information about the sodium polyacrylate polymer structure. The effect of water molecules (moisture) on the interactions was also examined. Calculations showed that molecular weight, branching and the orientation of sodium polyacrylate polymers influence the interactions between the calcite surface and the polymer. The force field applied, and also water molecules, were found to have an impact on all systems studied. Ab initio Hartree-Fock calculations indicated that there are two types of coordination between sodium atoms and carboxylate groups of the sodium polyacrylate polymer, inter- and intra-carboxylate group coordination. In addition, ab initio Hartree-Fock calculations of the structure of the sodium polyacrylate polymer produced important information regarding interactions between the polymers and carboxylated styrene-butadiene latex particles.

Lifshitz interaction can promote ice growth at water-silica interfaces

NASA Astrophysics Data System (ADS)

Boström, Mathias; Malyi, Oleksandr I.; Parashar, Prachi; Shajesh, K. V.; Thiyam, Priyadarshini; Milton, Kimball A.; Persson, Clas; Parsons, Drew F.; Brevik, Iver

2017-04-01

At air-water interfaces, the Lifshitz interaction by itself does not promote ice growth. On the contrary, we find that the Lifshitz force promotes the growth of an ice film, up to 1-8 nm thickness, near silica-water interfaces at the triple point of water. This is achieved in a system where the combined effect of the retardation and the zero frequency mode influences the short-range interactions at low temperatures, contrary to common understanding. Cancellation between the positive and negative contributions in the Lifshitz spectral function is reversed in silica with high porosity. Our results provide a model for how water freezes on glass and other surfaces.

Bioinspired Surface Treatments for Improved Decontamination: Icephobic Surfaces

DTIC Science & Technology

2017-06-26

standing droplets of water (left) and methyl salicylate (right) immediately following liquid application (top) and 5 min after liquid application...average of nine measurements for each liquid ). Geometric surface energy was calculated based on the water and ethylene glycol interactions using software...supporting platform angle was gradually increased up to 60°. Sliding angles for each of the liquids were identified as the angle for which movement

Spatial pattern analysis of cruise ship-humpback whale interactions in and near Glacier Bay National Park, Alaska.

PubMed

Harris, Karin; Gende, Scott M; Logsdon, Miles G; Klinger, Terrie

2012-01-01

Understanding interactions between large ships and large whales is important to estimate risks posed to whales by ships. The coastal waters of Alaska are a summer feeding area for humpback whales (Megaptera novaeangliae) as well as a prominent destination for large cruise ships. Lethal collisions between cruise ships and humpback whales have occurred throughout Alaska, including in Glacier Bay National Park (GBNP). Although the National Park Service (NPS) establishes quotas and operating requirements for cruise ships within GBNP in part to minimize ship-whale collisions, no study has quantified ship-whale interactions in the park or in state waters where ship traffic is unregulated. In 2008 and 2009, an observer was placed on ships during 49 different cruises that included entry into GBNP to record distance and bearing of whales that surfaced within 1 km of the ship's bow. A relative coordinate system was developed in ArcGIS to model the frequency of whale surface events using kernel density. A total of 514 whale surface events were recorded. Although ship-whale interactions were common within GBNP, whales frequently surfaced in front of the bow in waters immediately adjacent to the park (west Icy Strait) where cruise ship traffic is not regulated by the NPS. When ships transited at speeds >13 knots, whales frequently surfaced closer to the ship's midline and ship's bow in contrast to speeds slower than 13 knots. Our findings confirm that ship speed is an effective mitigation measure for protecting whales and should be applied to other areas where ship-whale interactions are common.

Spatial Pattern Analysis of Cruise Ship-Humpback Whale Interactions in and Near Glacier Bay National Park, Alaska

NASA Astrophysics Data System (ADS)

Harris, Karin; Gende, Scott M.; Logsdon, Miles G.; Klinger, Terrie

2012-01-01

Understanding interactions between large ships and large whales is important to estimate risks posed to whales by ships. The coastal waters of Alaska are a summer feeding area for humpback whales ( Megaptera novaeangliae) as well as a prominent destination for large cruise ships. Lethal collisions between cruise ships and humpback whales have occurred throughout Alaska, including in Glacier Bay National Park (GBNP). Although the National Park Service (NPS) establishes quotas and operating requirements for cruise ships within GBNP in part to minimize ship-whale collisions, no study has quantified ship-whale interactions in the park or in state waters where ship traffic is unregulated. In 2008 and 2009, an observer was placed on ships during 49 different cruises that included entry into GBNP to record distance and bearing of whales that surfaced within 1 km of the ship's bow. A relative coordinate system was developed in ArcGIS to model the frequency of whale surface events using kernel density. A total of 514 whale surface events were recorded. Although ship-whale interactions were common within GBNP, whales frequently surfaced in front of the bow in waters immediately adjacent to the park (west Icy Strait) where cruise ship traffic is not regulated by the NPS. When ships transited at speeds >13 knots, whales frequently surfaced closer to the ship's midline and ship's bow in contrast to speeds slower than 13 knots. Our findings confirm that ship speed is an effective mitigation measure for protecting whales and should be applied to other areas where ship-whale interactions are common.

The role of permafrost and seasonal frost in the hydrology of northern wetlands in North America

USGS Publications Warehouse

Woo, M.-K.; Winter, Thomas C.

1993-01-01

Wetlands are a common landscape feature in the Arctic, Subarctic, and north Temperate zones of North America. In all three-zones, the occurrnce of seasonal frost results in similar surface-water processes in the early spring. For example, surface ice and snow generally melt before the soil frost thaws, causing melt water to flow into depressions, over the land surface and at times, across low topographic divides. However, evapotranspiration and ground-water movement differ among the three climatic zones because they are more affected by permafrost than seasonal frost. The water source for plants in the Arctic is restricted to the small volume of subsurface water lying above the permafrost. Although this is also true in the Subarctic where permafrost exists, where it does not, plants may receive and possibly reflect, more regional ground-water sources. Where permafrost exists, the interaction of wetlands with subsurface water is largely restricted to shallow local flow systems. But where permafrost is absent in parts of the Subarctic and all of the Temperature zone, wetlands may have a complex interaction with ground-water-flow systems of all magnitudes.

Structure of a model TiO2 photocatalytic interface

NASA Astrophysics Data System (ADS)

Hussain, H.; Tocci, G.; Woolcot, T.; Torrelles, X.; Pang, C. L.; Humphrey, D. S.; Yim, C. M.; Grinter, D. C.; Cabailh, G.; Bikondoa, O.; Lindsay, R.; Zegenhagen, J.; Michaelides, A.; Thornton, G.

2017-04-01

The interaction of water with TiO2 is crucial to many of its practical applications, including photocatalytic water splitting. Following the first demonstration of this phenomenon 40 years ago there have been numerous studies of the rutile single-crystal TiO2(110) interface with water. This has provided an atomic-level understanding of the water-TiO2 interaction. However, nearly all of the previous studies of water/TiO2 interfaces involve water in the vapour phase. Here, we explore the interfacial structure between liquid water and a rutile TiO2(110) surface pre-characterized at the atomic level. Scanning tunnelling microscopy and surface X-ray diffraction are used to determine the structure, which is comprised of an ordered array of hydroxyl molecules with molecular water in the second layer. Static and dynamic density functional theory calculations suggest that a possible mechanism for formation of the hydroxyl overlayer involves the mixed adsorption of O2 and H2O on a partially defected surface. The quantitative structural properties derived here provide a basis with which to explore the atomistic properties and hence mechanisms involved in TiO2 photocatalysis.

Structure of a model TiO2 photocatalytic interface.

PubMed

Hussain, H; Tocci, G; Woolcot, T; Torrelles, X; Pang, C L; Humphrey, D S; Yim, C M; Grinter, D C; Cabailh, G; Bikondoa, O; Lindsay, R; Zegenhagen, J; Michaelides, A; Thornton, G

2017-04-01

The interaction of water with TiO 2 is crucial to many of its practical applications, including photocatalytic water splitting. Following the first demonstration of this phenomenon 40 years ago there have been numerous studies of the rutile single-crystal TiO 2 (110) interface with water. This has provided an atomic-level understanding of the water-TiO 2 interaction. However, nearly all of the previous studies of water/TiO 2 interfaces involve water in the vapour phase. Here, we explore the interfacial structure between liquid water and a rutile TiO 2 (110) surface pre-characterized at the atomic level. Scanning tunnelling microscopy and surface X-ray diffraction are used to determine the structure, which is comprised of an ordered array of hydroxyl molecules with molecular water in the second layer. Static and dynamic density functional theory calculations suggest that a possible mechanism for formation of the hydroxyl overlayer involves the mixed adsorption of O 2 and H 2 O on a partially defected surface. The quantitative structural properties derived here provide a basis with which to explore the atomistic properties and hence mechanisms involved in TiO 2 photocatalysis.

Molecular dynamics studies of interfacial water at the alumina surface.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Argyris, Dr. Dimitrios; Ho, Thomas; Cole, David

2011-01-01

Interfacial water properties at the alumina surface were investigated via all-atom equilibrium molecular dynamics simulations at ambient temperature. Al-terminated and OH-terminated alumina surfaces were considered to assess the structural and dynamic behavior of the first few hydration layers in contact with the substrates. Density profiles suggest water layering up to {approx}10 {angstrom} from the solid substrate. Planar density distribution data indicate that water molecules in the first interfacial layer are organized in well-defined patterns dictated by the atomic terminations of the alumina surface. Interfacial water exhibits preferential orientation and delayed dynamics compared to bulk water. Water exhibits bulk-like behavior atmore » distances greater than {approx}10 {angstrom} from the substrate. The formation of an extended hydrogen bond network within the first few hydration layers illustrates the significance of water?water interactions on the structural properties at the interface.« less

Impact of river restoration on groundwater - surface water - interactions

NASA Astrophysics Data System (ADS)

Kurth, Anne-Marie; Schirmer, Mario

2014-05-01

Since the end of the 19th century, flood protection was increasingly based on the construction of impermeable dams and side walls (BWG, 2003). In spite of providing flood protection, these measures also limited the connectivity between the river and the land, restricted the area available for flooding, and hampered the natural flow dynamics of the river. Apart from the debilitating effect on riverine ecosystems due to loss of habitats, these measures also limited bank filtration, inhibited the infiltration of storm water, and affected groundwater-surface water-interactions. This in turn had a profound effect on ecosystem health, as a lack of groundwater-surface water interactions led to decreased cycling of pollutants and nutrients in the hyporheic zone and limited the moderation of the water temperature (EA, 2009). In recent decades, it has become apparent that further damages to riverine ecosystems must be prohibited, as the damages to ecology, economy and society surmount any benefits gained from exploiting them. Nowadays, the restoration of rivers is a globally accepted means to restore ecosystem functioning, protect water resources and amend flood protection (Andrea et al., 2012; Palmer et al., 2005; Wortley et al., 2013). In spite of huge efforts regarding the restoration of rivers over the last 30 years, the question of its effectiveness remains, as river restorations often reconstruct a naturally looking rather than a naturally functioning stream (EA, 2009). We therefore focussed our research on the effectiveness of river restorations, represented by the groundwater-surface water-interactions. Given a sufficiently high groundwater level, a lack of groundwater-surface water-interactions after restoration may indicate that the vertical connectivity in the stream was not fully restored. In order to investigate groundwater-surface water-interactions we determined the thermal signature on the stream bed and in +/- 40 cm depth by using Distributed Temperature Sensing (DTS), a fibre optical method for temperature determination over long distances (Selker et al., 2006). Thermal signatures were determined in a small urban stream before and after restoration and compared to streams in natural and near-natural settings. BWG BUNDESAMT FÜR WASSER UND GEOLOGIE, 2003. Die Geschichte des Hochwasserschutzes in der Schweiz. Bericht des BWG, Serie Wasser. Biel. 208 p. EA ENVIRONMENT AGENCY (UK), 2009. The Hyporheic Handbook: A handbook on the groundwater-surface water interface and hyporheic zone for environment managers. Bristol. 280 p. ANDREA, F., GSCHÖPF, C., BLASCHKE, A.P., WEIGELHOFER, G., AND RECKENDORFER, W., 2012. Ecological niche models for the evaluation of management options in urban floodplain - conservation vs. restoration purposes. Environ. Sci. Policy, http://dx.doi.org/10.1016/j.envsci.2012.08.011. PALMER, M.A., BERNHARDT, E.S., ALLAN, J.D., LAKE, P.S., ALEXANDER, G., BROOKS, S., CARR, J., CLAYTON, S., DAHM, C.N., FOLLSTAD SHAH, J., GALAT, D.L., LOSS, S.G., GOODWIN, P., HART, D.D., HASSETT, B., JENKINSON, R., KONDOLF, G.M., LAVE, R., MEYER, J.L., O`DONNELL, T.K., PAGANO, L. AND SUDDUTH, E., 2005. Standards for ecologically successful river restoration. Journal of Applied Ecology, 42, pp. 208 - 217. DOI 10.1111/j.1365-2664.2005.01004.x. WORTLEY, L., HERO, J-M., HOWES, M., 2013. Evaluating Ecological Restoration Success: A Review of the Literature. Restoration Ecology, 21 (5), pp. 537 - 543. DOI 10.1111/rec.12028. SELKER, J.S., THEVENAZ, L., HUWALD, H., MALLET, A., LUXEMBURG, W., VAN DE GIESEN, N., STEJSKAL, M., ZEMAN, J., WESTHOFF, M., AND PARLANGE, M.B., 2006. Distributed fibre-optic temperature sensing for hydrologic systems. Water Resources Research, 42(12), W12202.

Study of Fluorinated Quantum Dots-Protein Interactions at the Oil/Water Interface by Interfacial Surface Tension Changes.

PubMed

Carrillo-Carrión, Carolina; Gallego, Marta; Parak, Wolfgang J; Carril, Mónica

2018-05-08

Understanding the interaction of nanoparticles with proteins and how this interaction modifies the nanoparticles’ surface is crucial before their use for biomedical applications. Since fluorinated materials are emerging as potential imaging probes and delivery vehicles, their interaction with proteins of biological interest must be studied in order to be able to predict their performance in real scenarios. It is known that fluorinated planar surfaces may repel the unspecific adsorption of proteins but little is known regarding the same process on fluorinated nanoparticles due to the scarce examples in the literature. In this context, the aim of this work is to propose a simple and fast methodology to study fluorinated nanoparticle-protein interactions based on interfacial surface tension (IFT) measurements. This technique is particularly interesting for fluorinated nanoparticles due to their increased hydrophobicity. Our study is based on the determination of IFT variations due to the interaction of quantum dots of ca. 5 nm inorganic core/shell diameter coated with fluorinated ligands (QD_F) with several proteins at the oil/water interface. Based on the results, we conclude that the presence of QD_F do not disrupt protein spontaneous film formation at the oil/water interface. Even if at very low concentrations of proteins the film formation in the presence of QD_F shows a slower rate, the final interfacial tension reached is similar to that obtained in the absence of QD_F. The differential behaviour of the studied proteins (bovine serum albumin, fibrinogen and apotransferrin) has been discussed on the basis of the adsorption affinity of each protein towards DCM/water interface and their different sizes. Additionally, it has been clearly demonstrated that the proposed methodology can serve as a complementary technique to other reported direct and indirect methods for the evaluation of nanoparticle-protein interactions at low protein concentrations.

Importance of hydrologic data for interpreting wetland maps and assessing wetland loss and mitigation

USGS Publications Warehouse

Carter, V.

1991-01-01

The US Geological Survey collects and disseminates, in written and digital formats, groundwater and surface-water information related to the tidal and nontidal wetlands of the United States. This information includes quantity, quality, and availability of groundwater and surface water; groundwater and surface-water interactions (recharge-discharge); groundwater flow; and the basic surface-water characteristics of streams, rivers, lakes, and wetlands. Water resources information in digital format can be used in geographic information systems (GISs) for many purposes related to wetlands. US Geological Survey wetland-related activities include collection of information important for assessing and mitigating coastal wetland loss and modification, hydrologic data collection and interpretation, GIS activities, identification of national trends in water quality and quantity, and process-oriented wetland research. -Author

Multi-tracer investigation of river and groundwater interactions: a case study in Nalenggele River basin, northwest China

NASA Astrophysics Data System (ADS)

Xu, Wei; Su, Xiaosi; Dai, Zhenxue; Yang, Fengtian; Zhu, Pucheng; Huang, Yong

2017-11-01

Environmental tracers (such as major ions, stable and radiogenic isotopes, and heat) monitored in natural waters provide valuable information for understanding the processes of river-groundwater interactions in arid areas. An integrated framework is presented for interpreting multi-tracer data (major ions, stable isotopes (2H, 18O), the radioactive isotope 222Rn, and heat) for delineating the river-groundwater interactions in Nalenggele River basin, northwest China. Qualitative and quantitative analyses were undertaken to estimate the bidirectional water exchange associated with small-scale interactions between groundwater and surface water. Along the river stretch, groundwater and river water exchange readily. From the high mountain zone to the alluvial fan, groundwater discharge to the river is detected by tracer methods and end-member mixing models, but the river has also been identified as a losing river using discharge measurements, i.e. discharge is bidirectional. On the delta-front of the alluvial fan and in the alluvial plain, in the downstream area, the characteristics of total dissolved solids values, 222Rn concentrations and δ18O values in the surface water, and patterns derived from a heat-tracing method, indicate that groundwater discharges into the river. With the environmental tracers, the processes of river-groundwater interaction have been identified in detail for better understanding of overall hydrogeological processes and of the impacts on water allocation policies.

Drivers and Effects of Groundwater-Surface Water Interaction in the Karstic Lower Flint River Basin, Southwestern Georgia, USA

NASA Astrophysics Data System (ADS)

Rugel, K.; Golladay, S. W.; Jackson, C. R.; Rasmussen, T. C.; Dowd, J. F.; Mcdowell, R. J.

2017-12-01

Groundwater provides the majority of global water resources for domestic and agricultural usage while contributing vital surface water baseflows which support healthy aquatic ecosystems. Understanding the extent and magnitude of hydrologic connectivity between groundwater and surface water components in karst watersheds is essential to the prudent management of these hydraulically-interactive systems. We examined groundwater and surface water connectivity between the Upper Floridan Aquifer (UFA) and streams in the Lower Flint River Basin (LFRB) in southwestern Georgia where development of agricultural irrigation intensified over the past 30 years. An analysis of USGS streamflow data for the pre- and post-irrigation period showed summer baseflows in some Lower Flint River tributaries were reduced by an order of magnitude in the post-irrigation period, reiterating the strong hydraulic connection between these streams and the underlying aquifer. Large and fine-scale monitoring of calcium, nitrate, specific conductance and stable isotopes (δ18O and δD) on 50 km of Ichawaynochaway Creek, a major tributary of the Lower Flint, detected discrete groundwater-surface water flow paths which accounted for 42% of total groundwater contributions in the 50 km study reach. This presentation will highlight a new analysis using the metadata EPA Reach File (1) and comparing stream reach and instream bedrock joint azimuths with stream geochemical results from previous field study. Our findings suggested that reaches with NNW bearing may be more likely to display enhanced groundwater-surface water connectivity. Our results show that local heterogeneity can significantly affect water budgets and quality within these watersheds, making the use of geomorphological stream attributes a valuable tool to water resource management for the prediction and protection of vulnerable regions of hydrologic connectivity in karst catchments.

Characterizing water-metal interfaces and machine learning potential energy surfaces

NASA Astrophysics Data System (ADS)

Ryczko, Kevin

In this thesis, we first discuss the fundamentals of ab initio electronic structure theory and density functional theory (DFT). We also discuss statistics related to computing thermodynamic averages of molecular dynamics (MD). We then use this theory to analyze and compare the structural, dynamical, and electronic properties of liquid water next to prototypical metals including platinum, graphite, and graphene. Our results are built on Born-Oppenheimer molecular dynamics (BOMD) generated using density functional theory (DFT) which explicitly include van der Waals (vdW) interactions within a first principles approach. All calculations reported use large simulation cells, allowing for an accurate treatment of the water-electrode interfaces. We have included vdW interactions through the use of the optB86b-vdW exchange correlation functional. Comparisons with the Perdew-Burke-Ernzerhof (PBE) exchange correlation functional are also shown. We find an initial peak, due to chemisorption, in the density profile of the liquid water-Pt interface not seen in the liquid water-graphite interface, liquid watergraphene interface, nor interfaces studied previously. To further investigate this chemisorption peak, we also report differences in the electronic structure of single water molecules on both Pt and graphite surfaces. We find that a covalent bond forms between the single water molecule and the platinum surface, but not between the single water molecule and the graphite surface. We also discuss the effects that defects and dopants in the graphite and graphene surfaces have on the structure and dynamics of liquid water. Lastly, we introduce artificial neural networks (ANNs), and demonstrate how they can be used to machine learn electronic structure calculations. As a proof of principle, we show the success of an ANN potential energy surfaces for a dimer molecule with a Lennard-Jones potential.

Effects of leaf area index on the coupling between water table, land surface energy fluxes, and planetary boundary layer at the regional scale

NASA Astrophysics Data System (ADS)

Lu, Y.; Rihani, J.; Langensiepen, M.; Simmer, C.

2013-12-01

Vegetation plays an important role in the exchange of moisture and energy at the land surface. Previous studies indicate that vegetation increases the complexity of the feedbacks between the atmosphere and subsurface through processes such as interception, root water uptake, leaf surface evaporation, and transpiration. Vegetation cover can affect not only the interaction between water table depth and energy fluxes, but also the development of the planetary boundary layer. Leaf Area Index (LAI) is shown to be a major factor influencing these interactions. In this work, we investigate the sensitivity of water table, surface energy fluxes, and atmospheric boundary layer interactions to LAI as a model input. We particularly focus on the role LAI plays on the location and extent of transition zones of strongest coupling and how this role changes over seasonal timescales for a real catchment. The Terrestrial System Modelling Platform (TerrSysMP), developed within the Transregional Collaborative Research Centre 32 (TR32), is used in this study. TerrSysMP consists of the variably saturated groundwater model ParFlow, the land surface model Community Land Model (CLM), and the regional climate and weather forecast model COSMO (COnsortium for Small-scale Modeling). The sensitivity analysis is performed over a range of LAI values for different vegetation types as extracted from the Moderate Resolution Imaging Spectroradiometer (MODIS) dataset for the Rur catchment in Germany. In the first part of this work, effects of vegetation structure on land surface energy fluxes and their connection to water table dynamics are studied using the stand-alone CLM and the coupled subsurface-surface components of TerrSysMP (ParFlow-CLM), respectively. The interconnection between LAI and transition zones of strongest coupling are investigated and analyzed through a subsequent set of subsurface-surface-atmosphere coupled simulations implementing the full TerrSysMP model system.

The Role of Water Distribution Controlled by Transmembrane Potentials in the Cytochrome c-Cardiolipin Interaction: Revealing from Surface-Enhanced Infrared Absorption Spectroscopy.

PubMed

Zeng, Li; Wu, Lie; Liu, Li; Jiang, Xiue

2017-11-02

The interaction of cytochrome c (cyt c) with cardiolipin (CL) plays a crucial role in apoptotic functions, however, the changes of the transmembrane potential in governing the protein behavior at the membrane-water interface have not been studied due to the difficulties in simultaneously monitoring the interaction and regulating the electric field. Herein, surface-enhanced infrared absorption (SEIRA) spectroelectrochemistry is employed to study the mechanism of how the transmembrane potentials control the interaction of cyt c with CL membranes by regulating the electrode potentials of an Au film. When the transmembrane potential decreases, the water content at the interface of the membranes can be increased to slow down protein adsorption through decreasing the hydrogen-bond and hydrophobic interactions, but regulates the redox behavior of CL-bound cyt c through a possible water-facilitated proton-coupled electron transfer process. Our results suggest that the potential drop-induced restructure of the CL conformation and the hydration state could modify the structure and function of CL-bound cyt c on the lipid membrane. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pyrite in contact with supercritical water: the desolation of steam.

PubMed

Stirling, András; Rozgonyi, Tamás; Krack, Matthias; Bernasconi, Marco

2015-07-14

The supercritical water-pyrite interface has been studied by ab initio molecular dynamics simulation. Extreme conditions are relevant in the iron-sulfur world (ISW) theory where prebiotic chemical reactions are postulated to occur at the mineral-water interface. We have investigated the properties of this interface under such conditions. We have come to the conclusion that hot-pressurized water on pyrite leads to an interface where a dry pyrite surface is in contact with the nearby SC water without significant chemical interactions. This picture is markedly different from that under ambient conditions where the surface is fully covered with adsorbed water molecules which is of relevance for the surface reactions of the ISW hypothesis.

Length-scale crossover of the hydrophobic interaction in a coarse-grained water model

NASA Astrophysics Data System (ADS)

Chaimovich, Aviel; Shell, M. Scott

2013-11-01

It has been difficult to establish a clear connection between the hydrophobic interaction among small molecules typically studied in molecular simulations (a weak, oscillatory force) and that found between large, macroscopic surfaces in experiments (a strong, monotonic force). Here, we show that both types of interaction can emerge with a simple, core-softened water model that captures water's unique pairwise structure. As in hydrophobic hydration, we find that the hydrophobic interaction manifests a length-scale dependence, exhibiting distinct driving forces in the molecular and macroscopic regimes. Moreover, the ability of this simple model to capture both regimes suggests that several features of the hydrophobic force can be understood merely through water's pair correlations.

Length-scale crossover of the hydrophobic interaction in a coarse-grained water model.

PubMed

Chaimovich, Aviel; Shell, M Scott

2013-11-01

It has been difficult to establish a clear connection between the hydrophobic interaction among small molecules typically studied in molecular simulations (a weak, oscillatory force) and that found between large, macroscopic surfaces in experiments (a strong, monotonic force). Here, we show that both types of interaction can emerge with a simple, core-softened water model that captures water's unique pairwise structure. As in hydrophobic hydration, we find that the hydrophobic interaction manifests a length-scale dependence, exhibiting distinct driving forces in the molecular and macroscopic regimes. Moreover, the ability of this simple model to capture both regimes suggests that several features of the hydrophobic force can be understood merely through water's pair correlations.

Variable exchange between a stream and an aquifer in the Rio Grande Project Area

NASA Astrophysics Data System (ADS)

Sheng, Z.; Abudu, S.; Michelsen, A.; King, P.

2016-12-01

Both surface water and groundwater in the Rio Grande Project area in southern New Mexico and Far West Texas have been stressed by natural conditions such as droughts and human activities, including urban development and agricultural irrigation. In some area pumping stress in the aquifer becomes so great that it depletes the river flow especially during the irrigation season, typically from March through October. Therefore understanding such relationship between surface water and groundwater becomes more important in regional water resources planning and management. In this area, stream flows are highly regulated by the upstream reservoirs during the irrigation season and greatly influenced by return flows during non-irrigation season. During a drought additional groundwater pumping to supplement surface water shortage further complicates the surface water and groundwater interaction. In this paper the authors will use observation data and results of numerical models (MODFLOW) to characterize and quantify hydrological exchange fluxes between groundwater in the aquifers and surface water as well as impacts of groundwater pumping. The interaction shows a very interesting seasonal variation (irrigation vs. non-irrigation) as well as impact of a drought. Groundwater has been pumped for both municipal supplies and agricultural irrigation, which has imposed stresses toward both stream flows and aquifer storage. The results clearly show that historic groundwater pumping has caused some reaches of the river change from gaining stream to losing stream. Beyond the exchange between surface water and groundwater in the shallow aquifer, groundwater pumping in a deep aquifer could also enhance the exchanges between different aquifers through leaky confining layers. In the earlier history of pumping, pumping from the shallow aquifer is compensated by simple depletion of surface water, while deep aquifer tends to use the aquifer storage. With continued pumping, the cumulative stresses from deeper aquifers migrate upward, resulting in additional depletion of surface water. Eventually such impacts turn some reaches of a gaining river into a losing stream. The research finding provides information needed for future regional water planning and conjunctive management of surface water and groundwater resources.

Acetone and Water on TiO₂(110): H/D Exchange

DOE Office of Scientific and Technical Information (OSTI.GOV)

Henderson, Michael A.

2005-04-12

Isotopic H/D exchange between coadsorbed acetone and water on the TiO?(110) surface was examined using temperature programmed desorption (TPD) as a function of coverage and two surface pretreatments (oxidation and reduction). Coadsorbed acetone and water interact repulsively on reduced TiO?(110) based on results from the companion paper to this study, with water exerting a greater influence in destabilizing acetone and acetone having only a nominal influence on water. Despite the repulsive interaction between these coadsorbates, about 0.02 ML of a 1 ML d6-acetone on the reduced surface exhibits H/D exchange with coadsorbed water, with the exchange occurring exclusively in themore » high temperature region of the d?-acetone TPD spectrum at {approx}340 K. The effect was confirmed with combinations of d?-acetone and D?O. The extent of exchange decreased on the reduced surface with water coverages above {approx}0.3 ML due to the ability of water to displace coadsorbed acetone from first layer sites to the multilayer. In contrast, the extent of exchange increased by a factor of 3 when the surface was pre-oxidized prior to coadsorption. In this case, there was no evidence for the negative influence of high water coverages on the extent of H/D exchange. Comparison of the TPD spectra from the exchange products (either d?- or d?-acetone depending on the coadsorption pairing) suggests that, in addition to the 340 K exchange process seen on the reduced surface, a second exchange process was observed on the oxidized surface at {approx}390 K. In both cases (oxidized and reduced), desorption of the H/D exchange products appeared to be reaction limited and to involve the influence of OH/OD groups (or water formed during recombinative desorption of OH/OD groups) instead of molecularly adsorbed water. The 340 K exchange process is assigned to reaction at step sites and the 390 K exchange process is attributed to the influence of oxygen adatoms deposited during surface oxidation. The H/D exchange mechanism likely involves an enolate or propenol surface intermediate formed transiently during the desorption of oxygen-stabilized acetone molecules.« less

Dynamics of water confined on the surface of titania and cassiterite nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ross, Dr. Nancy; Spencer, Elinor; Levchenko, Andrey A.

2011-01-01

We present low-temperature inelastic neutron scattering spectra collected on two metal oxide nanoparticle systems, isostructural TiO2 rutile and SnO2 cassiterite, between 0-550 meV. Data were collected on samples with varying levels of water coverage, and in the case of SnO2, particles of different sizes. This study provides a comprehensive understanding of the structure and dynamics of the water confined on the surface of these particles. The translational movement of water confined on the surface of these nanoparticles is suppressed relative to that in ice-Ih and water molecules on the surface of rutile nanoparticles are more strongly restrained that molecules residingmore » on the surface of cassiterite nanoparticles. The INS spectra also indicate that the hydrogen bond network within the hydration layers on rutile is more perturbed than for water on cassiterite. This result is indicative of stronger water-surface interactions between water on the rutile nanoparticles than for water confined on the surface of cassiterite nanoparticles. These differences are consistent with the recently reported differences in the surface energy of these two nanoparticle systems. The results of this study also support previous studies that suggest that water dissociation is more prevalent on the surface of SnO2 than TiO2.« less

Recent experimental advances on hydrophobic interactions at solid/water and fluid/water interfaces.

PubMed

Zeng, Hongbo; Shi, Chen; Huang, Jun; Li, Lin; Liu, Guangyi; Zhong, Hong

2015-03-15

Hydrophobic effects play important roles in a wide range of natural phenomena and engineering processes such as coalescence of oil droplets in water, air flotation of mineral particles, and folding and assembly of proteins and biomembranes. In this work, the authors highlight recent experimental attempts to reveal the physical origin of hydrophobic effects by directly quantifying the hydrophobic interaction on both solid/water and fluid/water interfaces using state-of-art nanomechanical techniques such as surface forces apparatus and atomic force microscopy (AFM). For solid hydrophobic surfaces of different hydrophobicity, the range of hydrophobic interaction was reported to vary from ∼10 to >100 nm. With various characterization techniques, the very long-ranged attraction (>100 nm) has been demonstrated to be mainly attributed to nonhydrophobic interaction mechanisms such as pre-existing nanobubbles and molecular rearrangement. By ruling out these factors, intrinsic hydrophobic interaction was measured to follow an exponential law with decay length of 1-2 nm with effective range less than 20 nm. On the other hand, hydrophobic interaction measured at fluid interfaces using AFM droplet/bubble probe technique was found to decay with a much shorter length of ∼0.3 nm. This discrepancy of measured decay lengths is proposed to be attributed to inherent physical distinction between solid and fluid interfaces, which impacts the structure of interface-adjacent water molecules. Direct measurement of hydrophobic interaction on a broader range of interfaces and characterization of interfacial water molecular structure using spectroscopic techniques are anticipated to help unravel the origin of this rigidity-related mismatch of hydrophobic interaction and hold promise to uncover the physical nature of hydrophobic effects. With improved understanding of hydrophobic interaction, intrinsic interaction mechanisms of many biological and chemical pathways can be better elucidated, and novel devices/processes can be developed with capacity to modulate and control the hydrophobic effects from the molecular to the macroscopic scale.

Jet atomization and cavitation induced by interactions between focused ultrasound and a water surfacea)

NASA Astrophysics Data System (ADS)

Tomita, Y.

2014-09-01

Atomization of a jet produced by the interaction of 1 MHz focused ultrasound with a water surface was investigated using high-speed photography. Viewing various aspects of jet behavior, threshold conditions were obtained necessary for water surface elevation and jet breakup, including drop separation and spray formation. In addition, the position of drop atomization, where a single drop separates from the tip of a jet without spraying, showed good correlation with the jet Weber number. For a set of specified conditions, multiple beaded water masses were formed, moving upwards to produce a vigorous jet. Cavitation phenomena occurred near the center of the primary drop-shaped water mass produced at the leading part of the jet; this was accompanied by fine droplets at the neck between the primary and secondary drop-shaped water masses, due to the collapse of capillary waves.

Spatial patterns and temporal dynamics of global scale climate-groundwater interactions

NASA Astrophysics Data System (ADS)

Cuthbert, M. O.; Gleeson, T. P.; Moosdorf, N.; Schneider, A. C.; Hartmann, J.; Befus, K. M.; Lehner, B.

2017-12-01

The interactions between groundwater and climate are important to resolve in both space and time as they influence mass and energy transfers at Earth's land surface. Despite the significance of these processes, little is known about the spatio-temporal distribution of such interactions globally, and many large-scale climate, hydrological and land surface models oversimplify groundwater or exclude it completely. In this study we bring together diverse global geomatic data sets to map spatial patterns in the sensitivity and degree of connectedness between the water table and the land surface, and use the output from a global groundwater model to assess the locations where the lateral import or export of groundwater is significant. We also quantify the groundwater response time, the characteristic time for groundwater systems to respond to a change in boundary conditions, and map its distribution globally to assess the likely dynamics of groundwater's interaction with climate. We find that more than half of the global land surface significantly exports or imports groundwater laterally. Nearly 40% of Earth's landmass has water tables that are strongly coupled to topography with water tables shallow enough to enable a bi-directional exchange of moisture with the climate system. However, only a small proportion (around 12%) of such regions have groundwater response times of 100 years or less and have groundwater fluxes that would significantly respond to rapid environmental changes over this timescale. We last explore fundamental relationships between aridity, groundwater response times and groundwater turnover times. Our results have wide ranging implications for understanding and modelling changes in Earth's water and energy balance and for informing robust future water management and security decisions.

An ecohydrologic model for a shallow groundwater urban environment.

PubMed

Arden, Sam; Ma, Xin Cissy; Brown, Mark

2014-01-01

The urban environment is a patchwork of natural and artificial surfaces that results in complex interactions with and impacts to natural hydrologic cycles. Evapotranspiration is a major hydrologic flow that is often altered through urbanization, although the mechanisms of change are sometimes difficult to tease out due to difficulty in effectively simulating soil-plant-atmosphere interactions. This paper introduces a simplified yet realistic model that is a combination of existing surface runoff and ecohydrology models designed to increase the quantitative understanding of complex urban hydrologic processes. Results demonstrate that the model is capable of simulating the long-term variability of major hydrologic fluxes as a function of impervious surface, temperature, water table elevation, canopy interception, soil characteristics, precipitation and complex mechanisms of plant water uptake. These understandings have potential implications for holistic urban water system management.

Elution Is a Critical Step for Recovering Human Adenovirus 40 from Tap Water and Surface Water by Cross-Flow Ultrafiltration

PubMed Central

Shi, Hang; Xagoraraki, Irene; Bruening, Merlin L.

2016-01-01

ABSTRACT This paper examines the recovery of the enteric adenovirus human adenovirus 40 (HAdV 40) by cross-flow ultrafiltration and interprets recovery values in terms of physicochemical interactions of virions during sample concentration. Prior to ultrafiltration, membranes were either blocked by exposure to calf serum (CS) or coated with a polyelectrolyte multilayer (PEM). HAdV 40 is a hydrophobic virus with a point of zero charge between pH 4.0 and pH 4.3. In accordance with predictions from the extended Derjaguin-Landau-Verwey-Overbeek theory, the preelution recovery of HAdV (rpre) from deionized water was higher with PEM-coated membranes (rprePEM = 74.8% ± 9.7%) than with CS-blocked membranes (rpreCS = 54.1% ± 6.2%). With either membrane type, the total virion recovery after elution (rpost) was high for both deionized water (rpostPEM = 99.5% ± 6.6% and rpostCS = 98.8% ± 7.7%) and tap water (rpostPEM = 89% ± 15% and rpostCS = 93.7% ± 6.9%). The nearly 100% recoveries suggest that the polyanion (sodium polyphosphate) and surfactant (Tween 80) in the eluent disrupt electrostatic and hydrophobic interactions between the virion and the membrane. Addition of EDTA to the eluent greatly improved the elution efficacy (rpostCS = 88.6% ± 4.3% and rpostPEM = 87.0% ± 6.9%) with surface water, even when the organic carbon concentration in the water was high (9.4 ± 0.1 mg/liter). EDTA likely disrupts cation bridging between virions and particles in the feed water matrix or the fouling layer on the membrane surface. For complex water matrices, the eluent composition is the most important factor for achieving high virion recovery. IMPORTANCE Herein we present the results of a comprehensive physicochemical characterization of HAdV 40, an important human pathogen. The data on HAdV 40 surface properties enabled rigorous modeling to gain an understanding of the energetics of virion-virion and virion-filter interactions. Cross-flow filtration for concentration and recovery of HAdV 40 was evaluated, with postelution recoveries from ultrapure water (99%), tap water (∼91%), and high-carbon-content surface water (∼84%) being demonstrated. These results are significant because of the very low adenovirus recoveries that have been reported, to date, for other methods. The recovery data were interpreted in terms of specific interactions, and the eluent composition was designed accordingly to maximize HAdV 40 recovery. PMID:27287319

A multiscale model for charge inversion in electric double layers

NASA Astrophysics Data System (ADS)

Mashayak, S. Y.; Aluru, N. R.

2018-06-01

Charge inversion is a widely observed phenomenon. It is a result of the rich statistical mechanics of the molecular interactions between ions, solvent, and charged surfaces near electric double layers (EDLs). Electrostatic correlations between ions and hydration interactions between ions and water molecules play a dominant role in determining the distribution of ions in EDLs. Due to highly polar nature of water, near a surface, an inhomogeneous and anisotropic arrangement of water molecules gives rise to pronounced variations in the electrostatic and hydration energies of ions. Classical continuum theories fail to accurately describe electrostatic correlations and molecular effects of water in EDLs. In this work, we present an empirical potential based quasi-continuum theory (EQT) to accurately predict the molecular-level properties of aqueous electrolytes. In EQT, we employ rigorous statistical mechanics tools to incorporate interatomic interactions, long-range electrostatics, correlations, and orientation polarization effects at a continuum-level. Explicit consideration of atomic interactions of water molecules is both theoretically and numerically challenging. We develop a systematic coarse-graining approach to coarse-grain interactions of water molecules and electrolyte ions from a high-resolution atomistic scale to the continuum scale. To demonstrate the ability of EQT to incorporate the water orientation polarization, ion hydration, and electrostatic correlations effects, we simulate confined KCl aqueous electrolyte and show that EQT can accurately predict the distribution of ions in a thin EDL and also predict the complex phenomenon of charge inversion.

Optimizing water resources management in large river basins with integrated surface water-groundwater modeling: A surrogate-based approach

NASA Astrophysics Data System (ADS)

Wu, Bin; Zheng, Yi; Wu, Xin; Tian, Yong; Han, Feng; Liu, Jie; Zheng, Chunmiao

2015-04-01

Integrated surface water-groundwater modeling can provide a comprehensive and coherent understanding on basin-scale water cycle, but its high computational cost has impeded its application in real-world management. This study developed a new surrogate-based approach, SOIM (Surrogate-based Optimization for Integrated surface water-groundwater Modeling), to incorporate the integrated modeling into water management optimization. Its applicability and advantages were evaluated and validated through an optimization research on the conjunctive use of surface water (SW) and groundwater (GW) for irrigation in a semiarid region in northwest China. GSFLOW, an integrated SW-GW model developed by USGS, was employed. The study results show that, due to the strong and complicated SW-GW interactions, basin-scale water saving could be achieved by spatially optimizing the ratios of groundwater use in different irrigation districts. The water-saving potential essentially stems from the reduction of nonbeneficial evapotranspiration from the aqueduct system and shallow groundwater, and its magnitude largely depends on both water management schemes and hydrological conditions. Important implications for water resources management in general include: first, environmental flow regulation needs to take into account interannual variation of hydrological conditions, as well as spatial complexity of SW-GW interactions; and second, to resolve water use conflicts between upper stream and lower stream, a system approach is highly desired to reflect ecological, economic, and social concerns in water management decisions. Overall, this study highlights that surrogate-based approaches like SOIM represent a promising solution to filling the gap between complex environmental modeling and real-world management decision-making.

Coupling surface water (Delft3D) to groundwater (MODFLOW) in the Bay-Delta community model: the effect of major abstractions in the Delta

NASA Astrophysics Data System (ADS)

Hendriks, D.; Ball, S. M.; Van der Wegen, M.; Verkaik, J.; van Dam, A.

2016-12-01

We present a coupled groundwater-surface water model for the San Francisco Bay and Sacramento Valley that consists of a combination of a spatially-distributed groundwater model (Modflow) based on the USGS Central Valley model(1) and the Flexible Mesh (FM) surface water model of the Bay Area(2). With this coupled groundwater-surface water model, we assessed effects of climate, surface water abstractions and groundwater pumping on surface water and groundwater levels, groundwater-surface water interaction and infiltration/seepage fluxes. Results show that the effect of climate (high flow and low flow) on surface water and groundwater is significant and most prominent in upstream areas. The surface water abstractions cause significant local surface water levels decrease (over 2 m), which may cause inflow of bay water during low flow periods, resulting in salinization of surface water in more upstream areas. Groundwater level drawdown due to surface water withdrawal is moderate and limited to the area of the withdrawals. The groundwater pumping causes large groundwater level drawdowns (up to 0.8 m) and significant changes in seepage/infiltration fluxes in the model. However, the effect on groundwater-surface water exchange is relatively small. The presented model instrument gives a sound first impression of the effects of climate and water abstraction on both surface water and groundwater. The combination of Modflow and Flexible Mesh has potential for modelling of groundwater-surface water exchange in deltaic areas, also in other parts of the world. However, various improvements need to be made in order to make the simulation results useful in practice. In addition, a water quality aspect could be added to assess salinization processes as well as groundwater-surface water aspects of water and soil pollution. (1) http://ca.water.usgs.gov/projects/central-valley/central-valley-hydrologic-model.html (2) www.d3d-baydelta.org

Interaction of gases with lunar materials. [surface properties of lunar fines, especially on exposure to water vapor

NASA Technical Reports Server (NTRS)

Holmes, H. F.; Gammage, R. B.

1975-01-01

The surface properties of lunar fines were investigated. Results indicate that, for the most part, these properties are independent of the chemical composition and location of the samples on the lunar surface. The leaching of channels and pores by adsorbed water vapor is a distinguishing feature of their surface chemistry. The elements of air, if adsorbed in conjunction with water vapor or liquid water, severely impedes the leaching process. In the absence of air, liquid water is more effective than water vapor in attacking the grains. The characteristics of Apollo 17 orange fines were evaluated and compared with those of other samples. The interconnecting channels produced by water vapor adsorption were found to be wider than usual for other types of fines. Damage tracks caused by heavy cosmic ray nuclei and an unusually high halogen content might provide for stronger etching conditions upon exposure to water vapor.

Adsorption of bovine serum albumin on nano and bulk oxide particles in deionized water.

PubMed

Song, Lei; Yang, Kun; Jiang, Wei; Du, Peng; Xing, Baoshan

2012-06-01

In this work, the influence of particle size and surface functional groups on the adsorption behavior of bovine serum albumin (BSA) by three types of oxide nanoparticles (NPs), TiO(2) (50±5 nm), SiO(2) (30±5 nm), and Al(2)O(3) (150±5 nm for α type and 60±5 nm for γ type) was investigated in deionized water, in order to explore their interaction mechanisms without competitive influence of other ions. Bulkparticles (BPs) were also used for comparison with NPs. BSA adsorption maxima on oxide particles were controlled by the surface area and hydrogen content, while adsorption process was primarily induced by electrostatic interaction, hydrophobic interaction and ligand exchange between BSA and oxide surfaces. With the increase of hydrogen content, the BSA adsorption mechanism switched from mainly hydrophobic interaction to hydrogen bonding and ligand exchange. Calculations, based on surface area and BSA size, suggested that a multilayer of BSA covered on α-Al(2)O(3), and single layer on the other oxide particle surfaces. BPs led to greater conformational change of BSA molecules after the adsorption on the surfaces of oxide particles though NPs adsorbed more BSA than BPs. Copyright © 2012 Elsevier B.V. All rights reserved.

Quantification of the hydrophobic interaction by simulations of the aggregation of small hydrophobic solutes in water

PubMed Central

Raschke, Tanya M.; Tsai, Jerry; Levitt, Michael

2001-01-01

The hydrophobic interaction, the tendency for nonpolar molecules to aggregate in solution, is a major driving force in biology. In a direct approach to the physical basis of the hydrophobic effect, nanosecond molecular dynamics simulations were performed on increasing numbers of hydrocarbon solute molecules in water-filled boxes of different sizes. The intermittent formation of solute clusters gives a free energy that is proportional to the loss in exposed molecular surface area with a constant of proportionality of 45 ± 6 cal/mol⋅Å2. The molecular surface area is the envelope of the solute cluster that is impenetrable by solvent and is somewhat smaller than the more traditional solvent-accessible surface area, which is the area transcribed by the radius of a solvent molecule rolled over the surface of the cluster. When we apply a factor relating molecular surface area to solvent-accessible surface area, we obtain 24 cal/mol⋅Å2. Ours is the first direct calculation, to our knowledge, of the hydrophobic interaction from molecular dynamics simulations; the excellent qualitative and quantitative agreement with experiment proves that simple van der Waals interactions and atomic point-charge electrostatics account for the most important driving force in biology. PMID:11353861

Spiers Memorial Lecture. Ions at aqueous interfaces.

PubMed

Jungwirth, Pavel

2009-01-01

Studies of aqueous interfaces and of the behavior of ions therein have been profiting from a recent remarkable progress in surface selective spectroscopies, as well as from developments in molecular simulations. Here, we summarize and place in context our investigations of ions at aqueous interfaces employing molecular dynamics simulations and electronic structure methods, performed in close contact with experiment. For the simplest of these interfaces, i.e. the open water surface, we demonstrate that the traditional picture of an ion-free surface is not valid for large, soft (polarizable) ions such as the heavier halides. Both simulations and spectroscopic measurements indicate that these ions can be present and even enhanced at surface of water. In addition we show that the ionic product of water exhibits a peculiar surface behavior with hydronium but not hydroxide accumulating at the air/water and alkane/water interfaces. This result is supported by surface-selective spectroscopic experiments and surface tension measurements. However, it contradicts the interpretation of electrophoretic and titration experiments in terms of strong surface adsorption of hydroxide; an issue which is further discussed here. The applicability of the observed behavior of ions at the water surface to investigations of their affinity for the interface between proteins and aqueous solutions is explored. Simulations show that for alkali cations the dominant mechanism of specific interactions with the surface of hydrated proteins is via ion pairing with negatively charged amino acid residues and with the backbone amide groups. As far as halide anions are concerned, the lighter ones tend to pair with positively charged amino acid residues, while heavier halides exhibit affinity to the amide group and to non-polar protein patches, the latter resembling their behavior at the air/water interface. These findings, together with results for more complex molecular ions, allow us to formulate a local model of interactions of ions with proteins with the aim to rationalize at the molecular level ion-specific Hofmeister effects, e.g. the salting out of proteins.

Assessing the Impact of Riparian Soil-Water Dynamics on Streambank Erosion

USDA-ARS?s Scientific Manuscript database

Occurrence of streambank failure is closely related to changes in pore-water pressure. Pore-water pressure in a streambank is affected, among others, by infiltrating rainfall, streambank-material texture, riparian vegetation, and interactions between surface water and groundwater. Also, the reduct...

PERCHLORATE-CROP INTERACTIONS FROM CONTAMINATED IRRIGATION WATER AND FERTILIZER APPLICATIONS

EPA Science Inventory

Perchlorate has contaminated water and soils at several locations in the United States. Perchlorate is water soluble, exceedingly mobile in aqueous systems, and can persist for many decades under typical ground and surface water conditions. Perchlorate is of concern because of un...

Shallow Alluvial Aquifer Ground Water System and Surface Water/Ground Water Interaction, Boulder Creek, Boulder, Colorado

NASA Astrophysics Data System (ADS)

Babcock, K. P.; Ge, S.; Crifasi, R. R.

2006-12-01

Water chemistry in Boulder Creek, Colorado, shows significant variation as the Creek flows through the City of Boulder [Barber et al., 2006]. This variation is partially due to ground water inputs, which are not quantitatively understood. The purpose of this study is (1) to understand ground water movement in a shallow alluvial aquifer system and (2) to assess surface water/ground water interaction. The study area, encompassing an area of 1 mi2, is located at the Sawhill and Walden Ponds area in Boulder. This area was reclaimed by the City of Boulder and Boulder County after gravel mining operations ceased in the 1970's. Consequently, ground water has filled in the numerous gravel pits allowing riparian vegetation regrowth and replanting. An integrated approach is used to examine the shallow ground water and surface water of the study area through field measurements, water table mapping, graphical data analysis, and numerical modeling. Collected field data suggest that lateral heterogeneity exists throughout the unconsolidated sediment. Alluvial hydraulic conductivities range from 1 to 24 ft/day and flow rates range from 0.01 to 2 ft/day. Preliminary data analysis suggests that ground water movement parallels surface topography and does not noticeably vary with season. Recharge via infiltrating precipitation is dependent on evapotranspiration (ET) demands and is influenced by preferential flow paths. During the growing season when ET demand exceeds precipitation rates, there is little recharge; however recharge occurs during cooler months when ET demand is insignificant. Preliminary data suggest that the Boulder Creek is gaining ground water as it traverses the study area. Stream flow influences the water table for distances up to 400 feet. The influence of stream flow is reflected in the zones relatively low total dissolved solids concentration. A modeling study is being conducted to synthesize aquifer test data, ground water levels, and stream flow data. The model will quantitatively assess the interaction between surface water and ground water, particularly the amount of exchange between the creek and ground water and to what extent these systems influence each other. Model sensitivity study will help identify important system parameters. A comprehensive model of the study area will serve as a tool for efficiently allocating water throughout the study area (from Boulder Creek). Water allocation is needed to prevent the eutrophication of the ponds, improve fishery management, and efficiently meet the water rights obligations in the watershed.

Surface-groundwater interactions in hard rocks in Sardon Catchment of western Spain: an integrated modeling approach

USGS Publications Warehouse

Hassan, S.M. Tanvir; Lubczynski, Maciek W.; Niswonger, Richard G.; Zhongbo, Su

2014-01-01

The structural and hydrological complexity of hard rock systems (HRSs) affects dynamics of surface–groundwater interactions. These complexities are not well described or understood by hydrogeologists because simplified analyses typically are used to study HRSs. A transient, integrated hydrologic model (IHM) GSFLOW (Groundwater and Surface water FLOW) was calibrated and post-audited using 18 years of daily groundwater head and stream discharge data to evaluate the surface–groundwater interactions in semi-arid, ∼80 km2 granitic Sardon hilly catchment in Spain characterized by shallow water table conditions, relatively low storage, dense drainage networks and frequent, high intensity rainfall. The following hydrological observations for the Sardon Catchment, and more generally for HRSs were made: (i) significant bi-directional vertical flows occur between surface water and groundwater throughout the HRSs; (ii) relatively large groundwater recharge represents 16% of precipitation (P, 562 mm.y−1) and large groundwater exfiltration (∼11% of P) results in short groundwater flow paths due to a dense network of streams, low permeability and hilly topographic relief; deep, long groundwater flow paths constitute a smaller component of the water budget (∼1% of P); quite high groundwater evapotranspiration (∼5% of P and ∼7% of total evapotranspiration); low permeability and shallow soils are the main reasons for relatively large components of Hortonian flow and interflow (15% and 11% of P, respectively); (iii) the majority of drainage from the catchment leaves as surface water; (iv) declining 18 years trend (4.44 mm.y−1) of groundwater storage; and (v) large spatio-temporal variability of water fluxes. This IHM study of HRSs provides greater understanding of these relatively unknown hydrologic systems that are widespread throughout the world and are important for water resources in many regions.

Fully-Integrated Simulation of Conjunctive Use from Field to Basin Scales: Development of a Surface Water Operations Module for MODFLOW-OWHM

NASA Astrophysics Data System (ADS)

Ferguson, I. M.; Boyce, S. E.; Hanson, R. T.; Llewellyn, D.

2014-12-01

It is well established that groundwater pumping affects surface-water availability by intercepting groundwater that would otherwise discharge to streams and/or by increasing seepage from surface-water channels. Conversely, surface-water management operations effect groundwater availability by altering the timing, location, and quantity of groundwater recharge and demand. Successful conjunctive use may require analysis with an integrated approach that accounts for the many interactions and feedbacks between surface-water and groundwater availability and their joint management. In order to improve simulation and analysis of conjunctive use, Bureau of Reclamation and USGS are collaborating to develop a surface-water operations module within MODFLOW One Water Hydrologic Flow Model (MF-OWHM), a new version of the USGS Modular Groundwater Flow Model (MODFLOW). Here we describe the development and application of the surface-water operations module. We provide an overview of the conceptual approach used to simulate surface-water operations—including surface-water storage, allocation, release, diversion, and delivery on monthly to seasonal time frames—in a fully-integrated manner. We then present results from a recent case study analysis of the Rio Grande Project, a large-scale irrigation project located in New Mexico and Texas, under varying surface-water operations criteria and climate conditions. Case study results demonstrate the importance of integrated hydrologic simulation of surface water and groundwater operations in analysis and management of conjunctive-use systems.

Isotopic Estimation of Water Balance and Groundwater-Surface Water Interactions of Tropical Wetland Lakes in the Pantanal, Brazil

NASA Astrophysics Data System (ADS)

Schwerdtfeger, J.; Johnson, M. S.; Weiler, M.; Couto, E. G.

2009-12-01

The Pantanal is the largest and most pristine wetland of the world, yet hydrological research there is still in its infancy. In particular the water balance of the millions of lakes and ponds and their interaction with the groundwater and the rivers are not known. The aim of this study was to assess the hydrological behaviour between different water bodies in the dry season of the northern Pantanal wetland, Brazil, to provide a more general understanding of the hydrological functioning of tropical floodplain lakes and surface water-groundwater interactions of wetlands. In the field 6-9 water sample of seven different lakes were taken during 3 months and were analyzed for stable water isotopes and chloride. In addition meteorological data from a nearby station was used to estimate daily evaporation from the water surface. This information was then used to predict the hydrological dynamics to determine whether the lakes are evaporation-controlled or throughflow-dominated systems. A chloride mass balance served to evaluate whether Cl- enrichment took place due to evaporation only, or whether the system has significant inflow and/or outflow rates. The results of those methods showed that for all lakes the water budget in the dry season, output was controlled by strong evaporation while significant inflow rates were also apparent. Inflow rates and their specific concentrations in stable isotopes and chloride were successfully estimated using the simple mass balance model MINA TrêS. This approach enabled us to calculate the water balance for the lakes as well as providing an information on source water flowing into the lakes.

Ab initio and classical molecular dynamics studies of the structural and dynamical behavior of water near a hydrophobic graphene sheet.

PubMed

Rana, Malay Kumar; Chandra, Amalendu

2013-05-28

The behavior of water near a graphene sheet is investigated by means of ab initio and classical molecular dynamics simulations. The wetting of the graphene sheet by ab initio water and the relation of such behavior to the strength of classical dispersion interaction between surface atoms and water are explored. The first principles simulations reveal a layered solvation structure around the graphene sheet with a significant water density in the interfacial region implying no drying or cavitation effect. It is found that the ab initio results of water density at interfaces can be reproduced reasonably well by classical simulations with a tuned dispersion potential between the surface and water molecules. Calculations of vibrational power spectrum from ab initio simulations reveal a shift of the intramolecular stretch modes to higher frequencies for interfacial water molecules when compared with those of the second solvation later or bulk-like water due to the presence of free OH modes near the graphene sheet. Also, a weakening of the water-water hydrogen bonds in the vicinity of the graphene surface is found in our ab initio simulations as reflected in the shift of intermolecular vibrational modes to lower frequencies for interfacial water molecules. The first principles calculations also reveal that the residence and orientational dynamics of interfacial water are somewhat slower than those of the second layer or bulk-like molecules. However, the lateral diffusion and hydrogen bond relaxation of interfacial water molecules are found to occur at a somewhat faster rate than that of the bulk-like water molecules. The classical molecular dynamics simulations with tuned Lennard-Jones surface-water interaction are found to produce dynamical results that are qualitatively similar to those of ab initio molecular dynamics simulations.

DNA base dimers are stabilized by hydrogen-bonding interactions including non-Watson-Crick pairing near graphite surfaces.

PubMed

Shankar, Akshaya; Jagota, Anand; Mittal, Jeetain

2012-10-11

Single- and double-stranded DNA are increasingly being paired with surfaces and nanoparticles for numerous applications, such as sensing, imaging, and drug delivery. Unlike the majority of DNA structures in bulk that are stabilized by canonical Watson-Crick pairing between Ade-Thy and Gua-Cyt, those adsorbed on surfaces are often stabilized by noncanonical base pairing, quartet formation, and base-surface stacking. Not much is known about these kinds of interactions. To build an understanding of the role of non-Watson-Crick pairing on DNA behavior near surfaces, one requires basic information on DNA base pair stacking and hydrogen-bonding interactions. All-atom molecular simulations of DNA bases in two cases--in bulk water and strongly adsorbed on a graphite surface--are conducted to study the relative strengths of stacking and hydrogen bond interactions for each of the 10 possible combinations of base pairs. The key information obtained from these simulations is the free energy as a function of distance between two bases in a pair. We find that stacking interactions exert the dominant influence on the stability of DNA base pairs in bulk water as expected. The strength of stability for these stacking interactions is found to decrease in the order Gua-Gua > Ade-Gua > Ade-Ade > Gua-Thy > Gua-Cyt > Ade-Thy > Ade-Cyt > Thy-Thy > Cyt-Thy > Cyt-Cyt. On the other hand, mutual interactions of surface-adsorbed base pairs are stabilized mostly by hydrogen-bonding interactions in the order Gua-Cyt > Ade-Gua > Ade-Thy > Ade-Ade > Cyt-Thy > Gua-Gua > Cyt-Cyt > Ade-Cyt > Thy-Thy > Gua-Thy. Interestingly, several non-Watson-Crick base pairings, which are commonly ignored, have similar stabilization free energies due to interbase hydrogen bonding as Watson-Crick pairs. This clearly highlights the importance of non-Watson-Crick base pairing in the development of secondary structures of oligonucleotides near surfaces.

A comparative study of surface energies and water adsorption on Ce-bastnäsite, La-bastnäsite, and calcite via density functional theory and water adsorption calorimetry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goverapet Srinivasan, Sriram; Shivaramaiah, Radha; Kent, Paul R. C.

Bastnäsite, a fluoro-carbonate mineral, is the single largest mineral source of light rare earth elements (REE), La, Ce and Nd. Enhancing the efficiency of separation of the mineral from gangue through froth flotation is the first step towards meeting an ever increasing demand for REE. To design and evaluate collector molecules that selectively bind to bastnäsite, a fundamental understanding of the structure and surface properties of bastnäsite is essential. In our earlier work (J Phys Chem C, 2016, 120, 16767), we carried out an extensive study of the structure, surface stability and water adsorption energies of La-bastnäsite. Here in thismore » work, we make a comparative study of the surface properties of Ce-bastnäsite, La-bastnäsite, and calcite using a combination of density functional theory (DFT) and water adsorption calorimetry. Spin polarized DFT+U calculations show that the exchange interaction between the electrons in Ce 4f orbitals is negligible and that these orbitals do not participate in bonding with the oxygen atom of the adsorbed water molecule. In agreement with calorimetry, DFT calculations predict larger surface energies and stronger water adsorption energies on Ce-bastnäsite than on La-bastnäsite. The order of stabilities for stoichiometric surfaces is as follows: [100] > [101] > [102] > [0001] > [112] > [104] and the most favorable adsorption sites for water molecules are the same as for La-bastnäsite. In agreement with water adsorption calorimetry, at low coverage water molecules are strongly stabilized via coordination to the surface Ce3+ ions, whereas at higher coverage they are adsorbed less strongly via hydrogen bonding interaction with the surface anions. Lastly, due to similar water adsorption energies on bastnäsite [101] and calcite [104] surfaces, the design of collector molecules that selectively bind to bastnäsite over calcite must exploit the structural differences in the predominantly exposed facets of these minerals.« less

A comparative study of surface energies and water adsorption on Ce-bastnäsite, La-bastnäsite, and calcite via density functional theory and water adsorption calorimetry

DOE PAGES

Goverapet Srinivasan, Sriram; Shivaramaiah, Radha; Kent, Paul R. C.; ...

2017-02-24

Bastnäsite, a fluoro-carbonate mineral, is the single largest mineral source of light rare earth elements (REE), La, Ce and Nd. Enhancing the efficiency of separation of the mineral from gangue through froth flotation is the first step towards meeting an ever increasing demand for REE. To design and evaluate collector molecules that selectively bind to bastnäsite, a fundamental understanding of the structure and surface properties of bastnäsite is essential. In our earlier work (J Phys Chem C, 2016, 120, 16767), we carried out an extensive study of the structure, surface stability and water adsorption energies of La-bastnäsite. Here in thismore » work, we make a comparative study of the surface properties of Ce-bastnäsite, La-bastnäsite, and calcite using a combination of density functional theory (DFT) and water adsorption calorimetry. Spin polarized DFT+U calculations show that the exchange interaction between the electrons in Ce 4f orbitals is negligible and that these orbitals do not participate in bonding with the oxygen atom of the adsorbed water molecule. In agreement with calorimetry, DFT calculations predict larger surface energies and stronger water adsorption energies on Ce-bastnäsite than on La-bastnäsite. The order of stabilities for stoichiometric surfaces is as follows: [100] > [101] > [102] > [0001] > [112] > [104] and the most favorable adsorption sites for water molecules are the same as for La-bastnäsite. In agreement with water adsorption calorimetry, at low coverage water molecules are strongly stabilized via coordination to the surface Ce3+ ions, whereas at higher coverage they are adsorbed less strongly via hydrogen bonding interaction with the surface anions. Lastly, due to similar water adsorption energies on bastnäsite [101] and calcite [104] surfaces, the design of collector molecules that selectively bind to bastnäsite over calcite must exploit the structural differences in the predominantly exposed facets of these minerals.« less

A comparative study of surface energies and water adsorption on Ce-bastnäsite, La-bastnäsite, and calcite via density functional theory and water adsorption calorimetry.

PubMed

Goverapet Srinivasan, Sriram; Shivaramaiah, Radha; Kent, Paul R C; Stack, Andrew G; Riman, Richard; Anderko, Andre; Navrotsky, Alexandra; Bryantsev, Vyacheslav S

2017-03-15

Bastnäsite, a fluoro-carbonate mineral, is the single largest mineral source of light rare earth elements (REE), La, Ce and Nd. Enhancing the efficiency of separation of the mineral from gangue through froth flotation is the first step towards meeting an ever increasing demand for REE. To design and evaluate collector molecules that selectively bind to bastnäsite, a fundamental understanding of the structure and surface properties of bastnäsite is essential. In our earlier work (J. Phys. Chem. C, 2016, 120, 16767), we carried out an extensive study of the structure, surface stability and water adsorption energies of La-bastnäsite. In this work, we make a comparative study of the surface properties of Ce-bastnäsite, La-bastnäsite, and calcite using a combination of density functional theory (DFT) and water adsorption calorimetry. Spin polarized DFT+U calculations show that the exchange interaction between the electrons in Ce 4f orbitals is negligible and that these orbitals do not participate in bonding with the oxygen atom of the adsorbed water molecule. In agreement with calorimetry, DFT calculations predict larger surface energies and stronger water adsorption energies on Ce-bastnäsite than on La-bastnäsite. The order of stabilities for stoichiometric surfaces is as follows: [101[combining macron]0] > [101[combining macron]1] > [101[combining macron]2] > [0001] > [112[combining macron]2] > [101[combining macron]4] and the most favorable adsorption sites for water molecules are the same as for La-bastnäsite. In agreement with water adsorption calorimetry, at low coverage water molecules are strongly stabilized via coordination to the surface Ce 3+ ions, whereas at higher coverage they are adsorbed less strongly via hydrogen bonding interaction with the surface anions. Due to similar water adsorption energies on bastnäsite [101[combining macron]1] and calcite [101[combining macron]4] surfaces, the design of collector molecules that selectively bind to bastnäsite over calcite must exploit the structural differences in the predominantly exposed facets of these minerals.

Global water cycle

NASA Technical Reports Server (NTRS)

Robertson, Franklin R.; Christy, John R.; Goodman, Steven J.; Miller, Tim L.; Fitzjarrald, Dan; Lapenta, Bill; Wang, Shouping

1991-01-01

The primary objective is to determine the scope and interactions of the global water cycle with all components of the Earth system and to understand how it stimulates and regulates changes on both global and regional scales. The following subject areas are covered: (1) water vapor variability; (2) multi-phase water analysis; (3) diabatic heating; (4) MSU (Microwave Sounding Unit) temperature analysis; (5) Optimal precipitation and streamflow analysis; (6) CCM (Community Climate Model) hydrological cycle; (7) CCM1 climate sensitivity to lower boundary forcing; and (8) mesoscale modeling of atmosphere/surface interaction.

Heterogeneous Ice Nucleation: Interplay of Surface Properties and Their Impact on Water Orientations.

PubMed

Glatz, Brittany; Sarupria, Sapna

2018-01-23

Ice is ubiquitous in nature, and heterogeneous ice nucleation is the most common pathway of ice formation. How surface properties affect the propensity to observe ice nucleation on that surface remains an open question. We present results of molecular dynamics studies of heterogeneous ice nucleation on model surfaces. The models surfaces considered emulate the chemistry of kaolinite, an abundant component of mineral dust. We investigate the interplay of surface lattice and hydrogen bonding properties in affecting ice nucleation. We find that lattice matching and hydrogen bonding are necessary but not sufficient conditions for observing ice nucleation at these surfaces. We correlate this behavior to the orientations sampled by the metastable supercooled water in contact with the surfaces. We find that ice is observed in cases where water molecules not only sample orientations favorable for bilayer formation but also do not sample unfavorable orientations. This distribution depends on both surface-water and water-water interactions and can change with subtle modifications to the surface properties. Our results provide insights into the diverse behavior of ice nucleation observed at different surfaces and highlight the complexity in elucidating heterogeneous ice nucleation.

Molecular dynamics study of a nanotube-binding amphiphilic helical peptide at different water/hydrophobic interfaces.

PubMed

Chiu, Chi-Cheng; Dieckmann, Gregg R; Nielsen, Steven O

2008-12-25

Many potential applications of single-walled carbon nanotubes (SWNTs) require that they be isolated from one another. This may be accomplished through covalent or noncovalent SWNT functionalization. The noncovalent approach preserves the intrinsic electrical, optical, and mechanical properties of SWNTs and can be achieved by dispersing SWNTs in aqueous solution using surfactants, polymers, or biomacromolecules like DNA or polypeptides. The designed amphiphilic helical peptide nano-1, which contains hydrophobic valine and aromatic phenylalanine residues for interaction with SWNTs and glutamic acid and lysine residues for water solubility, has been shown to debundle and disperse SWNTs, although the details of the peptide-SWNT interactions await elucidation. Here we use fully atomistic molecular dynamics simulations to investigate the nano-1 peptide at three different water/hydrophobic interfaces: water/oil, water/graphite, and water/SWNT. The amphiphilic nature of the peptide is characterized by its secondary structure, peptide-water hydrogen bonding, and peptide-hydrophobic surface van der Waals energy. We show that nano-1 has reduced amphiphilic character at the water/oil interface because the peptide helix penetrates into the hydrophobic phase. The peptide alpha-helix cannot match its hydrophobic face to the rigid planar graphite surface without partially unfolding. In contrast, nano-1 can curve on the SWNT surface in an alpha-helical conformation to simultaneously maximize its hydrophobic contacts with the SWNT and its hydrogen bonds with water. The molecular insight into the peptide conformation at the various hydrophobic surfaces provides guidelines for future peptide design.

Will the Arctic Land Surface become Wetter or Drier in Response to a Warming Climate

NASA Astrophysics Data System (ADS)

Hinzman, L. D.; Rawlins, M.; Serreze, M.; Vorosmarty, C. J.; Walsh, J. E.

2015-12-01

There is much concern about a potentially "accelerated" hydrologic cycle, with associated extremes in weather and climate-related phenomena. Whether this translates into wetter or drier conditions across arctic landscapes remains an open question. Arctic ecosystems differ substantially from those in temperate regions, largely due to the interactions of extremes in climate and land surface characteristics. Ice-rich permafrost prevents percolation of rainfall or snowmelt water, often maintaining a moist to saturated active layer where the permafrost table is shallow. Permafrost may also block the lateral movement of groundwater, and act as a confining unit for water in sub- or intra-permafrost aquifers. However, as permafrost degrades, profound changes in interactions between groundwater and surface water occur that affect the partitioning among the water balance components with subsequent impacts to the surface energy balance and essential ecosystem processes. Most simulations of arctic climate project sustained increases in temperature and gradual increases in precipitation over the 21st century. However, most climatic models do not correctly represent the essential controls that permafrost exerts on hydrological, ecological, and climatological processes. If warming continues as projected, we expect large-scale changes in surface hydrology as permafrost degrades. Where groundwater gradients are downward (i.e. surface water will infiltrate to subsurface groundwater), as in most cases, we may expect improved drainage and drier soils, which would result in reduced evaporation and transpiration (ET). In some special cases, where the groundwater gradient is upward (as in many wetlands or springs) surface soils may become wetter or inundated as permafrost degrades. Further, since soil moisture is a primary factor controlling ecosystem processes, interactions between ecosystems, GHG emissions, and high-latitude climate must also be considered highly uncertain. These inter-dependent processes will exert primary controls on several important feedback processes and vary across space and time in some as yet, unknown way.

Interaction of gases with lunar materials

NASA Technical Reports Server (NTRS)

Holmes, H. F.; Fuller, E. L., Jr.; Gammage, R. B.

1974-01-01

Quantitative efforts to assess the surface properties of lunar fines, particularly water induced porosity are discussed. Data show that: (1) changes induced in lunar fines are not visible in high energy electron micrographs, (2) scanning micrographs show no change in particle size distribution as a result of reaction with water, (3) water induced changes are internal to the particles themselves, (4) normal laboratory atmosphere blocks alteration reaction with water, and (5) surface properties of mature lunar soils appear to be almost independent of chemical composition and mineralogy, but there are some variations in their reactivity toward water.

MSATT Workshop on Innovative Instrumentation for the In Situ Study of Atmosphere-Surface Interactions on Mars

NASA Technical Reports Server (NTRS)

Fegley, Bruce, Jr. (Editor); Waenke, Heinrich (Editor)

1992-01-01

Papers accepted for the Mars Surface and Atmosphere Through Time (MSATT) Workshop on Innovative Instruments for the In Situ Study of Atmosphere-Surface Interaction of Mars, 8-9 Oct. 1992 in Mainz, Germany are included. Topics covered include: a backscatter Moessbauer spectrometer (BaMS) for use on Mars; database of proposed payloads and instruments for SEI missions; determination of martian soil mineralogy and water content using the Thermal Analyzer for Planetary Soils (TAPS); in situ identification of the martian surface material and its interaction with the martian atmosphere using DTA/GC; mass spectrometer-pyrolysis experiment for atmospheric and soil sample analysis on the surface of Mars; and optical luminescence spectroscopy as a probe of the surface mineralogy of Mars.

Surface temperatures and temperature gradient features of the US Gulf Coast waters

NASA Technical Reports Server (NTRS)

Huh, O. K.; Rouse, L. J., Jr.; Smith, G. W.

1977-01-01

Satellite thermal infrared data on the Gulf of Mexico show that a seasonal cycle exists in the horizontal surface temperature structure. In the fall, the surface temperatures of both coastal and deep waters are nearly uniform. With the onset of winter, atmospheric cold fronts, which are accompanied by dry, low temperature air and strong winds, draw heat from the sea. A band of cooler water forming on the inner shelf expands, until a thermal front develops seaward along the shelf break between the cold shelf waters and the warmer deep waters of the Gulf. Digital analysis of the satellite data was carried out in an interactive mode using a minicomputer and software. A time series of temperature profiles illustrates the temporal and spatial changes in the sea-surface temperature field.

Influence of LaFeO 3 Surface Termination on Water Reactivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R.

2017-02-17

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry, but are challenging to probe experimentally with atomic-scale understanding. Here we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO3 in humid conditions using ambient pressure X-ray photoelectron spectroscopy. Comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO surface is more reactive toward water, forming hydroxyl species andmore » adsorbing molecular water at lower relative humidity than its FeO2-terminated counterpart. Our results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight into the design of catalyst materials.« less

Monthly and seasonal variability of the land-atmosphere system

Treesearch

Yong-Qiang Liu

2003-01-01

The land surface and the atmosphere can interact with each other through exchanges of energy, water, and momentum. With the capacity of long memory, land surface processes can contribute to long-term variability of atmospheric processes. Great efforts have been made in the past three decades to study land-atmosphere interactions and their importance to long-term...

α-Chymotrypsin in water-ethanol mixtures: Effect of preferential interactions

NASA Astrophysics Data System (ADS)

Sirotkin, Vladimir A.; Kuchierskaya, Alexandra A.

2017-12-01

We investigated preferential interactions of α-chymotrypsin with water-ethanol mixtures at 25 °C. Our approach is based on the analysis of residual enzyme activity and water/alcohol sorption. There are three concentration regimes. α-Chymotrypsin is preferentially hydrated at high water content. The residual enzyme activity is close to 100%. α-Chymotrypsin has a higher affinity for alcohol than for water at intermediate water content. Residual enzyme activity is close to zero in this concentration range. At low water content, ethanol is preferentially excluded from the protein surface. This results in preferential hydration of α-chymotrypsin and significant residual catalytic activity (∼50%) in water-poor ethanol.

Geohydrology of the lower Apalachicola-Chattahoochee-Flint River basin, southwestern Georgia, northwestern Florida, and southeastern Alabama

USGS Publications Warehouse

Torak, Lynn J.; Painter, Jaime A.

2006-01-01

The lower Apalachicola-Chattahoochee-Flint (ACF) River Basin contains about 4,600 square miles of karstic and fluvial plains and nearly 100,000 cubic miles of predominantly karst limestone connected hydraulically to the principal rivers and lakes in the Coastal Plain of southwestern Georgia, northwestern Florida, and southwestern Alabama. Sediments of late-middle Eocene to Holocene in hydraulic connection with lakes, streams, and land surface comprise the surficial aquifer system, upper semiconfining unit, Upper Floridan aquifer, and lower semiconfining unit and contribute to the exchange of ground water and surface water in the stream-lake-aquifer flow system. Karst processes, hydraulic properties, and stratigraphic relations limit ground-water and surface-water interaction to the following hydrologic units of the stream-lake-aquifer flow system: the surficial aquifer system, upper semiconfining unit, Upper Floridan aquifer, and lower confining unit. Geologic units corresponding to these hydrologic units are, in ascending order: Lisbon Formation; Clinchfield Sand; Ocala, Marianna, Suwannee, and Tampa Limestones; Hawthorn Group; undifferentiated overburden (residuum); and terrace and undifferentiated (surficial) deposits. Similarities in hydraulic properties and direct or indirect interaction with surface water allow grouping sediments within these geologic units into the aforementioned hydrologic units, which transcend time-stratigraphic classifications and define the geohydrologic framework for the lower ACF River Basin. The low water-transmitting properties of the lower confining unit, principally the Lisbon Formation, allow it to act as a nearly impermeable base to the stream-lake-aquifer flow system. Hydraulic connection of the surficial aquifer system with surface water and the Upper Floridan aquifer is direct where sandy deposits overlie the limestone, or indirect where fluvial deposits overlie clayey limestone residuum. The water level in perched zones within the surficial aquifer system fluctuates independently of water-level changes in the underlying aquifer, adjacent streams, or lakes. Where the surficial aquifer system is connected with surface water and the Upper Floridan aquifer, water-table fluctuations parallel those in adjacent streams or the underlying aquifer. More...

Acoustic-gravity waves, theory and application

NASA Astrophysics Data System (ADS)

Kadri, Usama; Farrell, William E.; Munk, Walter

2015-04-01

Acoustic-gravity waves (AGW) propagate in the ocean under the influence of both the compressibility of sea water and the restoring force of gravity. The gravity dependence vanishes if the wave vector is normal to the ocean surface, but becomes increasingly important as the wave vector acquires a horizontal tilt. They are excited by many sources, including non-linear surface wave interactions, disturbances of the ocean bottom (submarine earthquakes and landslides) and underwater explosions. In this introductory lecture on acoustic-gravity waves, we describe their properties, and their relation to organ pipe modes, to microseisms, and to deep ocean signatures by short surface waves. We discuss the generation of AGW by underwater earthquakes; knowledge of their behaviour with water depth can be applied for the early detection of tsunamis. We also discuss their generation by the non-linear interaction of surface gravity waves, which explains the major role they play in transforming energy from the ocean surface to the crust, as part of the microseisms phenomenon. Finally, they contribute to horizontal water transport at depth, which might affect benthic life.

Analysis of discontinuities across thin inhomogeneities, groundwater/surface water interactions in river networks, and circulation about slender bodies using slit elements in the Analytic Element Method

USDA-ARS?s Scientific Manuscript database

Groundwater and surface water contain interfaces across which hydrologic functions are discontinuous. Thin elements with high hydraulic conductivity in a porous media focus groundwater, which flows through such inhomogeneities and causes an abrupt change in stream function across their interfaces, a...

Surface/Fluid Interactions in Micro and Nano-Channels

DTIC Science & Technology

2007-05-15

is highly dependent on the nanobubble or gas layer. However, further work with an array of gasses is necessary to fully elucidate the effects of...microchannels". Physics of Fluids 15, 2897 (2003). VJi J. Tyrell and P. Attard, "Images of nanobubbles on hydrophobic surfaces and their interactions...34 Nanobubbles and their precursor layer at the interface of water against a hydrophobic surface". Langmuir, 19, 2409-2418 (2003)."ix . K. Lum, D

Dynamic Ice-Water Interactions Form Europa's Chaos Terrains

NASA Astrophysics Data System (ADS)

Blankenship, D. D.; Schmidt, B. E.; Patterson, G. W.; Schenk, P.

2011-12-01

Unique to the surface of Europa, chaos terrain is diagnostic of the properties and dynamics of its icy shell. We present a new model that suggests large melt lenses form within the shell and that water-ice interactions above and within these lenses drive the production of chaos. This model is consistent with key observations of chaos, predicts observables for future missions, and indicates that the surface is likely still active today[1]. We apply lessons from ice-water interaction in the terrestrial cryosphere to hypothesize a dynamic lense-collapse model to for Europa's chaos terrain. Chaos terrain morphology, like that of Conamara chaos and Thera Macula, suggests a four-phase formation [1]: 1) Surface deflection occurs as ice melts over ascending thermal plumes, as regularly occurs on Earth as subglacial volcanoes activate. The same process can occur at Europa if thermal plumes cause pressure melt as they cross ice-impurity eutectics. 2) Resulting hydraulic gradients and driving forces produce a sealed, pressurized melt lense, akin to the hydraulic sealing of subglacial caldera lakes. On Europa, the water cannot escape the lense due to the horizontally continuous ice shell. 3) Extension of the brittle ice lid above the lense opens cracks, allowing for the ice to be hydrofractured by pressurized water. Fracture, brine injection and percolation within the ice and possible iceberg toppling produces ice-melange-like granular matrix material. 4) Refreezing of the melt lense and brine-filled pores and cracks within the matrix results in raised chaos. Brine soaking and injection concentrates the ice in brines and adds water volume to the shell. As this englacial water freezes, the now water-filled ice will expand, not unlike the process of forming pingos and other "expansion ice" phenomena on Earth. The refreezing can raise the surface and create the oft-observed matrix "domes" In this presentation, we describe how catastrophic ice-water interactions on Earth have informed us about how such dynamics occur on Europa. We will discuss the observations of iceberg and matrix properties that imply shallow liquid water bodies on Europa, argue for the importance of granular mechanics in the interpretation of Europa's geology and present constraints on the properties of its ice shell. [1] Schmidt, B. E., Blankenship, D. D., Patterson, W., Schenk, P: Active chaos formation over shallow subsurface water on Europa, in review, 2011.

Interaction of L-Phenylalanine with a Phospholipid Monolayer at the Water-Air Interface.

PubMed

Griffith, Elizabeth C; Perkins, Russell J; Telesford, Dana-Marie; Adams, Ellen M; Cwiklik, Lukasz; Allen, Heather C; Roeselová, Martina; Vaida, Veronica

2015-07-23

The interaction of L-phenylalanine with a 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) monolayer at the air-water interface was explored using a combination of experimental techniques and molecular dynamics (MD) simulations. By means of Langmuir trough methods and Brewster angle microscopy, L-phenylalanine was shown to significantly alter the interfacial tension and the surface domain morphology of the DPPC film. In addition, confocal microscopy was used to explore the aggregation state of L-phenylalanine in the bulk aqueous phase. Finally, MD simulations were performed to gain molecular-level information on the interactions of L-phenylalanine and DPPC at the interface. Taken together, these results show that L-phenylalanine intercalates into a DPPC film at the air-water interface, thereby affecting the surface tension, phase morphology, and ordering of the DPPC film. The results are discussed in the context of biological systems and the mechanism of diseases such as phenylketonuria.

Energetics of small molecule and water complexation in hydrophobic calixarene cavities.

PubMed

Notestein, Justin M; Katz, Alexander; Iglesia, Enrique

2006-04-25

Calixarenes grafted on silica are energetically uniform hosts that bind aromatic guests with 1:1 stoichiometry, as shown by binding energies that depend upon the calixarene upper rim composition but not on their grafted surface density (0.02-0.23 nm(-2)). These materials are unique in maintaining a hydrophilic silica surface, as probed by H2O physisorption measurements, while possessing a high density of hydrophobic binding sites that are orthogonal to the silica surface below them. The covalently enforced cone-shaped cavities and complete accessibility of these rigidly grafted calixarenes allow the first unambiguous measurements of the thermodynamics of guest interaction with the same calixarene cavities in aqueous solution and vapor phase. Similar to adsorption into nonpolar protein cavities, adsorption into these hydrophobic cavities from aqueous solution is enthalpy-driven, which is in contrast to entropy-driven adsorption into water-soluble hydrophobic hosts such as beta cyclodextrin. The adsorption thermodynamics of several substituted aromatics from vapor and liquid are compared by (i) describing guest chemical potentials relative to pure guest, which removes differences among guests because of aqueous solvation and van der Waals contacts in the pure condensed phase, and (ii) passivating residual guest binding sites on exposed silica, titrated by water during adsorption from aqueous solution, using inorganic salts before vapor adsorption. Adsorption isotherms depend only upon the saturation vapor pressure of each guest, indicating that guest binding from aqueous or vapor media is controlled by van der Waals contacts with hydrophobic calixarene cavities acting as covalently assembled condensation nuclei, without apparent contributions from CH-pi or other directional interactions. These data also provide the first direct quantification of free energies for interactions of water with the calixarene cavity interior. The calixarene-water interface is stabilized by approximately 20 kJ/mol relative to the water-vapor interface, indicating that water significantly competes with the aromatic guests for adsorption at these ostensibly hydrophobic cavities. This result is useful for understanding models of water interactions with other concave hydrophobic surfaces, including those commonly observed within proteins.

Adsorption of humic acids and trace metals in natural waters

NASA Technical Reports Server (NTRS)

Leung, W. H.

1982-01-01

Studies concerning the interactions between suspended hydrous iron oxide and dissolved humic acids and trace metals are reported. As a major component of dissolved organic matters and its readiness for adsorption at the solid/water interface, humic acids may play a very important role in the organometallic geochemistry of suspended sediments and in determining the fate and distribution of trace metals, pesticides and anions in natural water systems. Most of the solid phases in natural waters contain oxides and hydroxides. The most simple promising theory to describe the interactions of hydrous iron oxide interface is the surface complex formation model. In this model, the adsorptions of humic acids on hydrous iron oxide may be interpreted as complex formation of the organic bases (humic acid oxyanions) with surface Fe ions. Measurements on adsorptions were made in both fresh water and seawater. Attempts have been made to fit our data to Langmuir adsorption isotherm. Adsorption equilibrium constants were determined.

Quantifying Groundwater Fluctuations in the Southern High Plains with GIS and Geostatistics

NASA Astrophysics Data System (ADS)

Whitehead, B.

2008-12-01

Groundwater as a dwindling non-renewable natural resource has been an important research theme in agricultural studies coupled with human-environment interaction. This research incorporated contemporary Geographic Information System (GIS) methodologies and a universal kriging interpolator (geostatistics) to develop depth to groundwater surfaces for the southern portion of the High Plains, or Ogallala, aquifer. The variations in the interpolated surfaces were used to calculate the volume of water mined from the aquifer from 1980 to 2005. The findings suggest a nearly inverse relationship to the water withdrawal scenarios derived by the United States Geological Survey (USGS) during the Regional Aquifer System Analysis (RASA) performed in the early 1980's. These results advocate further research into regional climate change, groundwater-surface water interaction, and recharge mechanisms in the region, and provide a substantial contribution to the continuing and contentious issue concerning the environmental sustainability of the High Plains.

Biofilm-like properties of the sea surface and predicted effects on air-sea CO2 exchange

NASA Astrophysics Data System (ADS)

Wurl, Oliver; Stolle, Christian; Van Thuoc, Chu; The Thu, Pham; Mari, Xavier

2016-05-01

Because the sea surface controls various interactions between the ocean and the atmosphere, it has a profound function for marine biogeochemistry and climate regulation. The sea surface is the gateway for the exchange of climate-relevant gases, heat and particles. Thus, in order to determine how the ocean and the atmosphere interact and respond to environmental changes on a global scale, the characterization and understanding of the sea surface are essential. The uppermost part of the water column is defined as the sea-surface microlayer and experiences strong spatial and temporal dynamics, mainly due to meteorological forcing. Wave-damped areas at the sea surface are caused by the accumulation of surface-active organic material and are defined as slicks. Natural slicks are observed frequently but their biogeochemical properties are poorly understood. In the present study, we found up to 40 times more transparent exopolymer particles (TEP), the foundation of any biofilm, in slicks compared to the underlying bulk water at multiple stations in the North Pacific, South China Sea, and Baltic Sea. We found a significant lower enrichment of TEP (up to 6) in non-slick sea surfaces compared to its underlying bulk water. Moreover, slicks were characterized by a large microbial biomass, another shared feature with conventional biofilms on solid surfaces. Compared to non-slick samples (avg. pairwise similarity of 70%), the community composition of bacteria in slicks was increasingly (avg. pairwise similarity of 45%) different from bulk water communities, indicating that the TEP-matrix creates specific environments for its inhabitants. We, therefore, conclude that slicks can feature biofilm-like properties with the excessive accumulation of particles and microbes. We also assessed the potential distribution and frequency of slick-formation in coastal and oceanic regions, and their effect on air-sea CO2 exchange based on literature data. We estimate that slicks can reduce CO2 fluxes by up to 15%, and, therefore, play important local and regional roles in regulating air-sea interactions.

Hexagonal bubble formation and nucleation in sodium chloride solution

NASA Astrophysics Data System (ADS)

Wang, Lifen; Liu, Lei; Mohsin, Ali; Wen, Jianguo; Gu, Gong; Miller, Dean

The bubble is formed frequently at a solid-liquid interface when the surface of the solid or liquid has a tendency of accumulating molecular species due to unbalanced surface hydrophobicity attraction. Morphology and shape of the bubble are thought to be associated with the Laplace pressure that spherical-cap-shaped object are commonly observed. Dynamic surface nanobubble formation and nucleation in the controlled system have been not fully investigated due to the direct visualization challenge in liquid systems. Here, utilizing in situ TEM, dynamic formation and collapse of spherical-shaped nanobubbles were observed at the water-graphene interface, while hexagonal nanobubbles grew and merged with each other at water-crystalline sodium chloride interface. Our finding demonstrates that different hydrophobic-hydrophilic interaction systems give rise to the varied morphology of surface nanobubble, leading to the fundamental understanding of the interface-interaction-governed law on the formation of surface nanobubble.

Oxidation of MnO(100) and NaMnO2 formation: Characterization of Mn2+ and Mn3+ surfaces via XPS and water TPD

NASA Astrophysics Data System (ADS)

Feng, Xu; Cox, David F.

2018-09-01

The oxidation of clean and Na precovered MnO(100) has been investigated by X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED) and temperature programmed desorption (TPD) of adsorbed water. XPS results indicate that Mn3O4-like and Mn2O3-like surfaces can be formed by various oxidation treatments of clean and nearly-stoichiometric MnO(100), while a NaMnO2-like surface can be produced by the oxidation of MnO(100) pre-covered with multilayers of metallic Na. Water TPD results indicate that water adsorption/desorption is sensitive to the available oxidation states of surface Mn cations, and can be used to distinguish between surfaces exposing Mn2+and Mn3+ cations, or a combination of these oxidation states. Carbon dioxide and water TPD results from the NaMnO2-like surface indicate that pre-adsorbed water blocks the uptake of CO2, while water displaces pre-adsorbed CO2. No indication of a strong reactive interaction is observed between CO2, water and the NaMnO2-like surface under the conditions of our study.

Characterizing hydrophobicity at the nanoscale: a molecular dynamics simulation study.

PubMed

Bandyopadhyay, Dibyendu; Choudhury, Niharendu

2012-06-14

We use molecular dynamics (MD) simulations of water near nanoscopic surfaces to characterize hydrophobic solute-water interfaces. By using nanoscopic paraffin like plates as model solutes, MD simulations in isothermal-isobaric ensemble have been employed to identify characteristic features of such an interface. Enhanced water correlation, density fluctuations, and position dependent compressibility apart from surface specific hydrogen bond distribution and molecular orientations have been identified as characteristic features of such interfaces. Tetrahedral order parameter that quantifies the degree of tetrahedrality in the water structure and an orientational order parameter, which quantifies the orientational preferences of the second solvation shell water around a central water molecule, have also been calculated as a function of distance from the plate surface. In the vicinity of the surface these two order parameters too show considerable sensitivity to the surface hydrophobicity. The potential of mean force (PMF) between water and the surface as a function of the distance from the surface has also been analyzed in terms of direct interaction and induced contribution, which shows unusual effect of plate hydrophobicity on the solvent induced PMF. In order to investigate hydrophobic nature of these plates, we have also investigated interplate dewetting when two such plates are immersed in water.

Groundwater and surface water exchange and resulting Nitrate dynamics in the Bogue Phalia Basin in northwestern Mississippi

USGS Publications Warehouse

Barlow, Jeannie R.; Coupe, Richard H.

2012-01-01

During April 2007 through September 2008, the USGS collected hydrogeologic and water-quality data from a site on the Bogue Phalia to evaluate the role of groundwater and surface-water interaction on the transport of nitrate to the shallow sand and gravel aquifer underlying the Mississippi Alluvial Plain in northwestern Mississippi. A two-dimensional groundwater/surface-water exchange model was developed using temperature and head data and VS2DH, a variably saturated flow and energy transport model. Results from this model showed that groundwater/surface-water exchange at the site occurred regularly and recharge was laterally extensive into the alluvial aquifer. Nitrate was consistently reported in surface-water samples (n = 52, median concentration = 39.8 μmol/L) although never detected in samples collected from in-stream piezometers or shallow monitoring wells adjacent to the stream (n = 46). These two facts, consistent detections of nitrate in surface water and no detections of nitrate in groundwater, coupled with model results that indicate large amounts of surface water moving through an anoxic streambed, support the case for denitrification and nitrate loss through the streambed.

Water organization between oppositely charged surfaces: Implications for protein sliding along DNA a)

NASA Astrophysics Data System (ADS)

Marcovitz, Amir; Naftaly, Aviv; Levy, Yaakov

2015-02-01

Water molecules are abundant in protein-DNA interfaces, especially in their nonspecific complexes. In this study, we investigated the organization and energetics of the interfacial water by simplifying the geometries of the proteins and the DNA to represent them as two equally and oppositely charged planar surfaces immersed in water. We found that the potential of mean force for bringing the two parallel surfaces into close proximity comprises energetic barriers whose properties strongly depend on the charge density of the surfaces. We demonstrated how the organization of the water molecules into discretized layers and the corresponding energetic barriers to dehydration can be modulated by the charge density on the surfaces, salt, and the structure of the surfaces. The 1-2 layers of ordered water are tightly bound to the charged surfaces representing the nonspecific protein-DNA complex. This suggests that water might mediate one-dimensional diffusion of proteins along DNA (sliding) by screening attractive electrostatic interactions between the positively charged molecular surface on the protein and the negatively charged DNA backbone and, in doing so, reduce intermolecular friction in a manner that smoothens the energetic landscape for sliding, and facilitates the 1D diffusion of the protein.

Protein-lipid interactions at the air/water interface.

PubMed

Lad, Mitaben D; Birembaut, Fabrice; Frazier, Richard A; Green, Rebecca J

2005-10-07

Surface pressure measurements and external reflection FTIR spectroscopy have been used to probe protein-lipid interactions at the air/water interface. Spread monomolecular layers of stearic acid and phosphocholine were prepared and held at different compressed phase states prior to the introduction of protein to the buffered subphase. Contrasting interfacial behaviour of the proteins, albumin and lysozyme, was observed and revealed the role of both electrostatic and hydrophobic interactions in protein adsorption. The rate of adsorption of lysozyme to the air/water interface increased dramatically in the presence of stearic acid, due to strong electrostatic interactions between the negatively charged stearic acid head group and lysozyme, whose net charge at pH 7 is positive. Introduction of albumin to the subphase resulted in solubilisation of the stearic acid via the formation of an albumin-stearic acid complex and subsequent adsorption of albumin. This observation held for both human and bovine serum albumin. Protein adsorption to a PC layer held at low surface pressure revealed adsorption rates similar to adsorption to the bare air/water interface and suggested very little interaction between the protein and the lipid. For PC layers in their compressed phase state some adsorption of protein occurred after long adsorption times. Structural changes of both lysozyme and albumin were observed during adsorption, but these were dramatically reduced in the presence of a lipid layer compared to that of adsorption to the pure air/water interface.

A Study of Drop-Microstructured Surface Interactions during Dropwise Condensation with Quartz Crystal Microbalance

PubMed Central

Su, Junwei; Charmchi, Majid; Sun, Hongwei

2016-01-01

Dropwise condensation (DWC) on hydrophobic surfaces is attracting attention for its great potential in many industrial applications, such as steam power plants, water desalination, and de-icing of aerodynamic surfaces, to list a few. The direct dynamic characterization of liquid/solid interaction can significantly accelerate the progress toward a full understanding of the thermal and mass transport mechanisms during DWC processes. This work reports a novel Quartz Crystal Microbalance (QCM) based method that can quantitatively analyze the interaction between water droplets and micropillar surfaces during different condensation states such as filmwise, Wenzel, and partial Cassie states. A combined nanoimprinting lithography and chemical surface treatment approach was utilized to fabricate the micropillar based superhydrophobic and superhydrophilic surfaces on the QCM substrates. The normalized frequency shift of the QCM device together with the microscopic observation of the corresponding drop motion revealed the droplets growth and their coalescence processes and clearly demonstrated the differences between the three aforementioned condensation states. In addition, the transition between Cassie and Wenzel states was successfully captured by this method. The newly developed QCM system provides a valuable tool for the dynamic characterization of different condensation processes. PMID:27739452

A Semi-Analytical Solution to Time Dependent Groundwater Flow Equation Incorporating Stream-Wetland-Aquifer Interactions

NASA Astrophysics Data System (ADS)

Boyraz, Uǧur; Melek Kazezyılmaz-Alhan, Cevza

2017-04-01

Groundwater is a vital element of hydrologic cycle and the analytical & numerical solutions of different forms of groundwater flow equations play an important role in understanding the hydrological behavior of subsurface water. The interaction between groundwater and surface water bodies can be determined using these solutions. In this study, new hypothetical approaches are implemented to groundwater flow system in order to contribute to the studies on surface water/groundwater interactions. A time dependent problem is considered in a 2-dimensional stream-wetland-aquifer system. The sloped stream boundary is used to represent the interaction between stream and aquifer. The rest of the aquifer boundaries are assumed as no-flux boundary. In addition, a wetland is considered as a surface water body which lies over the whole aquifer. The effect of the interaction between the wetland and the aquifer is taken into account with a source/sink term in the groundwater flow equation and the interaction flow is calculated by using Darcy's approach. A semi-analytical solution is developed for the 2-dimensional groundwater flow equation in 5 steps. First, Laplace and Fourier cosine transforms are employed to obtain the general solution in Fourier and Laplace domain. Then, the initial and boundary conditions are applied to obtain the particular solution. Finally, inverse Fourier transform is carried out analytically and inverse Laplace transform is carried out numerically to obtain the final solution in space and time domain, respectively. In order to verify the semi-analytical solution, an explicit finite difference algorithm is developed and analytical and numerical solutions are compared for synthetic examples. The comparison of the analytical and numerical solutions shows that the analytical solution gives accurate results.

Effect of Ionic Strength and Surface Charge Density on the Kinetics of Cellulose Nanocrystal Thin Film Swelling.

PubMed

Reid, Michael S; Kedzior, Stephanie A; Villalobos, Marco; Cranston, Emily D

2017-08-01

This work explores cellulose nanocrystal (CNC) thin films (<50 nm) and particle-particle interactions by investigating film swelling in aqueous solutions with varying ionic strength (1-100 mM). CNC film hydration was monitored in situ via surface plasmon resonance, and the kinetics of liquid uptake were quantified. The contribution of electrostatic double-layer forces to film swelling was elucidated by using CNCs with different surface charges (anionic sulfate half ester groups, high and low surface charge density, and cationic trimethylammonium groups). Total water uptake in the thin films was found to be independent of ionic strength and surface chemistry, suggesting that in the aggregated state van der Waals forces dominate over double-layer forces to hold the films together. However, the rate of swelling varied significantly. The water uptake followed Fickian behavior, and the measured diffusion constants decreased with the ionic strength gradient between the film and the solution. This work highlights that nanoparticle interactions and dispersion are highly dependent on the state of particle aggregation and that the rate of water uptake in aggregates and thin films can be tailored based on surface chemistry and solution ionic strength.

Water response to ganglioside GM1 surface remodelling.

PubMed

Brocca, P; Rondelli, V; Mallamace, F; Di Bari, M T; Deriu, A; Lohstroh, W; Del Favero, E; Corti, M; Cantu', L

2017-01-01

Gangliosides are biological glycolipids participating in rafts, structural and functional domains of cell membranes. Their headgroups are able to assume different conformations when packed on the surface of an aggregate, more lying or standing. Switching between different conformations is possible, and is a collective event. Switching can be induced, in model systems, by concentration or temperature increase, then possibly involving ganglioside-water interaction. In the present paper, the effect of GM1 ganglioside headgroup conformation on the water structuring and interactions is addressed. Depolarized Rayleigh Scattering, Raman Scattering, Quasielastic Neutron Scattering and NMR measurements were performed on GM1 ganglioside solutions, focusing on solvent properties. All used techniques agree in evidencing differences in the structure and dynamics of solvent water on different time-and-length scales in the presence of either GM1 headgroup conformations. In general, all results indicate that both the structural properties of solvent water and its interactions with the sugar headgroups of GM1 respond to surface remodelling. The extent of this modification is much higher than expected and, interestingly, ganglioside headgroups seem to turn from cosmotropes to chaotropes upon collective rearrangement from the standing- to the lying-conformation. In a biological perspective, water structure modulation could be one of the physico-chemical elements contributing to the raft strategy, both for rafts formation and persistence and for their functional aspects. In particular, the interaction with approaching bodies could be favoured or inhibited or triggered by complex-sugar-sequence conformational switch. This article is part of a Special Issue entitled "Science for Life" Guest Editor: Dr. Austen Angell, Dr. Salvatore Magazù and Dr. Federica Migliardo. Copyright © 2016 Elsevier B.V. All rights reserved.

Deprotonated Water Dimers: The Building Blocks of Segmented Water Chains on Rutile RuO2(110)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mu, Rentao; Cantu Cantu, David; Glezakou, Vassiliki Alexandra

2015-10-15

Despite the importance of RuO2 in photocatalytic water splitting and catalysis in general, the interactions of water with even its most stable (110) surface are not well-understood. In this study we employ a combination of high-resolution scanning tunneling microscopy imaging with density functional theory based ab initio molecular dynamics, and we follow the formation and binding of linear water clusters on coordinatively unsaturated ruthenium rows. We find that clusters of all sizes (dimers, trimers, tetramers, extended chains) are stabilized by donating one proton per every two water molecules to the surface bridge bonded oxygen sites, in contrast with water monomersmore » that do not show a significant propensity for dissociation. The clusters with odd number of water molecules are less stable than the clusters with even number, and are generally not observed under thermal equilibrium. For all clusters with even numbers, the dissociated dimers represent the fundamental building blocks with strong intra-dimer hydrogen bonds and only very weak inter-dimer interactions resulting in segmented water chains.« less

Adsorption Study of a Water Molecule on Vacancy-Defected Nonpolar CdS Surfaces

PubMed Central

2017-01-01

A detailed understanding of the water–semiconductor interface is of major importance for elucidating the molecular interactions at the photocatalyst’s surface. Here, we studied the effect of vacancy defects on the adsorption of a water molecule on the (101̅0) and (112̅0) CdS surfaces, using spin-polarized density functional theory. We observed that the local spin polarization did not persist for most of the cationic vacancies on the surfaces, unlike in bulk, owing to surface reconstructions caused by displaced S atoms. This result suggests that cationic vacancies on these surfaces may not be the leading cause of the experimentally observed magnetism in CdS nanostructures. The surface vacancies are predominantly nonmagnetic except for one case, where a magnetic cationic vacancy is relatively stable due to constraints posed by the (101̅0) surface geometry. At this particular magnetic defect site, we found a very strong interaction with the H2O molecule leading to a case of chemisorption, where the local spin polarization vanishes concurrently. At the same defect site, adsorption of an O2 molecule was also simulated, and the results were found to be consistent with experimental electron paramagnetic resonance findings for powdered CdS. The anion vacancies on these surfaces were always found to be nonmagnetic and did not affect the water adsorption at these surfaces. PMID:28539988

Groundwater sustainability and groundwater/surface-water interaction in arid Dunhuang Basin, northwest China

NASA Astrophysics Data System (ADS)

Lin, Jingjing; Ma, Rui; Hu, Yalu; Sun, Ziyong; Wang, Yanxin; McCarter, Colin P. R.

2018-03-01

The Dunhuang Basin, a typical inland basin in northwestern China, suffers a net loss of groundwater and the occasional disappearance of the Crescent Lake. Within this region, the groundwater/surface-water interactions are important for the sustainability of the groundwater resources. A three-dimensional transient groundwater flow model was established and calibrated using MODFLOW 2000, which was used to predict changes to these interactions once a water diversion project is completed. The simulated results indicate that introducing water from outside of the basin into the Shule and Danghe rivers could reverse the negative groundwater balance in the Basin. River-water/groundwater interactions control the groundwater hydrology, where river leakage to the groundwater in the Basin will increase from 3,114 × 104 m3/year in 2017 to 11,875 × 104 m3/year in 2021, and to 17,039 × 104 m3/year in 2036. In comparison, groundwater discharge to the rivers will decrease from 3277 × 104 m3/year in 2017 to 1857 × 104 m3/year in 2021, and to 510 × 104 m3/year by 2036; thus, the hydrology will switch from groundwater discharge to groundwater recharge after implementing the water diversion project. The simulation indicates that the increased net river infiltration due to the water diversion project will raise the water table and then effectively increasing the water level of the Crescent Lake, as the lake level is contiguous with the water table. However, the regional phreatic evaporation will be enhanced, which may intensify soil salinization in the Dunhuang Basin. These results can guide the water allocation scheme for the water diversion project to alleviate groundwater depletion and mitigate geo-environmental problem.

Coupling a three-dimensional subsurface flow model with a land surface model to simulate stream-aquifer-land interactions

NASA Astrophysics Data System (ADS)

Huang, M.; Bisht, G.; Zhou, T.; Chen, X.; Dai, H.; Hammond, G. E.; Riley, W. J.; Downs, J.; Liu, Y.; Zachara, J. M.

2016-12-01

A fully coupled three-dimensional surface and subsurface land model is developed and applied to a site along the Columbia River to simulate three-way interactions among river water, groundwater, and land surface processes. The model features the coupling of the Community Land Model version 4.5 (CLM4.5) and a massively-parallel multi-physics reactive tranport model (PFLOTRAN). The coupled model (CLM-PFLOTRAN) is applied to a 400m×400m study domain instrumented with groundwater monitoring wells in the Hanford 300 Area along the Columbia River. CLM-PFLOTRAN simulations are performed at three different spatial resolutions over the period 2011-2015 to evaluate the impact of spatial resolution on simulated variables. To demonstrate the difference in model simulations with and without lateral subsurface flow, a vertical-only CLM-PFLOTRAN simulation is also conducted for comparison. Results show that the coupled model is skillful in simulating stream-aquifer interactions, and the land-surface energy partitioning can be strongly modulated by groundwater-river water interactions in high water years due to increased soil moisture availability caused by elevated groundwater table. In addition, spatial resolution does not seem to impact the land surface energy flux simulations, although it is a key factor for accurately estimating the mass exchange rates at the boundaries and associated biogeochemical reactions in the aquifer. The coupled model developed in this study establishes a solid foundation for understanding co-evolution of hydrology and biogeochemistry along the river corridors under historical and future hydro-climate changes.

Near-surface turbulence as a missing link in modeling evapotranspiration-soil moisture relationships

NASA Astrophysics Data System (ADS)

Haghighi, Erfan; Kirchner, James W.

2017-07-01

Despite many efforts to develop evapotranspiration (ET) models with improved parametrizations of resistance terms for water vapor transfer into the atmosphere, estimates of ET and its partitioning remain prone to bias. Much of this bias could arise from inadequate representations of physical interactions near nonuniform surfaces from which localized heat and water vapor fluxes emanate. This study aims to provide a mechanistic bridge from land-surface characteristics to vertical transport predictions, and proposes a new physically based ET model that builds on a recently developed bluff-rough bare soil evaporation model incorporating coupled soil moisture-atmospheric controls. The newly developed ET model explicitly accounts for (1) near-surface turbulent interactions affecting soil drying and (2) soil-moisture-dependent stomatal responses to atmospheric evaporative demand that influence leaf (and canopy) transpiration. Model estimates of ET and its partitioning were in good agreement with available field-scale data, and highlight hidden processes not accounted for by commonly used ET schemes. One such process, nonlinear vegetation-induced turbulence (as a function of vegetation stature and cover fraction) significantly influences ET-soil moisture relationships. Our results are particularly important for water resources and land use planning of semiarid sparsely vegetated ecosystems where soil surface interactions are known to play a critical role in land-climate interactions. This study potentially facilitates a mathematically tractable description of the strength (i.e., the slope) of the ET-soil moisture relationship, which is a core component of models that seek to predict land-atmosphere coupling and its feedback to the climate system in a changing climate.

Response of groundwater level and surface-water/groundwater interaction to climate variability: Clarence-Moreton Basin, Australia

NASA Astrophysics Data System (ADS)

Cui, Tao; Raiber, Matthias; Pagendam, Dan; Gilfedder, Mat; Rassam, David

2018-03-01

Understanding the response of groundwater levels in alluvial and sedimentary basin aquifers to climatic variability and human water-resource developments is a key step in many hydrogeological investigations. This study presents an analysis of groundwater response to climate variability from 2000 to 2012 in the Queensland part of the sedimentary Clarence-Moreton Basin, Australia. It contributes to the baseline hydrogeological understanding by identifying the primary groundwater flow pattern, water-level response to climate extremes, and the resulting dynamics of surface-water/groundwater interaction. Groundwater-level measurements from thousands of bores over several decades were analysed using Kriging and nonparametric trend analysis, together with a newly developed three-dimensional geological model. Groundwater-level contours suggest that groundwater flow in the shallow aquifers shows local variations in the close vicinity of streams, notwithstanding general conformance with topographic relief. The trend analysis reveals that climate variability can be quickly reflected in the shallow aquifers of the Clarence-Moreton Basin although the alluvial aquifers have a quicker rainfall response than the sedimentary bedrock formations. The Lockyer Valley alluvium represents the most sensitively responding alluvium in the area, with the highest declining (-0.7 m/year) and ascending (2.1 m/year) Sen's slope rates during and after the drought period, respectively. Different surface-water/groundwater interaction characteristics were observed in different catchments by studying groundwater-level fluctuations along hydrogeologic cross-sections. The findings of this study lay a foundation for future water-resource management in the study area.

Understanding Groundwater and Surface Water Exchange Processes Along a Controlled Stream Using Thermal Remote Sensing and In-Situ Measurements

NASA Astrophysics Data System (ADS)

Varli, D.; Yilmaz, K. K.

2016-12-01

Effective management of water resources requires understanding and quantification of interaction between groundwater and surface water bodies. Moreover, the exchange processes have recently received increasing attention due to important influences on biogeochemical and ecological status of watersheds. In this study we investigated the exchange processes between surface water and groundwater along Kirmir stream - a controlled stream nearby Kizilcahamam, Ankara, Turkey. At the first stage, potential stream reaches where the exchange processes could occur were pinpointed using geological and geomorphological information. Then, thermal remote sensing was utilized to further narrow down the potential locations in which interaction could occur at a smaller scale. Nested piezometers were installed at identified locations to observe the variations in vertical hydraulic gradient over time. Differential discharge measurements were performed to understand the gains and losses along the stream reach. Streambed temperature measurements were taken at two different depths for a period of time using temperature loggers to calculate the vertical fluid fluxes through the streambed at various locations. Basic water quality field parameters (temperature, electrical conductivity, total dissolved solid amount, dissolved oxygen, pH and oxidation - reduction potential) were measured along the stream reach, from surface water and the piezometers as wells as from the nearby springs and wells. Chloride mass balance was performed to find the contribution of groundwater and chloride concentrations were associated with the geology of the area. This hierarchical, multi-scale methodology provided an efficient and effective way to determine the locations and the direction of groundwater and surface water exchange processes within the study area.

The Soil-Plant-Atmosphere System - Past and Present.

NASA Astrophysics Data System (ADS)

Berry, J. A.; Baker, I. T.; Randall, D. A.; Sellers, P. J.

2012-12-01

Plants with stomata, roots and a vascular system first appeared on earth about 415 million years ago. This evolutionary innovation helped to set in motion non-linear feedback mechanisms that led to an acceleration of the hydrologic cycle over the continents and an expansion of the climate zones favorable for plant (and animal) life. Skeletal soils that developed long before plants came onto the land would have held water and nutrients in their pore space, yet these resources would have been largely unavailable to primitive, surface-dwelling non-vascular plants due to physical limitations on water transport once the surface layer of soil dries. Plants with roots and a vascular system that could span this dry surface layer could gain increased and prolonged access to the water and nutrients stored in the soil for photosynthesis. Maintenance of the hydraulic connections permitting water to be drawn through the vascular system from deep in the soil to the sites of evaporation in the leaves required a cuticle and physiological regulation of stomata. These anatomical and physiological innovations changed properties of the terrestrial surface (albedo, roughness, a vascular system and control of surface conductance) and set in motion complex interactions of the soil - plant - atmosphere system. We will use coupled physiological and meteorological models to examine some of these interactions.

Adsorption Behavior of Surfactant on Lignite Surface: A Comparative Experimental and Molecular Dynamics Simulation Study

PubMed Central

He, Meng; Zhang, Wei; Cao, Xiaoqiang; You, Xiaofang; Li, Lin

2018-01-01

Experimental and computational simulation methods are used to investigate the adsorption behavior of the surfactant nonylphenol ethoxylate (NPEO10), which contains 10 ethylene oxide groups, on the lignite surface. The adsorption of NPEO10 on lignite follow a Langmuir-type isotherm. The thermodynamic parameters of the adsorption process show that the whole process is spontaneous. X-ray photoelectron spectroscopic (XPS) analysis indicates that a significant fraction of the oxygen-containing functional groups on the lignitic surface were covered by NPEO10. Molecular dynamics (MD) simulations show that the NPEO10 molecules were found to adsorb at the water-coal interface. Moreover, polar interactions are the main effect in the adsorption process. The density distributions of coal, NPEO10, and water molecules along the Z axis show that the remaining hydrophobic portions of the surfactant extend into the solution, creating a more hydrophobic coal surface that repels water molecules. The negative interaction energy calculated from the density profiles of the head and tail groups along the three spatial directions between the surfactant and the lignitic surface suggest that the adsorption process is spontaneous. The self-diffusion coefficients show that the presence of NPEO10 causes higher water mobility by improving the hydrophobicity of lignite. PMID:29389899

The Dynamic Surface Tension of Water

PubMed Central

2017-01-01

The surface tension of water is an important parameter for many biological or industrial processes, and roughly a factor of 3 higher than that of nonpolar liquids such as oils, which is usually attributed to hydrogen bonding and dipolar interactions. Here we show by studying the formation of water drops that the surface tension of a freshly created water surface is even higher (∼90 mN m–1) than under equilibrium conditions (∼72 mN m–1) with a relaxation process occurring on a long time scale (∼1 ms). Dynamic adsorption effects of protons or hydroxides may be at the origin of this dynamic surface tension. However, changing the pH does not significantly change the dynamic surface tension. It also seems unlikely that hydrogen bonding or dipole orientation effects play any role at the relatively long time scale probed in the experiments. PMID:28301160

The Dynamic Surface Tension of Water.

PubMed

Hauner, Ines M; Deblais, Antoine; Beattie, James K; Kellay, Hamid; Bonn, Daniel

2017-04-06

The surface tension of water is an important parameter for many biological or industrial processes, and roughly a factor of 3 higher than that of nonpolar liquids such as oils, which is usually attributed to hydrogen bonding and dipolar interactions. Here we show by studying the formation of water drops that the surface tension of a freshly created water surface is even higher (∼90 mN m -1 ) than under equilibrium conditions (∼72 mN m -1 ) with a relaxation process occurring on a long time scale (∼1 ms). Dynamic adsorption effects of protons or hydroxides may be at the origin of this dynamic surface tension. However, changing the pH does not significantly change the dynamic surface tension. It also seems unlikely that hydrogen bonding or dipole orientation effects play any role at the relatively long time scale probed in the experiments.

Adsorption of guanidinium collectors on aluminosilicate minerals - a density functional study.

PubMed

Nulakani, Naga Venkateswara Rao; Baskar, Prathab; Patra, Abhay Shankar; Subramanian, Venkatesan

2015-10-07

In this density functional theory based investigation, we have modelled and studied the adsorption behaviour of guanidinium cations and substituted (phenyl, methoxy phenyl, nitro phenyl and di-nitro phenyl) guanidinium cationic collectors on the basal surfaces of kaolinite and goethite. The adsorption behaviour is assessed in three different media, such as gas, explicit water and pH medium, to understand the affinity of GC collectors to the SiO4 tetrahedral and AlO6 octahedral surfaces of kaolinite. The tetrahedral siloxane surface possesses a larger binding affinity to GC collectors than the octahedral sites due to the presence of surface exposed oxygen atoms that are active in the intermolecular interactions. Furthermore, the inductive electronic effects of substituted guanidinium cations also play a key role in the adsorption mechanism. Highly positive cations result in a stronger electrostatic interaction and preferential adsorption with the kaolinite surfaces than low positive cations. Computed interaction energies and electron densities at the bond critical points suggest that the adsorption of guanidinium cations on the surfaces of kaolinite and goethite is due to the formation of intra/inter hydrogen bonding networks. Also, the electrostatic interaction favours the high adsorption ability of GC collectors in the pH medium than gas phase and water medium. The structures and energies of GC collectors pave an intuitive view for future experimental studies on mineral flotation.

Imaging molecular interaction of NO on Cu(110) with a scanning tunneling microscope.

PubMed

Okuyama, Hiroshi

2014-10-01

Molecular interaction on metal surfaces is one of the central issues of surface science for the microscopic understanding of heterogeneous catalysis. In this Personal Account, I review the recent studies on NO/Cu(110) employing a scanning tunneling microscope (STM) to probe and control the molecule-molecule interaction on the surface. An individual NO molecule was observed as a characteristic dumbbell-shaped protrusion, visualizing the 2π* orbital. By manipulating the intermolecular distance with the STM, the overlap of the 2π* orbital between two NO molecules was controlled. The interaction causes the formation of the bonding and antibonding orbitals below and above the Fermi level, respectively, as a function of the intermolecular distance. The 2π* orbital also plays a role in the reaction of NO with water molecules. A water molecule donates a H-bond to NO, giving rise to the down-shift of the 2π* level below the Fermi level. This causes electron transfer from the substrate to NO, weakening, and eventually rupturing, the N-O bond. The facile bond cleavage by water molecules has implications for the catalytic reduction of NO under ambient conditions. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Integrated Water Flow Model (IWFM), A Tool For Numerically Simulating Linked Groundwater, Surface Water And Land-Surface Hydrologic Processes

NASA Astrophysics Data System (ADS)

Dogrul, E. C.; Brush, C. F.; Kadir, T. N.

2006-12-01

The Integrated Water Flow Model (IWFM) is a comprehensive input-driven application for simulating groundwater flow, surface water flow and land-surface hydrologic processes, and interactions between these processes, developed by the California Department of Water Resources (DWR). IWFM couples a 3-D finite element groundwater flow process and 1-D land surface, lake, stream flow and vertical unsaturated-zone flow processes which are solved simultaneously at each time step. The groundwater flow system is simulated as a multilayer aquifer system with a mixture of confined and unconfined aquifers separated by semiconfining layers. The groundwater flow process can simulate changing aquifer conditions (confined to unconfined and vice versa), subsidence, tile drains, injection wells and pumping wells. The land surface process calculates elemental water budgets for agricultural, urban, riparian and native vegetation classes. Crop water demands are dynamically calculated using distributed soil properties, land use and crop data, and precipitation and evapotranspiration rates. The crop mix can also be automatically modified as a function of pumping lift using logit functions. Surface water diversions and groundwater pumping can each be specified, or can be automatically adjusted at run time to balance water supply with water demand. The land-surface process also routes runoff to streams and deep percolation to the unsaturated zone. Surface water networks are specified as a series of stream nodes (coincident with groundwater nodes) with specified bed elevation, conductance and stage-flow relationships. Stream nodes are linked to form stream reaches. Stream inflows at the model boundary, surface water diversion locations, and one or more surface water deliveries per location are specified. IWFM routes stream flows through the network, calculating groundwater-surface water interactions, accumulating inflows from runoff, and allocating available stream flows to meet specified or calculated deliveries. IWFM utilizes a very straight-forward input file structure, allowing rapid development of complex simulations. A key feature of IWFM is a new algorithm for computation of groundwater flow across element faces. Enhancements to version 3.0 include automatic time-tracking of input and output data sets, linkage with the HEC-DSS database, and dynamic crop allocation using logit functions. Utilities linking IWFM to the PEST automated calibration suite are also available. All source code, executables and documentation are available for download from the DWR web site. IWFM is currently being used to develop hydrologic simulations of California's Central Valley (C2VSIM); the west side of California's San Joaquin Valley (WESTSIM); Butte County, CA; Solano County, CA; Merced County, CA; and the Oregon side of the Walla Walla River Basin.

Nitroimidazoles adsorption on activated carbon cloth from aqueous solution.

PubMed

Ocampo-Pérez, R; Orellana-Garcia, F; Sánchez-Polo, M; Rivera-Utrilla, J; Velo-Gala, I; López-Ramón, M V; Alvarez-Merino, M A

2013-07-01

The objective of this study was to analyze the equilibrium and adsorption kinetics of nitroimidazoles on activated carbon cloth (ACC), determining the main interactions responsible for the adsorption process and the diffusion mechanism of these compounds on this material. The influence of the different operational variables, such as ionic strength, pH, temperature, and type of water (ultrapure, surface, and waste), was also studied. The results obtained show that the ACC has a high capacity to adsorb nitroimidazoles in aqueous solution. Electrostatic interactions play an important role at pH<3, which favors the repulsive forces between dimetridazole or metronidazole and the ACC surface. The formation of hydrogen bonds and dispersive interactions play the predominant role at higher pH values. Modifications of the ACC with NH3, K2S2O8, and O3 demonstrated that its surface chemistry plays a predominant role in nitroimidazole adsorption on this material. The adsorption capacity of ACC is considerably high in surface waters and reduced in urban wastewater, due to the levels of alkalinity and dissolved organic matter present in the different types of water. Finally, the results of applying kinetic models revealed that the global adsorption rate of dimetridazole and metronidazole is controlled by intraparticle diffusion. Copyright © 2013 Elsevier Inc. All rights reserved.

Microscale Mechanism of Age Dependent Wetting Properties of Prickly Pear Cacti (Opuntia).

PubMed

Rykaczewski, Konrad; Jordan, Jacob S; Linder, Rubin; Woods, Erik T; Sun, Xiaoda; Kemme, Nicholas; Manning, Kenneth C; Cherry, Brian R; Yarger, Jeffery L; Majure, Lucas C

2016-09-13

Cacti thrive in xeric environments through specialized water storage and collection tactics such as a shallow, widespread root system that maximizes rainwater absorption and spines adapted for fog droplet collection. However, in many cacti, the epidermis, not the spines, dominates the exterior surface area. Yet, little attention has been dedicated to studying interactions of the cactus epidermis with water drops. Surprisingly, the epidermis of plants in the genus Opuntia, also known as prickly pear cacti, has water-repelling characteristics. In this work, we report that surface properties of cladodes of 25 taxa of Opuntia grown in an arid Sonoran climate switch from water-repelling to superwetting under water impact over the span of a single season. We show that the old cladode surfaces are not superhydrophilic, but have nearly vanishing receding contact angle. We study water drop interactions with, as well as nano/microscale topology and chemistry of, the new and old cladodes of two Opuntia species and use this information to uncover the microscopic mechanism underlying this phenomenon. We demonstrate that composition of extracted wax and its contact angle do not change significantly with time. Instead, we show that the reported age dependent wetting behavior primarily stems from pinning of the receding contact line along multilayer surface microcracks in the epicuticular wax that expose the underlying highly hydrophilic layers.

Detection of variable groundwater inflow in rivers with geochemical tracers: Using major ion chemistry and radiochemistry to evaluate radon 222Rn as possible tracer, an example from the Avon and Mitchell rivers, southeast Australia

NASA Astrophysics Data System (ADS)

Hofmann, H.; Cartwright, I.

2010-12-01

Surface water-groundwater interactions are an important part of the hydrological cycle from ecological and resource perspectives. The dynamics have implications for ecosystems, pollutant transport, and the quality and quantity of water supply for domestic use, agriculture and recreational purposes. Chemical tracers are a valuable tool for understanding the interaction of rivers and the surrounding groundwater. The Gippsland Basin is a significant agricultural area in Southeast Australia. Increasing population has resulted in increased demand of water resources for domestic and agricultural supply. Despite the fact that the Gippsland area receives substantial rainfall, irrigation is still necessary to maintain agricultural production during summer and drier years. The used water resources encompass mostly shallow groundwater and surface water (reservoirs and streams). The effect on the environment range from rising water levels and soil salinisation in the case of irrigation and falling water levels with subsequent necrotization of the vegetation and land subsidence in the case of communal and industrial water extraction. While the surface water components of the hydrological cycle are relatively well understood, groundwater has often been neglected. In particular, constraining the interaction between surface water and groundwater is required for sustainable water management. Gaining and loosing conditions in streams are subject to high temporal and spatial variability and hence, influence the amount of water accessible for agricultural purposes. Following a general assumption recharge to the aquifer occurs during the winter and spring month whereas the river receives water from the aquifer mainly during low flow (base flow) conditions in summer and autumn on a larger scale. Spatial variation, however, are a function of the hydraulic conductivity of the riverbed and the head differences between the aquifer and the river along the river banks. Infiltration and exfiltration rates from changing water levels in the river based on hydraulic models are often underestimated. The hydraulic models do not take into account the complexity of the system and are purely based on discharge figures. Radon (222Rn), stable isotopes and major ion chemistry were used to locate groundwater inputs to the Mitchell and Avon rivers. While stable isotopes and major ion chemistry are useful tracers to determine long-term variability, radon can be used to detect very localised groundwater discharge. Using hydrogeochemistry to locate and quantify groundwater discharge to rivers allows a more accurate assumption on the dynamics of the interaction between surface water and groundwater in the Gippsland area. Radon has been used in similar applications elsewhere. Input parameters for mass balance equations, however, were often approximated and averaged. Radioisotope concentrations in groundwater has been assessed from 20 bores and 5 soil profiles to deliver a more confidential groundwater input water radon concentration by assessing spatial variability and emanation potential of the above-mentioned elements.

Supramolecular Structures with Blood Plasma Proteins, Sugars and Nanosilica

NASA Astrophysics Data System (ADS)

Turov, V. V.; Gun'ko, V. M.; Galagan, N. P.; Rugal, A. A.; Barvinchenko, V. M.; Gorbyk, P. P.

Supramolecular structures with blood plasma proteins (albumin, immunoglobulin and fibrinogen (HPF)), protein/water/silica and protein/water/ silica/sugar (glucose, fructose and saccharose) were studied by NMR, adsorption, IR and UV spectroscopy methods. Hydration parameters, amounts of weakly and strongly bound waters and interfacial energy (γ S) were determined over a wide range of component concentrations. The γ S(C protein,C silica) graphs were used to estimate the energy of protein-protein, protein-surface and particle-particle interactions. It was shown that interfacial energy of self-association (γ as) of protein molecules depends on a type of proteins. A large fraction of water bound to proteins can be displaced by sugars, and the effect of disaccharide (saccharose) was greater than that of monosugars. Changes in the structural parameters of cavities in HPF molecules and complexes with HPF/silica nanoparticles filled by bound water were analysed using NMR-cryoporometry showing that interaction of proteins with silica leads to a significant decrease in the amounts of water bound to both protein and silica surfaces. Bionanocomposites with BSA/nanosilica/sugar can be used to influence states of living cells and tissues after cryopreservation or other treatments. It was shown that interaction of proteins with silica leads to strong decrease in the volume of all types of internal cavities filled by water.

Evidence From Hydrogen Isotopes in Meteorites for a Martian Permafrost

NASA Technical Reports Server (NTRS)

Usui, T.; Alexander, C. M. O'D.; Wang, J.; Simon, J. I.; Jones, J. H.

2014-01-01

Fluvial landforms on Mars suggest that it was once warm enough to maintain persistent liquid water on its surface. The transition to the present cold and dry Mars is closely linked to the history of surface water, yet the evolution of surficial water is poorly constrained. We have investigated the evolution of surface water/ ice and its interaction with the atmosphere by measurements of hydrogen isotope ratios (D/H: deuterium/ hydrogen) of martian meteorites. Hydrogen is a major component of water (H2O) and its isotopes fractionate significantly during hydrological cycling between the atmosphere, surface waters, ground ice, and polar cap ice. Based on in situ ion microprobe analyses of three geochemically different shergottites, we reported that there is a water/ice reservoir with an intermediate D/H ratio (delta D = 1,000?2500 %) on Mars. Here we present the possibility that this water/ice reservoir represents a ground-ice/permafrost that has existed relatively intact over geologic time.

Surface-Water and Ground-Water Interactions in the Central Everglades, Florida

USGS Publications Warehouse

Harvey, Judson W.; Newlin, Jessica T.; Krest, James M.; Choi, Jungyill; Nemeth, Eric A.; Krupa, Steven L.

2004-01-01

Recharge and discharge are hydrological processes that cause Everglades surface water to be exchanged for subsurface water in the peat soil and the underlying sand and limestone aquifer. These interactions are thought to be important to water budgets, water quality, and ecology in the Everglades. Nonetheless, relatively few studies of surface water and ground water interactions have been conducted in the Everglades, especially in its vast interior areas. This report is a product of a cooperative investigation conducted by the USGS and the South Florida Water Management District (SFWMD) aimed at developing and testing techniques that would provide reliable estimates of recharge and discharge in interior areas of WCA-2A (Water Conservation Area 2A) and several other sites in the central Everglades. The new techniques quantified flow from surface water to the subsurface (recharge) and the opposite (discharge) using (1) Darcy-flux calculations based on measured vertical gradients in hydraulic head and hydraulic conductivity of peat; (2) modeling transport through peat and decay of the naturally occurring isotopes 224Ra and 223Ra (with half-lives of 4 and 11 days, respectively); and (3) modeling transport and decay of naturally occurring and 'bomb-pulse' tritium (half-life of 12.4 years) in ground water. Advantages and disadvantages of each method for quantifying recharge and discharge were compared. In addition, spatial and temporal variability of recharge and discharge were evaluated and controlling factors identified. A final goal was to develop appropriately simplified (that is, time averaged) expressions of the results that will be useful in addressing a broad range of hydrological and ecological problems in the Everglades. Results were compared with existing information about water budgets from the South Florida Water Management Model (SFWMM), a principal tool used by the South Florida Water Management District to plan many of the hydrological aspects of the Everglades restoration. A century of water management for flood control and water storage in the Everglades resulted in the creation of the Water Conservation Areas (WCAs). Construction of the major canals began in the 1910s and the systems of levees that enclose the basins and structures that move water between basins were largely completed by the 1950s. The abandoned wetlands that remained outside of the Water Conservation areas tended to dry out and subside by 10 feet or more, which created abrupt transitions in land-surface elevations and water levels across the levees. The increases in topographic and hydraulic gradients near the margins of the WCAs, along with rapid pumping of water between basins to achieve management objectives, have together altered the patterns of recharge and discharge in the Everglades. The most evident change is the increase in the magnitude of recharge (on the upgradient side) and discharge (on the downgradient side) of levees separating WCA-2A from other basins or areas outside. Recharge and discharge in the vast interior of WCA-2A also likely have increased, but fluxes in the interior wetlands are more subtle and more difficult to quantify compared with areas close to the levees. Surface-water and ground-water interactions differ in fundamental ways between wetlands near WCA-2A's boundaries and wetlands in the basin's interior. The levees that form the WCA's boundaries have introduced step functions in the topographic and hydraulic gradients that are important as a force to drive water flow across the wetland ground surface. The resulting recharge and discharge fluxes tend to be unidirectional (connecting points of recharge on the upgradient side of the levee with points of discharge on the downgradient side), and fluxes are also relatively steady in magnitude compared with fluxes in the interior. Recharge flow paths are also relatively deep in their extent near levees, with fluxes passing entirely through the 1-m peat layer and inte

Water interaction with laboratory-simulated fossil fuel combustion particles.

PubMed

Popovicheva, O B; Kireeva, E D; Shonija, N K; Khokhlova, T D

2009-10-01

To clarify the impact of fossil fuel combustion particles' composition on their capacity to take up water, we apply a laboratory approach in which the method of deposition of compounds, identified in the particulate coverage of diesel and aircraft engine soot particles, is developed. It is found that near-monolayer organic/inorganic coverage of the soot particles may be represented by three groups of fossil fuel combustion-derived particulate matter with respect to their Hansh's coefficients related to hydrophilic properties. Water adsorption measurements show that nonpolar organics (aliphatic and aromatic hydrocarbons) lead to hydrophobization of the soot surface. Acidic properties of organic compounds such as those of oxidized PAHs, ethers, ketones, aromatic, and aliphatic acids are related to higher water uptake, whereas inorganic acids and ionic compounds such as salts of organic acids are shown to be responsible for soot hydrophilization. This finding allows us to quantify the role of the chemical identity of soot surface compounds in water uptake and the water interaction with fossil fuel combustion particles in the humid atmosphere.

Water-quality characteristics in runoff for three discovery farms in North Dakota, 2008-12

USGS Publications Warehouse

Nustad, Rochelle A.; Rowland, Kathleen M.; Wiederholt, Ronald

2015-01-01

Consistent patterns in water quality emerged at each individual farm, but similarities among farms also were observed. Suspended sediment, total phosphorus, and ammonia concentrations generally decreased downstream from feeding areas, and were primarily affected by surface runoff processes such as dilution, settling out of sediment, or vegetative uptake. Because surface runoff affects these constituents, increased annual surface runoff volume tended to result in increased loads and yields. No significant change in nitrate plus nitrite concentration were observed downstream from feeding areas because additional processes such as high solubility, nitrification, denitrification, and surface-groundwater interaction affect nitrate plus nitrite. For nitrate plus nitrite, increases in annual runoff volume did not consistently relate to increases in annual loads and yields. It seems that temporal distribution of precipitation and surface-groundwater interaction affected nitrate plus nitrite loads and yields. For surface drainage sites, the primary form of nitrogen was organic nitrogen whereas for subsurface drainage sites, the primary form of nitrogen was nitrate plus nitrite nitrogen.

Photogenerated Lectin Sensors Produced by Thiol-Ene/Yne Photo-Click Chemistry in Aqueous Solution

PubMed Central

Norberg, Oscar; Lee, Irene H.; Aastrup, Teodor; Yan, Mingdi; Ramström, Olof

2012-01-01

The photoinitiated radical reactions between thiols and alkenes/alkynes (thiol-ene and thiol-yne chemistry) have been applied to a functionalization methodology to produce carbohydrate-presenting surfaces for analyses of biomolecular interactions. Polymer-coated quartz surfaces were functionalized with alkenes or alkynes in a straightforward photochemical procedure utilizing perfluorophenylazide (PFPA) chemistry. The alkene/alkyne surfaces were subsequently allowed to react with carbohydrate thiols in water under UV-irradiation. The reaction can be carried out in a drop of water directly on the surface without photoinitiator and any disulfide side products were easily washed away after the functionalization process. The resulting carbohydrate-presenting surfaces were evaluated in real-time studies of protein-carbohydrate interactions using a quartz crystal microbalance flow-through system with recurring injections of selected lectins with intermediate regeneration steps using low pH buffer. The resulting methodology proved fast, efficient and scalable to high-throughput analysis formats, and the produced surfaces showed significant protein binding with expected selectivities of the lectins used in the study. PMID:22341757

Selected field and analytical methods and analytical results in the Dutch Flats area, western Nebraska, 1995-99

USGS Publications Warehouse

Verstraeten, Ingrid M.; Steele, G.V.; Cannia, J.C.; Bohlke, J.K.; Kraemer, T.E.; Hitch, D.E.; Wilson, K.E.; Carnes, A.E.

2001-01-01

A study of the water resources of the Dutch Flats area in the western part of the North Platte Natural Resources District, western Nebraska, was conducted from 1995 through 1999 to describe the surface water and hydrogeology, the spatial distribution of selected water-quality constituents in surface and ground water, and the surface-water/ground-water interaction in selected areas. This report describes the selected field and analytical methods used in the study and selected analytical results from the study not previously published. Specifically, dissolved gases, age-dating data, and other isotopes collected as part of an intensive sampling effort in August and November 1998 and all uranium and uranium isotope data collected through the course of this study are included in the report.

Tuning the interaction between propagating and localized surface plasmons for surface enhanced Raman scattering in water for biomedical and environmental applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shioi, Masahiko, E-mail: shioi.masahiko@jp.panasonic.com; Department of Electric and Electronic Engineering, Graduate School of Engineering, Kobe University, Rokkodai, Nada, Kobe 657-8501; Jans, Hilde

With a view to biomedical and environmental applications, we investigate the plasmonic properties of a rectangular gold nanodisk array in water to boost surface enhanced Raman scattering (SERS) effects. To control the resonance wavelengths of the surface plasmon polariton and the localized surface plasmon, their dependence on the array period and diameter in water is studied in detail using a finite difference time domain method. A good agreement is obtained between calculated resonant wavelengths and those of gold nanodisk arrays fabricated using electron beam lithography. For the optimized structure, a SERS enhancement factor of 7.8 × 10{sup 7} is achieved in watermore » experimentally.« less

Low-Dimensional Materials for Optoelectronic and Bioelectronic Applications

NASA Astrophysics Data System (ADS)

Hong, Tu

In this thesis, we first discuss the fundamentals of ab initio electronic structure theory and density functional theory (DFT). We also discuss statistics related to computing thermodynamic averages of molecular dynamics (MD). We then use this theory to analyze and compare the structural, dynamical, and electronic properties of liquid water next to prototypical metals including platinum, graphite, and graphene. Our results are built on Born-Oppenheimer molecular dynamics (BOMD) generated using density functional theory (DFT) which explicitly include van der Waals (vdW) interactions within a first principles approach. All calculations reported use large simulation cells, allowing for an accurate treatment of the water-electrode interfaces. We have included vdW interactions through the use of the optB86b-vdW exchange correlation functional. Comparisons with the Perdew-Burke-Ernzerhof (PBE) exchange correlation functional are also shown. We find an initial peak, due to chemisorption, in the density profile of the liquid water-Pt interface not seen in the liquid water-graphite interface, liquid watergraphene interface, nor interfaces studied previously. To further investigate this chemisorption peak, we also report differences in the electronic structure of single water molecules on both Pt and graphite surfaces. We find that a covalent bond forms between the single water molecule and the platinum surface, but not between the single water molecule and the graphite surface. We also discuss the effects that defects and dopants in the graphite and graphene surfaces have on the structure and dynamics of liquid water. Lastly, we introduce artificial neural networks (ANNs), and demonstrate how they can be used to machine learn electronic structure calculations. As a proof of principle, we show the success of an ANN potential energy surfaces for a dimer molecule with a Lennard-Jones potential.

The Modelling Analysis of the Response of Convective Transport of Energy and Water to Multiscale Surface Heterogeneity over Tibetan Plateau

NASA Astrophysics Data System (ADS)

SUN, G.; Hu, Z.; Ma, Y.; Ma, W.

2017-12-01

The land-atmospheric interactions over a heterogeneous surface is a tricky issue for accurately understanding the energy-water exchanges between land surface and atmosphere. We investigate the vertical transport of energy and water over a heterogeneous land surface in Tibetan Plateau during the evolution of the convective boundary layer using large eddy simulation (WRF_LES). The surface heterogeneity is created according to remote sensing images from high spatial resolution LandSat ETM+ images. The PBL characteristics over a heterogeneous surface are analyzed in terms of secondary circulations under different background wind conditions based on the horizontal and vertical distribution and evolution of wind. The characteristics of vertical transport of energy and heat over a heterogeneous surface are analyzed in terms of the horizontal distribution as well as temporal evolution of sensible and latent heat fluxes at different heights under different wind conditions on basis of the simulated results from WRF_LES. The characteristics of the heat and water transported into the free atmosphere from surface are also analyzed and quantified according to the simulated results from WRF_LES. The convective transport of energy and water are analyzed according to horizontal and vertical distributions of potential temperature and vapor under different background wind conditions. With the analysis based on the WRF_LES simulation, the performance of PBL schemes of mesoscale simulation (WRF_meso) is evaluated. The comparison between horizontal distribution of vertical fluxes and domain-averaged vertical fluxes of the energy and water in the free atmosphere is used to evaluate the performance of PBL schemes of WRF_meso in the simulation of vertical exchange of energy and water. This is an important variable because only the energy and water transported into free atmosphere is able to influence the regional and even global climate. This work would will be of great significance not only for understanding the land atmosphere interactions over a heterogeneous surface by evaluating and improving the performance PBL schemes in WRF-meso, but also for the understanding the profound effect of Tibetan Plateau on the regional and global climate.

Uranyl interaction with the hydrated (001) basal face of gibbsite: a combined theoretical and spectroscopic study.

PubMed

Veilly, Edouard; Roques, Jérôme; Jodin-Caumon, Marie-Camille; Humbert, Bernard; Drot, Romuald; Simoni, Eric

2008-12-28

The sorption of uranyl cations and water molecules on the basal (001) face of gibbsite was studied by combining vibrational and fluorescence spectroscopies together with density functional theory (DFT) computations. Both the calculated and experimental values of O-H bond lengths for the gibbsite bulk are in good agreement. In the second part, water sorption with this surface was studied to take into account the influence of hydration with respect to the uranyl adsorption. The computed water configurations agreed with previously published molecular dynamics studies. The uranyl adsorption in acidic media was followed by time-resolved laser-induced fluorescence spectroscopy and Raman spectrometry measurements. The existence of only one kind of adsorption site for the uranyl cation was then indicated in good agreement with the DFT calculations. The computation of the uranyl adsorption has been performed by means of a bidentate interaction with two surface oxygen atoms. The optimized structures displayed strong hydrogen bonds between the surface and the -yl oxygen of uranyl. The uranium-surface bond strength depends on the protonation state of the surface oxygen atoms. The calculated U-O(surface) bond lengths range between 2.1-2.2 and 2.6-2.7 A for the nonprotonated and protonated surface O atoms, respectively.

Modeling and optimization of trihalomethanes formation potential of surface water (a drinking water source) using Box-Behnken design.

PubMed

Singh, Kunwar P; Rai, Premanjali; Pandey, Priyanka; Sinha, Sarita

2012-01-01

The present research aims to investigate the individual and interactive effects of chlorine dose/dissolved organic carbon ratio, pH, temperature, bromide concentration, and reaction time on trihalomethanes (THMs) formation in surface water (a drinking water source) during disinfection by chlorination in a prototype laboratory-scale simulation and to develop a model for the prediction and optimization of THMs levels in chlorinated water for their effective control. A five-factor Box-Behnken experimental design combined with response surface and optimization modeling was used for predicting the THMs levels in chlorinated water. The adequacy of the selected model and statistical significance of the regression coefficients, independent variables, and their interactions were tested by the analysis of variance and t test statistics. The THMs levels predicted by the model were very close to the experimental values (R(2) = 0.95). Optimization modeling predicted maximum (192 μg/l) TMHs formation (highest risk) level in water during chlorination was very close to the experimental value (186.8 ± 1.72 μg/l) determined in laboratory experiments. The pH of water followed by reaction time and temperature were the most significant factors that affect the THMs formation during chlorination. The developed model can be used to determine the optimum characteristics of raw water and chlorination conditions for maintaining the THMs levels within the safe limit.

Trends in water monomer adsorption and dissociation on flat insulating surfaces.

PubMed

Hu, Xiao Liang; Carrasco, Javier; Klimeš, Jiří; Michaelides, Angelos

2011-07-21

The interaction of water with solid surfaces is key to a wide variety of industrial and natural processes. However, the basic principles that dictate how stable and in which state (intact or dissociated) water will be on a given surface are not fully understood. Towards this end, we have used density functional theory to examine water monomer adsorption on the (001) surfaces of a broad range of alkaline earth oxides, alkaline earth sulfides, alkali fluorides, and alkali chlorides. Some interesting general conclusions are arrived at: (i) on all the surfaces considered only a few specific adsorption structures are favoured; (ii) water becomes more stable upon descending the oxide and fluoride series but does not vary much upon going down the chloride and sulfide series; (iii) water is stabilised both by an increase in the lattice constant, which facilitates hydrogen bonding to the substrate, and by the flexibility of the substrate. These are also factors that favour water dissociation. We hope that this study is of some value in better understanding the surface science of water in general, and in assisting in the interpretation and design of future experiments. This journal is © the Owner Societies 2011

Synthesis of water soluble glycine capped silver nanoparticles and their surface selective interaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Agasti, Nityananda, E-mail: nnagasti@gmail.com; Singh, Vinay K.; Kaushik, N.K.

Highlights: • Synthesis of water soluble silver nanoparticles at ambient reaction conditions. • Glycine as stabilizing agent for silver nanoparticles. • Surface selective interaction of glycine with silver nanoparticles. • Glycine concentration influences crystalinity and optical property of silver nanoparticles. - Abstract: Synthesis of biocompatible metal nanoparticles has been an area of significant interest because of their wide range of applications. In the present study, we have successfully synthesized water soluble silver nanoparticles assisted by small amino acid glycine. The method is primarily based on reduction of AgNO{sub 3} with NaBH{sub 4} in aqueous solution under atmospheric air in themore » presence of glycine. UV–vis spectroscopy, transmission electron microscopy (TEM), X–ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, thermogravimetry (TG) and differential thermal analysis (DTA) techniques used for characterization of resulting silver nanoparticles demonstrated that, glycine is an effective capping agent to stabilize silver nanoparticles. Surface selective interaction of glycine on (1 1 1) face of silver nanoparticles has been investigated. The optical property and crystalline behavior of silver nanoparticles were found to be sensitive to concentration of glycine. X–ray diffraction studies ascertained the phase specific interaction of glycine on silver nanoparticles. Silver nanoparticles synthesized were of diameter 60 nm. We thus demonstrated an efficient synthetic method for synthesis of water soluble silver nanoparticles capped by amino acid under mild reaction conditions with excellent reproducibility.« less

Surface properties and morphology of mixed POSS-DPPC monolayers at the air/water interface.

PubMed

Rojewska, Monika; Skrzypiec, Marta; Prochaska, Krystyna

2017-02-01

From the point of view of the possible medical applications of POSS (polyhedral oligomeric silsesquioxanes), it is crucial to analyse interactions occurring between POSS and model biological membrane at molecular level. Knowledge of the interaction between POSS and DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine) allows prediction of the impact of POSS contained in biomaterials or cosmetics on a living organism. In the study presented, the surface properties and morphology of Langmuir monolayers formed by mixtures of POSS and the phospholipid (DPPC) at the air/water surface are examined. We selected two POSS derivatives, with completely different chemical structure of substituents attached to the corner of the silicon open cage, which allowed the analysis of the impact of the character of organic moieties (strongly hydrophobic or clearly hydrophilic) on the order of POSS molecules and their tendency to form self-aggregates at the air/water surface. POSS derivatives significantly changed the profile of the π-A isotherms obtained for DPPC but in different ways. On the basis of the regular solution theory, the miscibility and stability of the two components in the monolayer were analysed in terms of compression modulus (C s -1 ), excess Gibbs free energy (ΔG exc ), activity coefficients (γ) and interaction parameter (ξ). The results obtained indicate the existence of two different interaction mechanisms between DPPC and POSS which depend on the chemical character of moieties present in POSS molecules. Copyright © 2016 Elsevier B.V. All rights reserved.

Modeling interactions of agriculture and groundwater nitrate contaminants: application of The STICS-Eau-Dyssée coupled models over the Seine River Basin

NASA Astrophysics Data System (ADS)

Tavakoly, A. A.; Habets, F.; Saleh, F.; Yang, Z. L.

2017-12-01

Human activities such as the cultivation of N-fixing crops, burning of fossil fuels, discharging of industrial and domestic effluents, and extensive usage of fertilizers have recently accelerated the nitrogen loading to watersheds worldwide. Increasing nitrate concentration in surface water and groundwater is a major concern in watersheds with extensive agricultural activities. Nutrient enrichment is one of the major environmental problems in the French coastal zone. To understand and predict interactions between agriculture, surface water and groundwater nitrate contaminants, this study presents a modeling framework that couples the agronomic STICS model with Eau-Dyssée, a distributed hydrologic modeling system to simulate groundwater-surface water interaction. The coupled system is implemented on the Seine River Basin with an area of 88,000 km2 to compute daily nitrate contaminants. Representing a sophisticated hydrosystem with several aquifers and including the megalopolis of Paris, the Seine River Basin is well-known as one of the most productive agricultural areas in France. The STICS-EauDyssée framework is evaluated for a long-term simulation covering 39 years (1971-2010). Model results show that the simulated nitrate highly depends on the inflow produced by surface and subsurface waters. Daily simulation shows that the model captures the seasonal variation of observations and that the overall long-term simulation of nitrate contaminant is satisfactory at the regional scale.

Origins of the Non-DLVO Force between Glass Surfaces in Aqueous Solution.

PubMed

Adler, Joshua J.; Rabinovich, Yakov I.; Moudgil, Brij M.

2001-05-15

Direct measurement of surface forces has revealed that silica surfaces seem to have a short-range repulsion that is not accounted for in classical DLVO theory. The two leading hypotheses for the origin of the non-DLVO force are (i) structuring of water at the silica interface or (ii) water penetration into the surface resulting in a gel layer. In this article, the interaction of silica surfaces will be reviewed from the perspective of the non-DLVO force origin. In an attempt to more accurately describe the behavior of silica and glass surfaces, alternative models of how surfaces with gel layers should interact are proposed. It is suggested that a lessened van der Waals attraction originating from a thin gel layer may explain both the additional stability and the coagulation behavior of silica. It is important to understand the mechanisms underlying the existence of the non-DLVO force which is likely to have a major influence on the adsorption of polymers and surfactants used to modify the silica surface for practical applications in the ceramic, mineral, and microelectronic industries. Copyright 2001 Academic Press.

Effects of functionalization of carbon nanotubes on their dispersion in an ethylene glycol-water binary mixture--a molecular dynamics and ONIOM investigation.

PubMed

Balamurugan, Kanagasabai; Baskar, Prathab; Kumar, Ravva Mahesh; Das, Sumitesh; Subramanian, Venkatesan

2014-11-28

The present work utilizes classical molecular dynamics simulations to investigate the covalent functionalization of carbon nanotubes (CNTs) and their interaction with ethylene glycol (EG) and water molecules. The MD simulation reveals the dispersion of functionalized carbon nanotubes and the prevention of aggregation in aqueous medium. Further, residue-wise radial distribution function (RRDF) and atomic radial distribution function (ARDF) calculations illustrate the extent of interaction of -OH and -COOH functionalized CNTs with water molecules and the non-functionalized CNT surface with EG. As the presence of the number of functionalized nanotubes increases, enhancement in the propensity for the interaction with water molecules can be observed. However, the same trend decreases for the interaction of EG molecules. In addition, the ONIOM (M06-2X/6-31+G**:AM1) calculations have also been carried out on model systems to quantitatively determine the interaction energy (IE). It is found from these calculations that the relative enhancement in the interaction of water molecules with functionalized CNTs is highly favorable when compared to the interaction of EG.

Subsurface water and clay mineral formation during the early history of Mars.

PubMed

Ehlmann, Bethany L; Mustard, John F; Murchie, Scott L; Bibring, Jean-Pierre; Meunier, Alain; Fraeman, Abigail A; Langevin, Yves

2011-11-02

Clay minerals, recently discovered to be widespread in Mars's Noachian terrains, indicate long-duration interaction between water and rock over 3.7 billion years ago. Analysis of how they formed should indicate what environmental conditions prevailed on early Mars. If clays formed near the surface by weathering, as is common on Earth, their presence would indicate past surface conditions warmer and wetter than at present. However, available data instead indicate substantial Martian clay formation by hydrothermal groundwater circulation and a Noachian rock record dominated by evidence of subsurface waters. Cold, arid conditions with only transient surface water may have characterized Mars's surface for over 4 billion years, since the early-Noachian period, and the longest-duration aqueous, potentially habitable environments may have been in the subsurface.

Coupling a three-dimensional subsurface flow and transport model with a land surface model to simulate stream-aquifer-land interactions (CP v1.0)

NASA Astrophysics Data System (ADS)

Bisht, Gautam; Huang, Maoyi; Zhou, Tian; Chen, Xingyuan; Dai, Heng; Hammond, Glenn E.; Riley, William J.; Downs, Janelle L.; Liu, Ying; Zachara, John M.

2017-12-01

A fully coupled three-dimensional surface and subsurface land model is developed and applied to a site along the Columbia River to simulate three-way interactions among river water, groundwater, and land surface processes. The model features the coupling of the Community Land Model version 4.5 (CLM4.5) and a massively parallel multiphysics reactive transport model (PFLOTRAN). The coupled model, named CP v1.0, is applied to a 400 m × 400 m study domain instrumented with groundwater monitoring wells along the Columbia River shoreline. CP v1.0 simulations are performed at three spatial resolutions (i.e., 2, 10, and 20 m) over a 5-year period to evaluate the impact of hydroclimatic conditions and spatial resolution on simulated variables. Results show that the coupled model is capable of simulating groundwater-river-water interactions driven by river stage variability along managed river reaches, which are of global significance as a result of over 30 000 dams constructed worldwide during the past half-century. Our numerical experiments suggest that the land-surface energy partitioning is strongly modulated by groundwater-river-water interactions through expanding the periodically inundated fraction of the riparian zone, and enhancing moisture availability in the vadose zone via capillary rise in response to the river stage change. Meanwhile, CLM4.5 fails to capture the key hydrologic process (i.e., groundwater-river-water exchange) at the site, and consequently simulates drastically different water and energy budgets. Furthermore, spatial resolution is found to significantly impact the accuracy of estimated the mass exchange rates at the boundaries of the aquifer, and it becomes critical when surface and subsurface become more tightly coupled with groundwater table within 6 to 7 meters below the surface. Inclusion of lateral subsurface flow influenced both the surface energy budget and subsurface transport processes as a result of river-water intrusion into the subsurface in response to an elevated river stage that increased soil moisture for evapotranspiration and suppressed available energy for sensible heat in the warm season. The coupled model developed in this study can be used for improving mechanistic understanding of ecosystem functioning and biogeochemical cycling along river corridors under historical and future hydroclimatic changes. The dataset presented in this study can also serve as a good benchmarking case for testing other integrated models.

Coupling a three-dimensional subsurface flow and transport model with a land surface model to simulate stream–aquifer–land interactions (CP v1.0)

DOE PAGES

Bisht, Gautam; Huang, Maoyi; Zhou, Tian; ...

2017-12-12

A fully coupled three-dimensional surface and subsurface land model is developed and applied to a site along the Columbia River to simulate three-way interactions among river water, groundwater, and land surface processes. The model features the coupling of the Community Land Model version 4.5 (CLM4.5) and a massively parallel multiphysics reactive transport model (PFLOTRAN). The coupled model, named CP v1.0, is applied to a 400 m × 400 m study domain instrumented with groundwater monitoring wells along the Columbia River shoreline. CP v1.0 simulations are performed at three spatial resolutions (i.e., 2, 10, and 20 m) over a 5-year periodmore » to evaluate the impact of hydroclimatic conditions and spatial resolution on simulated variables. Results show that the coupled model is capable of simulating groundwater–river-water interactions driven by river stage variability along managed river reaches, which are of global significance as a result of over 30 000 dams constructed worldwide during the past half-century. Our numerical experiments suggest that the land-surface energy partitioning is strongly modulated by groundwater–river-water interactions through expanding the periodically inundated fraction of the riparian zone, and enhancing moisture availability in the vadose zone via capillary rise in response to the river stage change. Meanwhile, CLM4.5 fails to capture the key hydrologic process (i.e., groundwater–river-water exchange) at the site, and consequently simulates drastically different water and energy budgets. Furthermore, spatial resolution is found to significantly impact the accuracy of estimated the mass exchange rates at the boundaries of the aquifer, and it becomes critical when surface and subsurface become more tightly coupled with groundwater table within 6 to 7 meters below the surface. Inclusion of lateral subsurface flow influenced both the surface energy budget and subsurface transport processes as a result of river-water intrusion into the subsurface in response to an elevated river stage that increased soil moisture for evapotranspiration and suppressed available energy for sensible heat in the warm season. The coupled model developed in this study can be used for improving mechanistic understanding of ecosystem functioning and biogeochemical cycling along river corridors under historical and future hydroclimatic changes. The dataset presented in this study can also serve as a good benchmarking case for testing other integrated models.« less

Coupling a three-dimensional subsurface flow and transport model with a land surface model to simulate stream–aquifer–land interactions (CP v1.0)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bisht, Gautam; Huang, Maoyi; Zhou, Tian

A fully coupled three-dimensional surface and subsurface land model is developed and applied to a site along the Columbia River to simulate three-way interactions among river water, groundwater, and land surface processes. The model features the coupling of the Community Land Model version 4.5 (CLM4.5) and a massively parallel multiphysics reactive transport model (PFLOTRAN). The coupled model, named CP v1.0, is applied to a 400 m × 400 m study domain instrumented with groundwater monitoring wells along the Columbia River shoreline. CP v1.0 simulations are performed at three spatial resolutions (i.e., 2, 10, and 20 m) over a 5-year period to evaluate themore » impact of hydroclimatic conditions and spatial resolution on simulated variables. Results show that the coupled model is capable of simulating groundwater–river-water interactions driven by river stage variability along managed river reaches, which are of global significance as a result of over 30 000 dams constructed worldwide during the past half-century. Our numerical experiments suggest that the land-surface energy partitioning is strongly modulated by groundwater–river-water interactions through expanding the periodically inundated fraction of the riparian zone, and enhancing moisture availability in the vadose zone via capillary rise in response to the river stage change. Meanwhile, CLM4.5 fails to capture the key hydrologic process (i.e., groundwater–river-water exchange) at the site, and consequently simulates drastically different water and energy budgets. Furthermore, spatial resolution is found to significantly impact the accuracy of estimated the mass exchange rates at the boundaries of the aquifer, and it becomes critical when surface and subsurface become more tightly coupled with groundwater table within 6 to 7 meters below the surface. Inclusion of lateral subsurface flow influenced both the surface energy budget and subsurface transport processes as a result of river-water intrusion into the subsurface in response to an elevated river stage that increased soil moisture for evapotranspiration and suppressed available energy for sensible heat in the warm season. The coupled model developed in this study can be used for improving mechanistic understanding of ecosystem functioning and biogeochemical cycling along river corridors under historical and future hydroclimatic changes. The dataset presented in this study can also serve as a good benchmarking case for testing other integrated models.« less

Coupling a three-dimensional subsurface flow and transport model with a land surface model to simulate stream–aquifer–land interactions (CP v1.0)

DOE PAGES

Bisht, Gautam; Huang, Maoyi; Zhou, Tian; ...

2017-01-01

A fully coupled three-dimensional surface and subsurface land model is developed and applied to a site along the Columbia River to simulate three-way interactions among river water, groundwater, and land surface processes. The model features the coupling of the Community Land Model version 4.5 (CLM4.5) and a massively parallel multiphysics reactive transport model (PFLOTRAN). The coupled model, named CP v1.0, is applied to a 400 m × 400 m study domain instrumented with groundwater monitoring wells along the Columbia River shoreline. CP v1.0 simulations are performed at three spatial resolutions (i.e., 2, 10, and 20 m) over a 5-year period to evaluate themore » impact of hydroclimatic conditions and spatial resolution on simulated variables. Results show that the coupled model is capable of simulating groundwater–river-water interactions driven by river stage variability along managed river reaches, which are of global significance as a result of over 30 000 dams constructed worldwide during the past half-century. Our numerical experiments suggest that the land-surface energy partitioning is strongly modulated by groundwater–river-water interactions through expanding the periodically inundated fraction of the riparian zone, and enhancing moisture availability in the vadose zone via capillary rise in response to the river stage change. Meanwhile, CLM4.5 fails to capture the key hydrologic process (i.e., groundwater–river-water exchange) at the site, and consequently simulates drastically different water and energy budgets. Furthermore, spatial resolution is found to significantly impact the accuracy of estimated the mass exchange rates at the boundaries of the aquifer, and it becomes critical when surface and subsurface become more tightly coupled with groundwater table within 6 to 7 meters below the surface. Inclusion of lateral subsurface flow influenced both the surface energy budget and subsurface transport processes as a result of river-water intrusion into the subsurface in response to an elevated river stage that increased soil moisture for evapotranspiration and suppressed available energy for sensible heat in the warm season. The coupled model developed in this study can be used for improving mechanistic understanding of ecosystem functioning and biogeochemical cycling along river corridors under historical and future hydroclimatic changes. The dataset presented in this study can also serve as a good benchmarking case for testing other integrated models.« less

Coupling a three-dimensional subsurface flow and transport model with a land surface model to simulate stream–aquifer–land interactions (CP v1.0)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bisht, Gautam; Huang, Maoyi; Zhou, Tian

A fully coupled three-dimensional surface and subsurface land model is developed and applied to a site along the Columbia River to simulate three-way interactions among river water, groundwater, and land surface processes. The model features the coupling of the Community Land Model version 4.5 (CLM4.5) and a massively parallel multiphysics reactive transport model (PFLOTRAN). The coupled model, named CP v1.0, is applied to a 400 m × 400 m study domain instrumented with groundwater monitoring wells along the Columbia River shoreline. CP v1.0 simulations are performed at three spatial resolutions (i.e., 2, 10, and 20 m) over a 5-year periodmore » to evaluate the impact of hydroclimatic conditions and spatial resolution on simulated variables. Results show that the coupled model is capable of simulating groundwater–river-water interactions driven by river stage variability along managed river reaches, which are of global significance as a result of over 30 000 dams constructed worldwide during the past half-century. Our numerical experiments suggest that the land-surface energy partitioning is strongly modulated by groundwater–river-water interactions through expanding the periodically inundated fraction of the riparian zone, and enhancing moisture availability in the vadose zone via capillary rise in response to the river stage change. Meanwhile, CLM4.5 fails to capture the key hydrologic process (i.e., groundwater–river-water exchange) at the site, and consequently simulates drastically different water and energy budgets. Furthermore, spatial resolution is found to significantly impact the accuracy of estimated the mass exchange rates at the boundaries of the aquifer, and it becomes critical when surface and subsurface become more tightly coupled with groundwater table within 6 to 7 meters below the surface. Inclusion of lateral subsurface flow influenced both the surface energy budget and subsurface transport processes as a result of river-water intrusion into the subsurface in response to an elevated river stage that increased soil moisture for evapotranspiration and suppressed available energy for sensible heat in the warm season. The coupled model developed in this study can be used for improving mechanistic understanding of ecosystem functioning and biogeochemical cycling along river corridors under historical and future hydroclimatic changes. The dataset presented in this study can also serve as a good benchmarking case for testing other integrated models.« less

A miniature surface tension-driven robot using spatially elliptical moving legs to mimic a water strider's locomotion.

PubMed

Yan, J H; Zhang, X B; Zhao, J; Liu, G F; Cai, H G; Pan, Q M

2015-08-04

The highly agile and efficient water-surface locomotion of the water strider has stimulated substantial interest in biomimetic research. In this paper, we propose a new miniature surface tension-driven robot inspired by the water strider. A key feature of this robot is that its actuating leg possesses an ellipse-like spatial trajectory similar to that of a water strider by using a cam-link mechanism. Simplified models are presented to discuss the leg-water interactions as well as critical conditions for a leg penetrating the water surface, and simulations are performed on the robot's dynamic properties. The final fabricated robot weighs about 3.9 g, and can freely and stably walk on water at different gaits. The maximum forward and turning speeds of the robot are measured as 16 cm s(-1) and 23°/s, respectively. Furthermore, a similarity analysis with Bond number and Weber number demonstrates that the locomotion of this robot is quite analogous to that of a real water strider: the surface tension force dominates the lifting force and plays a major role in the propulsion force. This miniature surface tension-driven robot might have potential applications in many areas such as water quality monitoring and aquatic search and rescue.

Water structuring and collagen adsorption at hydrophilic and hydrophobic silicon surfaces.

PubMed

Cole, Daniel J; Payne, Mike C; Ciacchi, Lucio Colombi

2009-12-28

The adsorption of a collagen fragment on both a hydrophobic, hydrogen-terminated and a hydrophilic, natively oxidised Si surface is investigated using all-atom molecular dynamics. While favourable direct protein-surface interactions via localised contact points characterise adhesion to the hydrophilic surface, evenly spread surface/molecule contacts and stabilisation of the helical structure occurs upon adsorption on the hydrophobic surface. In the latter case, we find that adhesion is accompanied by a mutual fit between the hydrophilic/hydrophobic pattern within the protein and the layered water structure at the solid/liquid interface, which may provide an additional driving force to the classic hydrophobic effect.

GROUND WATER/SURFACE WATER INTERACTIONS IN A GREAT BASIN WET MEADOW ECOSYSTEM

EPA Science Inventory

Riparian corridors within upland watersheds of the Great Basin locally contain wet meadow ecosystems that support much of the region's biodiversity. Plant communities in these riparian and wet meadow ecosystems can be highly dependent on the depth to and fluctuations in the water...

Characterization of the Cell Surface Properties of Drinking Water Pathogens by Microbial Adhesion to Hydrocarbon and Electrophoretic Mobility Measurements

EPA Science Inventory

The surface characteristics of microbial cells directly influence their mobility and behavior within aqueous environments. The cell surface hydrophobicity (CSH) and electrophoretic mobility (EPM) of microbial cells impact a number of interactions and processes including aggregati...

Electron spin-echo envelope modulation (ESEEM) reveals water and phosphate interactions with the KcsA potassium channel.

PubMed

Cieslak, John A; Focia, Pamela J; Gross, Adrian

2010-02-23

Electron spin-echo envelope modulation (ESEEM) spectroscopy is a well-established technique for the study of naturally occurring paramagnetic metal centers. The technique has been used to study copper complexes, hemes, enzyme mechanisms, micellar water content, and water permeation profiles in membranes, among other applications. In the present study, we combine ESEEM spectroscopy with site-directed spin labeling (SDSL) and X-ray crystallography in order to evaluate the technique's potential as a structural tool to describe the native environment of membrane proteins. Using the KcsA potassium channel as a model system, we demonstrate that deuterium ESEEM can detect water permeation along the lipid-exposed surface of the KcsA outer helix. We further demonstrate that (31)P ESEEM is able to identify channel residues that interact with the phosphate headgroup of the lipid bilayer. In combination with X-ray crystallography, the (31)P data may be used to define the phosphate interaction surface of the protein. The results presented here establish ESEEM as a highly informative technique for SDSL studies of membrane proteins.

Modeling Coupled Movement of Water, Vapor, and Energy in Soils and at the Soil-Atmosphere Interface Using HYDRUS

NASA Astrophysics Data System (ADS)

Simunek, Jiri; Brunetti, Giuseppe; Saito, Hirotaka; Bristow, Keith

2017-04-01

Mass and energy fluxes in the subsurface are closely coupled and cannot be evaluated without considering their mutual interactions. However, only a few numerical models consider coupled water, vapor and energy transport in both the subsurface and at the soil-atmosphere interface. While hydrological and thermal processes in the subsurface are commonly implemented in existing models, which often consider both isothermally and thermally induced water and vapor flow, the interactions at the soil-atmosphere interface are often simplified, and the effects of slope inclination, slope azimuth, variable surface albedo and plant shading on incoming radiation and spatially variable surface mass and energy balance, and consequently on soil moisture and temperature distributions, are rarely considered. In this presentation we discuss these missing elements and our attempts to implement them into the HYDRUS model. We demonstrate implications of some of these interactions and their impact on the spatial distributions of soil temperature and water content, and their effect on soil evaporation. Additionally, we will demonstrate the use of the HYDRUS model to simulate processes relevant to the ground source heat pump systems.

Book Review: Near infrared surface-enhanced Raman spectroscopic study of antiretroviraly drugs hypericin and emodin in aqueous silver colloids

NASA Astrophysics Data System (ADS)

Sánchez-Cortés, S.; Jancura, D.; Miskovsky, P.; Bertoluzza, A.

1997-05-01

The near infrared surface-enhanced Raman spectra (NIR SERS) of antiretroviraly drugs hypericin and its analogs emodin and bianthrone were studied at different drug concentration, dimethylsulfoxide concentration, pH and time. The differences observed in the SERS spectra when varying some of these parameters are attributed to changes in the adsorbate coverage and orientation of these molecules on the silver colloids, and can be related to the monomeric drug concentration existing in the solution. Two different drug orientations on the metal surface can be deduced: perpendicular and planar, which can be characterized by two different SERS profiles. The drug reorientation on the surface is indicative of a change in the oligomer-monomer equilibrium in the solution, what implies that the SERS technique can be used as an indirect method to monitor the intermolecular interactions of these molecules in water. In addition the UV-visible absorption spectra of these drugs also reveals the existence of intermolecular interactions in water and the temperature dependence of these interactions.

Groundwater-surface water interactions across scales in a boreal landscape investigated using a numerical modelling approach

NASA Astrophysics Data System (ADS)

Jutebring Sterte, Elin; Johansson, Emma; Sjöberg, Ylva; Huseby Karlsen, Reinert; Laudon, Hjalmar

2018-05-01

Groundwater and surface-water interactions are regulated by catchment characteristics and complex inter- and intra-annual variations in climatic conditions that are not yet fully understood. Our objective was to investigate the influence of catchment characteristics and freeze-thaw processes on surface and groundwater interactions in a boreal landscape, the Krycklan catchment in Sweden. We used a numerical modelling approach and sub-catchment evaluation method to identify and evaluate fundamental catchment characteristics and processes. The model reproduced observed stream discharge patterns of the 14 sub-catchments and the dynamics of the 15 groundwater wells with an average accumulated discharge error of 1% (15% standard deviation) and an average groundwater-level mean error of 0.1 m (0.23 m standard deviation). We show how peatland characteristics dampen the effect of intense rain, and how soil freeze-thaw processes regulate surface and groundwater partitioning during snowmelt. With these results, we demonstrate the importance of defining, understanding and quantifying the role of landscape heterogeneity and sub-catchment characteristics for accurately representing catchment hydrological functioning.

Water on BN doped benzene: A hard test for exchange-correlation functionals and the impact of exact exchange on weak binding

DOE PAGES

Al-Hamdani, Yasmine S.; Alfè, Dario; von Lilienfeld, O. Anatole; ...

2014-10-22

Density functional theory (DFT) studies of weakly interacting complexes have recently focused on the importance of van der Waals dispersion forces, whereas the role of exchange has received far less attention. Here, by exploiting the subtle binding between water and a boron and nitrogen doped benzene derivative (1,2-azaborine) we show how exact exchange can alter the binding conformation within a complex. Benchmark values have been calculated for three orientations of the water monomer on 1,2-azaborine from explicitly correlated quantum chemical methods, and we have also used diffusion quantum Monte Carlo. For a host of popular DFT exchange-correlation functionals we showmore » that the lack of exact exchange leads to the wrong lowest energy orientation of water on 1,2-azaborine. As such, we suggest that a high proportion of exact exchange and the associated improvement in the electronic structure could be needed for the accurate prediction of physisorption sites on doped surfaces and in complex organic molecules. Meanwhile to predict correct absolute interaction energies an accurate description of exchange needs to be augmented by dispersion inclusive functionals, and certain non-local van der Waals functionals (optB88- and optB86b-vdW) perform very well for absolute interaction energies. Through a comparison with water on benzene and borazine (B₃N₃H₆) we show that these results could have implications for the interaction of water with doped graphene surfaces, and suggest a possible way of tuning the interaction energy.« less

Intermolecular and interfacial forces: Elucidating molecular mechanisms using chemical force microscopy

NASA Astrophysics Data System (ADS)

Ashby, Paul David

Investigation into the origin of forces dates to the early Greeks. Yet, only in recent decades have techniques for elucidating the molecular origin of forces been developed. Specifically, Chemical Force Microscopy uses the high precision and nanometer scale probe of Atomic Force Microscopy to measure molecular and interfacial interactions. This thesis presents the development of many novel Chemical Force Microscopy techniques for measuring equilibrium and time-dependant force profiles of molecular interactions, which led to a greater understanding of the origin of interfacial forces in solution. In chapter 2, Magnetic Feedback Chemical Force Microscopy stiffens the cantilever for measuring force profiles between self-assembled monolayer (SAM) surfaces. Hydroxyl and carboxyl terminated SAMs produce long-range interactions that extend one or three nanometers into the solvent, respectively. In chapter 3, an ultra low noise AFM is produced through multiple modifications to the optical deflection detection system and signal processing electronics. In chapter 4, Brownian Force Profile Reconstruction is developed for accurate measurement of steep attractive interactions. Molecular ordering is observed for OMCTS, 1-nonanol, and water near flat surfaces. The molecular ordering of the solvent produces structural or solvation forces, providing insight into the orientation and possible solidification of the confined solvent. Seven molecular layers of OMCTS are observed but the oil remains fluid to the last layer. 1-nonanol strongly orders near the surface and becomes quasi-crystalline with four layers. Water is oriented by the surface and symmetry requires two layers of water (3.7 A) to be removed simultaneously. In chapter 5, electronic control of the cantilever Q (Q-control) is used to obtain the highest imaging sensitivity. In chapter 6, Energy Dissipation Chemical Force Microscopy is developed to investigate the time dependence and dissipative characteristics of SAM interfacial interactions in solution. Long-range adhesive forces for hydroxyl and carboxyl terminated SAM surfaces arise from solvent, not ionic, interactions. Exclusion of the solvent and contact between the SAM surfaces leads to rearrangement of the SAM headgroups. The isolation of the chemical and physical interfacial properties from the topography by Energy Dissipation Chemical Force Microscopy produces a new quantitative high-sensitivity imaging mode.

The cellular environment of cancerous human tissue. Interfacial and dangling water as a "hydration fingerprint".

PubMed

Abramczyk, Halina; Brozek-Pluska, Beata; Krzesniak, Marta; Kopec, Monika; Morawiec-Sztandera, Alina

2014-08-14

Despite a large number of publications, the role of water in the cellular environment of biological tissue has not been clarified. Characterizing the biological interface is a key challenge in understanding the interactions of water in the tissue. Although we often assume that the properties of the bulk water can be translated to the crowded biological environment, this approach must be considerably revised when considering the biological interface. To our knowledge, few studies have directly monitored the interactions and accumulation of water in the restricted environments of the biological tissue upon realistic crowding conditions. The present study focuses on a molecular picture of water molecules at the biological interface, or specifically, water molecules adjacent to the hydrophobic and hydrophilic surfaces of normal and cancerous tissues. We recorded and analyzed the IR and Raman spectra of the νs(OH) stretching modes of water at the biological interfaces of the human breast and neck tissues. The results revealed dramatic changes in the water content in the tissue and are potentially relevant to both the fundamental problems of interfacial water modeling and the molecular diagnostics of cancer as a 'hydration fingerprint'. Herein, we will discuss the origin of the vibrational substructures observed for the νs(OH) stretching modes of water, showing that the interfacial water interacting via H-bond with other water molecules and biomolecules at the biological surface and free OH vibration of the dangling water are sensitive indicators of the pathology between the normal (noncancerous) and cancerous tissue and cancer types. Copyright © 2014 Elsevier B.V. All rights reserved.

The hydration structure at yttria-stabilized cubic zirconia (110)-water interface with sub-Ångström resolution

DOE PAGES

Hou, Binyang; Kim, Seunghyun; Kim, Taeho; ...

2016-06-15

The interfacial hydration structure of yttria-stabilized cubic zirconia (110) surface in contact with water was determined with ~0.5 Å resolution by high-resolution X-ray reflectivity measurement. The terminal layer shows a reduced electron density compared to the following substrate lattice layers, which indicates there are additional defects generated by metal depletion as well as intrinsic oxygen vacancies, both of which are apparently filled by water species. Above this top surface layer, two additional adsorbed layers are observed forming a characteristic interfacial hydration structure. The first adsorbed layer shows abnormally high density as pure water and likely includes metal species, whereas themore » second layer consists of pure water. The observed interfacial hydration structure seems responsible for local equilibration of the defective surface in water and eventually regulating the long-term degradation processes. As a result, the multitude of water interactions with the zirconia surface results in the complex but highly ordered interfacial structure constituting the reaction front.« less

High-resolution Continental Scale Land Surface Model incorporating Land-water Management in United States

NASA Astrophysics Data System (ADS)

Shin, S.; Pokhrel, Y. N.

2016-12-01

Land surface models have been used to assess water resources sustainability under changing Earth environment and increasing human water needs. Overwhelming observational records indicate that human activities have ubiquitous and pertinent effects on the hydrologic cycle; however, they have been crudely represented in large scale land surface models. In this study, we enhance an integrated continental-scale land hydrology model named Leaf-Hydro-Flood to better represent land-water management. The model is implemented at high resolution (5km grids) over the continental US. Surface water and groundwater are withdrawn based on actual practices. Newly added irrigation, water diversion, and dam operation schemes allow better simulations of stream flows, evapotranspiration, and infiltration. Results of various hydrologic fluxes and stores from two sets of simulation (one with and the other without human activities) are compared over a range of river basin and aquifer scales. The improved simulations of land hydrology have potential to build consistent modeling framework for human-water-climate interactions.

The Value of GRACE Data in Improving, Assessing and Evaluating Land Surface and Climate Models

NASA Astrophysics Data System (ADS)

Yang, Z.

2011-12-01

I will review how the Gravity Recovery and Climate Experiment (GRACE) satellite measurements have improved land surface models that are developed for weather, climate, and hydrological studies. GRACE-derived terrestrial water storage (TWS) changes have been successfully used to assess and evaluate the improved representations of land-surface hydrological processes such as groundwater-soil moisture interaction, frozen soil and infiltration, and the topographic control on runoff production, as evident in the simulations from the latest Noah-MP, the Community Land Model, and the Community Climate System Model. GRACE data sets have made it possible to estimate key terrestrial water storage components (snow mass, surface water, groundwater or water table depth), biomass, and surface water fluxes (evapotranspiration, solid precipitation, melt of snow/ice). Many of the examples will draw from my Land, Environment and Atmosphere Dynamics group's work on land surface model developments, snow mass retrieval, and multi-sensor snow data assimilation using the ensemble Karman filter and the ensemble Karman smoother. Finally, I will briefly outline some future directions in using GRACE in land surface modeling.

The role of water in slip casting

NASA Technical Reports Server (NTRS)

Mccauley, R. A.; Phelps, G. W.

1984-01-01

Slips and casting are considered in terms of physical and colloidal chemistry. Casting slips are polydisperse suspensions of lyophobic particles in water, whose degree of coagulation is controlled by interaction of flocculating and deflocculating agents. Slip casting rate and viscosity are functions of temperature. Slip rheology and response to deflocculating agents varies significantly as the kinds and amounts of colloid modifiers change. Water is considered as a raw material. Various concepts of water/clay interactions and structures are discussed. Casting is a de-watering operation in which water moves from slip to cast to mold in response to a potential energy termed moisture stress. Drying is an evaporative process from a free water surface.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Al-Hamdani, Yasmine S.; Alfè, Dario; von Lilienfeld, O. Anatole

Density functional theory (DFT) studies of weakly interacting complexes have recently focused on the importance of van der Waals dispersion forces, whereas the role of exchange has received far less attention. Here, by exploiting the subtle binding between water and a boron and nitrogen doped benzene derivative (1,2-azaborine) we show how exact exchange can alter the binding conformation within a complex. Benchmark values have been calculated for three orientations of the water monomer on 1,2-azaborine from explicitly correlated quantum chemical methods, and we have also used diffusion quantum Monte Carlo. For a host of popular DFT exchange-correlation functionals we showmore » that the lack of exact exchange leads to the wrong lowest energy orientation of water on 1,2-azaborine. As such, we suggest that a high proportion of exact exchange and the associated improvement in the electronic structure could be needed for the accurate prediction of physisorption sites on doped surfaces and in complex organic molecules. Meanwhile to predict correct absolute interaction energies an accurate description of exchange needs to be augmented by dispersion inclusive functionals, and certain non-local van der Waals functionals (optB88- and optB86b-vdW) perform very well for absolute interaction energies. Through a comparison with water on benzene and borazine (B₃N₃H₆) we show that these results could have implications for the interaction of water with doped graphene surfaces, and suggest a possible way of tuning the interaction energy.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Al-Hamdani, Yasmine S.; Michaelides, Angelos, E-mail: angelos.michaelides@ucl.ac.uk; Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ

Density functional theory (DFT) studies of weakly interacting complexes have recently focused on the importance of van der Waals dispersion forces, whereas the role of exchange has received far less attention. Here, by exploiting the subtle binding between water and a boron and nitrogen doped benzene derivative (1,2-azaborine) we show how exact exchange can alter the binding conformation within a complex. Benchmark values have been calculated for three orientations of the water monomer on 1,2-azaborine from explicitly correlated quantum chemical methods, and we have also used diffusion quantum Monte Carlo. For a host of popular DFT exchange-correlation functionals we showmore » that the lack of exact exchange leads to the wrong lowest energy orientation of water on 1,2-azaborine. As such, we suggest that a high proportion of exact exchange and the associated improvement in the electronic structure could be needed for the accurate prediction of physisorption sites on doped surfaces and in complex organic molecules. Meanwhile to predict correct absolute interaction energies an accurate description of exchange needs to be augmented by dispersion inclusive functionals, and certain non-local van der Waals functionals (optB88- and optB86b-vdW) perform very well for absolute interaction energies. Through a comparison with water on benzene and borazine (B{sub 3}N{sub 3}H{sub 6}) we show that these results could have implications for the interaction of water with doped graphene surfaces, and suggest a possible way of tuning the interaction energy.« less

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. Copyright © 2015 Elsevier Inc. All rights reserved.

Simulation of groundwater and surface-water interaction and effects of pumping in a complex glacial-sediment aquifer, east central Massachusetts

USGS Publications Warehouse

Eggleston, Jack R.; Carlson, Carl S.; Fairchild, Gillian M.; Zarriello, Phillip J.

2012-01-01

The effects of groundwater pumping on surface-water features were evaluated by use of a numerical groundwater model developed for a complex glacial-sediment aquifer in northeastern Framingham, Massachusetts, and parts of surrounding towns. The aquifer is composed of sand, gravel, silt, and clay glacial-fill sediments up to 270 feet thick over an irregular fractured bedrock surface. Surface-water bodies, including Cochituate Brook, the Sudbury River, Lake Cochituate, Dudley Pond, and adjoining wetlands, are in hydraulic connection with the aquifer and can be affected by groundwater withdrawals. Groundwater and surface-water interaction was simulated with MODFLOW-NWT under current conditions and a variety of hypothetical pumping conditions. Simulations of hypothetical pumping at reactivated water supply wells indicate that captured groundwater would decrease baseflow to the Sudbury River and induce recharge from Lake Cochituate. Under constant (steady-state) pumping, induced groundwater recharge from Lake Cochituate was equal to about 32 percent of the simulated pumping rate, and flow downstream in the Sudbury River decreased at the same rate as pumping. However, surface water responded quickly to pumping stresses. When pumping was simulated for 1 month and then stopped, streamflow depletions decreased by about 80 percent within 2 months and by about 90 percent within about 4 months. The fast surface water response to groundwater pumping offers the potential to substantially reduce streamflow depletions during periods of low flow, which are of greatest concern to the ecological integrity of the river. Results indicate that streamflow depletion during September, typically the month of lowest flow, can be reduced by 29 percent by lowering the maximum pumping rates to near zero during September. Lowering pumping rates for 3 months (July through September) reduces streamflow depletion during September by 79 percent as compared to constant pumping. These results demonstrate that a seasonal or streamflow-based groundwater pumping schedule can reduce the effects of pumping during periods of low flow.

Polymer adsorption on silica and wettability of graphene oxide surfaces, experiments and simulations

NASA Astrophysics Data System (ADS)

Mortazavian, Hamid

Among the various classifications of polymer composites, studying polymers adsorbed to a surface such as silica is important due to their numerous applications. Adsorbed polymers usually show different properties than their bulk counterparts due to their interactions with the surface. In this study, we observed tightly- and loosely-bound polymer and mobile components in poly(vinyl acetate) (PVAc) on silica both with temperature-modulated differential scanning calorimetry (TMDSC) experiments and computer simulations. The more-mobile component which correlated to the region of low density at the air interface is reported for the first time using TMDSC thermograms. Pore size distribution and pore volume development of adsorbed PMMA samples showed different behavior below and above the tightly-bound amount of the polymer. The amount of tightly-bound polymer was obtained by a linear regression analysis of the ratio of the area under the two glass transitions. The values obtained vary from 0.52 to 0.86 mg PVAc/m2 silica depending upon the molecular mass for the amounts of PVAc and the specific surface area of fumed silica. Direct comparisons of the thermal properties and intermolecular interactions were performed between PVAc and poly(methyl methacrylate) (PMMA) with similar molecular masses and adsorbed amounts on silica. A larger amount of tightly-bound polymer and a greater change in glass transition were observed for adsorbed PMMA compared to adsorbed PVAc. These observations suggested that the interactions between PMMA and silica were stronger than those between PVAc and silica. Molecular modeling of these surface polymers showed that PMMA associates more strongly with silica than does PVAc through additional hydrogen-bonding interactions. Graphene oxide (GO) material surface characteristics make it easy to functionalize, making it a water repellant surface. To test the effect of chemical makeup and size of attached groups on the surface wettability of GO, we performed experimental water contact angle measurements and molecular modeling investigations on functionalized GO surfaces. Experimental and molecular simulation water contact angle measurements showed quantitative agreement for functionalizing groups with the same chain length at a variety of surface coverages.

Interplay of confinement and surface energetics in the interaction of water with a metal–organic framework

DOE PAGES

Wu, Di; Guo, Xiaofeng; Sun, Hui; ...

2016-03-24

Here, the enthalpy of water adsorption (Δh) on the metal–organic framework (MOF) HKUST-1 has been determined directly by calorimetry. The most exothermic value of Δh [–119.4 ± 0.5 kJ/(mol of water)] occurs at zero coverage and perhaps represents water confinement in the smallest (4-Å) cages. An intermediate Δh value of –50.2 ± 1.8 kJ/(mol of water) at higher loading probably corresponds to the binding of water on the available Cu nodes and subsequent filling of the largest (11-Å) pores. The weakest interactions take place in the medium (10-Å) cages, showing weak inclusion of water clusters in a limited hydrophobic environment.more » By combining ethanol adsorption calorimetry, mathematical analysis of the slope of the water adsorption isotherm, and the differential enthalpy of water adsorption curve, we are able not only to develop an approach to separate energetically multistage guest–host interactions in complex MOF architectures but also to distinguish a sequence of interactions with very similar energetic effects.« less

Measurement of the adsorption energy difference between ortho- and para-D2 on an amorphous ice surface.

PubMed

Amiaud, L; Momeni, A; Dulieu, F; Fillion, J H; Matar, E; Lemaire, J-L

2008-02-08

Molecular hydrogen interaction on water ice surfaces is a major process taking place in interstellar dense clouds. By coupling laser detection and classical thermal desorption spectroscopy, it is possible to study the effect of rotation of D(2) on adsorption on amorphous solid water ice surfaces. The desorption profiles of ortho- and para-D(2) are different. This difference is due to a shift in the adsorption energy distribution of the two lowest rotational states. Molecules in J''=1 rotational state are on average more strongly bound to the ice surface than those in J''=0 rotational state. This energy difference is estimated to be 1.4+/-0.3 meV. This value is in agreement with previous calculation and interpretation. The nonspherical wave function J'' =1 has an interaction with the asymmetric part of the adsorption potential and contributes positively in the binding energy.

Phenolic Polymer Solvation in Water and Ethylene Glycol, II: Ab Initio Computations.

PubMed

Bauschlicher, Charles W; Bucholz, Eric W; Haskins, Justin B; Monk, Joshua D; Lawson, John W

2017-04-06

Ab initio techniques are used to study the interaction of ethylene glycol and water with a phenolic polymer. The water bonds more strongly with the phenolic OH than with the ring. The phenolic OH groups can form hydrogen bonds between themselves. For more than one water molecule, there is a competition between water-water and water-phenolic interactions. Ethylene glycol shows the same effects as those of water, but the potential energy surface is further complicated by CH 2 -phenolic interactions, different conformers of ethylene glycol, and two OH groups on each molecule. Thus, the ethylene glycol-phenolic potential is more complicated than the water-phenolic potential. The results of the ab initio calculations are compared to those obtained using a force field. These calibration studies show that the water system is easier to describe than the ethylene glycol system. The calibration studies confirm the reliability of force fields used in our companion molecular dynamics study of a phenolic polymer in water and ethylene solutions.

Molecular dynamics simulation of water at mineral surfaces: Structure, dynamics, energetics and hydrogen bonding

NASA Astrophysics Data System (ADS)

Kalinichev, A. G.; Wang, J.; Kirkpatrick, R.

2006-05-01

Fundamental molecular-level understanding of the properties of aqueous mineral interfaces is of great importance for many geochemical and environmental systems. Interaction between water and mineral surfaces substantially affects the properties of both phases, including the reactivity and functionality of the substrate surface, and the structure, dynamics, and energetics of the near surface aqueous phase. Experimental studies of interfacial water structure and dynamics using surface-sensitive techniques such as sum-frequency vibrational spectroscopy or X-ray and neutron reflectivity are not always possible for many practically important substrates, and their results often require interpretation concerning the atomistic mechanisms responsible for the observed behavior. Molecular computer simulations can provide new insight into the underlying molecular- level relationships between the inorganic substrate structure and composition and the structure, ordering, and dynamics of interfacial water. We have performed a series of molecular dynamics (MD) computer simulations of aqueous interfaces with several silicates (quartz, muscovite, and talc) and hydroxides (brucite, portlandite, gibbsite, Ca/Al and Mg/Al double hydroxides) to quantify the effects of the substrate mineral structure and composition on the structural, transport, and thermodynamic properties of water on these mineral surfaces. Due to the prevalent effects of the development of well-interconnected H-bonding networks across the mineral- water interfaces, all the hydroxide surfaces (including a fully hydroxylated quartz surface) show very similar H2O density profiles perpendicular to the interface. However, the predominant orientations of the interfacial H2O molecules and their detailed 2-dimensional near-surface structure and dynamics parallel to the interface are quite different reflecting the differences in the substrate structural charge distribution and the density and orientations of the surface OH groups. The H2O density profiles and other structural and dynamic characteristics of water at the two siloxane surfaces are very different from each other and from the hydroxide surfaces, since the muscovite surface is negatively charged and hydrophilic, while the talc surface is electrostatically neutral and hydrophobic. In general, at hydrophilic neutral surfaces both donating and accepting H-bonds from the H2O molecules are contributing to the development of the interfacial H-bond network, whereas at hydrophilic but charged surfaces only accepting or donating H-bonds with H2O molecules are possible. At the hydrophobic talc surface H-bonds among H2O molecules dominate the interfacial H-bond network and the water-surface interactions are very weak. The first water layer at all substrates is well ordered parallel to the surface, reflecting substrate crystal structures and indicating the reduced translational and orientational mobility of interfacial H2O molecules. At longer time scale (~100ps) their dynamics can be decomposed into a slow, virtually frozen, regime due to the substrate- bound H2O and a faster regime of almost free water reflecting the dynamics far from the surface. At shorter times (>10ps) the two dynamical regimes are superimposed. The much higher ordering of interfacial water (compared to bulk liquid) can not be adequately described as simply "ice-like". To some extent, it rather resembles the behavior of supercooled water.

Controlling Ionic Transport for Device Design in Synthetic Nanopores

NASA Astrophysics Data System (ADS)

Kalman, Eric Boyd

Polymer nanopores present a number of behaviors not seen in microscale systems, such as ion current rectification, ionic selectivity, size exclusion and potential dependent ion concentrations in and near the pore. The existence of these effects stems from the small size of nanopores with respect to the characteristic length scales of surface interactions at the interface between the nanopore surface and the solution within it. The large surface-to-volume ratio due to the nanoscale geometry of a nanopore, as well as similarity in scale between geometry and interaction demands the solution interact with the nanopore walls. As surfaces in solution almost always carry residual charge, these surface forces are primarily the electrostatic interactions between the charge groups on the pore surface and the ions in solution. These interactions may be used by the experimentalist to control ionic transport through synthetic nanopores, and use them as a template for the construction of devices. In this research, we present our work on creating a number of ionic analogs to seminal electronic devices, specifically diodes, and transistors, by controlling ionic transport through the electrostatic interactions between a single synthetic nanopore and ions. Control is achieved by "doping" the effective charge carrier concentration in specific regions of the nanopore through manipulation of the pore's surface charge. This manipulation occurs through two mechanisms: chemical modification of the surface charge and electrostatic manipulation of the local internal nanopore potential using a gate electrode. Additionally, the innate selectivity of the charged nanopores walls allows for the separation of charges in solution. This well-known effect, which spawns measureable quantities, the streaming potential and current, has been used to create nanoscale water desalination membranes. We attempt to create a device using membranes with large nanopore densities for the desalination of water which should theoretically outperform currently available devices, as through our previous work we have developed techniques allowing for transport manipulation not current accessible in traditional membrane motifs.

Characterising the dynamics of surface water-groundwater interactions in intermittent and ephemeral streams using streambed thermal signatures

NASA Astrophysics Data System (ADS)

Rau, Gabriel C.; Halloran, Landon J. S.; Cuthbert, Mark O.; Andersen, Martin S.; Acworth, R. Ian; Tellam, John H.

2017-09-01

Ephemeral and intermittent flow in dryland stream channels infiltrates into sediments, replenishes groundwater resources and underpins riparian ecosystems. However, the spatiotemporal complexity of the transitory flow processes that occur beneath such stream channels are poorly observed and understood. We develop a new approach to characterise the dynamics of surface water-groundwater interactions in dryland streams using pairs of temperature records measured at different depths within the streambed. The approach exploits the fact that the downward propagation of the diel temperature fluctuation from the surface depends on the sediment thermal diffusivity. This is controlled by time-varying fractions of air and water contained in streambed sediments causing a contrast in thermal properties. We demonstrate the usefulness of this method with multi-level temperature and pressure records of a flow event acquired using 12 streambed arrays deployed along a ∼ 12 km dryland channel section. Thermal signatures clearly indicate the presence of water and characterise the vertical flow component as well as the occurrence of horizontal hyporheic flow. We jointly interpret thermal signatures as well as surface and groundwater levels to distinguish four different hydrological regimes: [A] dry channel, [B] surface run-off, [C] pool-riffle sequence, and [D] isolated pools. The occurrence and duration of the regimes depends on the rate at which the infiltrated water redistributes in the subsurface which, in turn, is controlled by the hydraulic properties of the variably saturated sediment. Our results have significant implications for understanding how transitory flows recharge alluvial sediments, influence water quality and underpin dryland ecosystems.

Validation of a new device to quantify groundwater-surface water exchange

NASA Astrophysics Data System (ADS)

Cremeans, Mackenzie M.; Devlin, J. F.

2017-11-01

Distributions of flow across the groundwater-surface water interface should be expected to be as complex as the geologic deposits associated with stream or lake beds and their underlying aquifers. In these environments, the conventional Darcy-based method of characterizing flow systems (near streams) has significant limitations, including reliance on parameters with high uncertainties (e.g., hydraulic conductivity), the common use of drilled wells in the case of streambank investigations, and potentially lengthy measurement times for aquifer characterization and water level measurements. Less logistically demanding tools for quantifying exchanges across streambeds have been developed and include drive-point mini-piezometers, seepage meters, and temperature profiling tools. This project adds to that toolbox by introducing the Streambed Point Velocity Probe (SBPVP), a reusable tool designed to quantify groundwater-surface water interactions (GWSWI) at the interface with high density sampling, which can effectively, rapidly, and accurately complement conventional methods. The SBPVP is a direct push device that measures in situ water velocities at the GWSWI with a small-scale tracer test on the probe surface. Tracer tests do not rely on hydraulic conductivity or gradient information, nor do they require long equilibration times. Laboratory testing indicated that the SBPVP has an average accuracy of ± 3% and an average precision of ± 2%. Preliminary field testing, conducted in the Grindsted Å in Jutland, Denmark, yielded promising agreement between groundwater fluxes determined by conventional methods and those estimated from the SBPVP tests executed at similar scales. These results suggest the SBPVP is a viable tool to quantify groundwater-surface water interactions in high definition in sandy streambeds.

Modeling stream-groundwater interactions and associated groundwater salinization in an urban floodplain

NASA Astrophysics Data System (ADS)

Ledford, S. H.; Lautz, L.

2014-12-01

The salinization of freshwater in the Northeastern United States from road salt application is well documented by the observed long-term increases in chloride concentrations in groundwater over the last fifty years. However, the processes controlling exchange of chloride between surface water and groundwater have not been fully investigated, particularly in urban streams where stream-groundwater interactions can be reduced due to bank armoring and channelization. Our research builds on previous findings that showed the potential for an urban riparian floodplain to buffer seasonal changes in chloride concentrations in an urban stream, resulting in smaller annual ranges of chloride in areas with intact riparian floodplains. A reach of Meadowbrook Creek, in Syracuse, New York, that is disconnected from the groundwater had large seasonal shifts in chloride concentration, varying from 2173 mg/L Cl- in the winter to 161.2 mg/L Cl- in the summer. This is in contrast to a downstream reach of the stream that receives groundwater discharge from a riparian floodplain, where chloride concentrations ranged from 657.0 mg/L in the winter to 252.0 mg/L in the summer. We originally hypothesized that winter snowmelt events caused overbank flooding of saline surface water, which recharged the floodplain groundwater, causing salinization. This saline water was then slowly discharged as baseflow throughout the year and was replaced with freshwater overbank events in the summer. However, a three dimensional model of the floodplain created using Visual MODFLOW indicates that surface water-groundwater interactions, such as hyporheic exchange, may have a greater control on winter salt input than overbank events, while summer flooding recharges the aquifer with freshwater. The model was compared to riparian aquifer samples collected from May 2013 until June 2014 to qualitatively study the impact of different types of surface water-groundwater interactions (e.g. groundwater recharge and discharge, hyporheic interaction) on salt storage and to identify the mechanisms by which urban riparian floodplains buffer seasonal variability of stream chloride concentrations in urban systems impacted by road salt.

Simulation of Wave-Current Interaction Using a Three-Dimensional Hydrodynamic Model Coupled With a Phase Averaged Wave Model

NASA Astrophysics Data System (ADS)

Marsooli, R.; Orton, P. M.; Georgas, N.; Blumberg, A. F.

2016-02-01

The Stevens Institute of Technology Estuarine and Coastal Ocean Model (sECOM) has been coupled with a more advanced surface wave model to simulate wave‒current interaction, and results have been validated in estuarine and nearshore waters. sECOM is a three‒dimensional, hydrostatic, free surface, primitive equation model. It solves the Navier‒Stokes equations and the conservation equations for temperature and salinity using a finite‒difference method on an Arakawa C‒grid with a terrain‒following (sigma) vertical coordinate and orthogonal curvilinear horizontal coordinate system. The model is coupled with the surface wave model developed by Mellor et al. (2008), which solves the spectral equation and takes into account depth and current refraction, and deep and shallow water. The wave model parameterizes the energy distribution in frequency space and the wave‒wave interaction process by using a specified spectrum shape. The coupled wave‒hydrodynamic model considers the wave‒current interaction through wave‒induced bottom stress, depth‒dependent radiation stress, and wave effects on wind‒induced surface stress. The model is validated using the data collected at a natural sandy beach at Duck, North Carolina, during the DUCK94 experiment. This test case reveals the capability of the model to simulate the wave‒current interaction in nearshore coastal systems. The model is further validated using the data collected in Jamaica Bay, a semi‒enclosed body of water located in New York City region. This test reveals the applicability of the model to estuarine systems. These validations of the model and comparisons to its prior wave model, the Great Lakes Environmental Research Laboratory (GLERL) wave model (Donelan 1977), are presented and discussed. ReferencesG.L. Mellor, M.A. Donelan, and L‒Y. Oey, 2008, A Surface Wave Model for Coupling with Numerical Ocean Circulation Models. J. Atmos. Oceanic Technol., 25, 1785‒1807.Donelan, M. A 1977. A simple numerical model for wave and wind stress application. Report, National Water Research Institute, Burlington, Ontario, Canada, 28 pp.

Developing a framework for integrating turbulence measurements and modeling of ecosystem-atmosphere interactions

NASA Astrophysics Data System (ADS)

Markfort, C. D.

2017-12-01

Aquatic ecosystems are integrators of nutrient and carbon from their watersheds. The effects of climate change in many cases will enhance the rate of these inputs and change the thermodynamics within aquatic environments. It is unclear the extent these changes will have on water quality and carbon assimilation, but the drivers of these processes will be determined by the complex interactions at the land-water and air-water interfaces. For example, flow over and beneath wind-driven surface waves generate turbulence that plays an important role in aquatic ecology and biogeochemistry, exchange of gases such as oxygen and carbon dioxide, and it is important for the transfer of energy and controlling evaporation. Energy transferred from the atmosphere promotes the generation and maintenance of waves. A fraction of the energy is transferred to the surface mixed layer through the generation of turbulence. Energy is also transferred back to the atmosphere by waves. There is a need to quantify the details of the coupled boundary layers of the air-water system to better understand how turbulence plays a role in the interactions. We have developed capabilities to conduct field and laboratory experiments using eddy covariance on tall-towers and rafts, UAS platforms integrated with remote sensing, and detailed wind-wave measurements with time-resolved PIV in a new boundary layer wind-wave tunnel. We will show measurements of the detailed structure of the air and water boundary layers under varying wind and wave conditions in the newly developed IIHR Boundary-Layer Wind-Wave Tunnel. The facility combines a 30-m long recirculating water channel with an open-return boundary layer wind tunnel. A thick turbulent boundary layer is developed in the 1 m high air channel, over the water surface, allowing for the study of boundary layer turbulence interacting with a wind-driven wave field. Results will help interpret remote sensing, energy budget measurements, and turbulence transport models for sheltered lakes influenced by terrain and tall trees.

Using SWAT-MODFLOW to simulate groundwater flow and groundwater-surface water interactions in an intensively irrigated stream-aquifer system

NASA Astrophysics Data System (ADS)

Wei, X.; Bailey, R. T.

2017-12-01

Agricultural irrigated watersheds in semi-arid regions face challenges such as waterlogging, high soil salinity, reduced crop yield, and leaching of chemical species due to extreme shallow water tables resulting from long-term intensive irrigation. Hydrologic models can be used to evaluate the impact of land management practices on water yields and groundwater-surface water interactions in such regions. In this study, the newly developed SWAT-MODFLOW, a coupled surface/subsurface hydrologic model, is applied to a 950 km2 watershed in the Lower Arkansas River Valley (southeastern Colorado). The model accounts for the influence of canal diversions, irrigation applications, groundwater pumping, and earth canal seepage losses. The model provides a detailed description of surface and subsurface flow processes, thereby enabling detailed description of watershed processes such as runoff, infiltration, in-streamflow, three-dimensional groundwater flow in a heterogeneous aquifer system with sources and sinks (e.g. pumping, seepage to subsurface drains), and spatially-variable surface and groundwater exchange. The model was calibrated and tested against stream discharge from 5 stream gauges in the Arkansas River and its tributaries, groundwater levels from 70 observation wells, and evapotranspiration (ET) data estimated from satellite (ReSET) data during the 1999 to 2007 period. Since the water-use patterns within the study area are typical of many other irrigated river valleys in the United States and elsewhere, this modeling approach is transferable to other regions.

Explicit modeling of groundwater-surface water interactions using a simple bucket-type model

NASA Astrophysics Data System (ADS)

Staudinger, Maria; Carlier, Claire; Brunner, Philip; Seibert, Jan

2017-04-01

Longer dry spells can become critical for water supply and groundwater dependent ecosystems. During these dry spells groundwater is often the most relevant source for streams. Hence, the hydrological behavior of a catchment is often dominated by groundwater surface water interactions, which can vary considerably in space and time. While classical hydrological approaches hardly consider this spatial dependence, quantitative, hydrogeological modeling approaches can couple surface runoff processes and groundwater processes. Hydrogeological modeling can help to gain an improved understanding of catchment processes during low flow. However, due to their complex parametrization and large computational requirements, such hydrogeological models are difficult to employ at catchment scale, particularly for a larger set of catchments. Then bucket-type hydrological models remain a practical alternative. In this study we combine the strengths of both the hydrogeological and bucket-type hydrological models to better understand low flow processes and ultimately to use this knowledge for low flow projections. Bucket-type hydrological models have traditionally not been developed with focus on the simulation of low flow. One consequence is that interactions between surface and groundwater are not explicitly considered. Water fluxes in bucket-type hydrological models are commonly simulated only in one direction, namely from the groundwater to the stream but not from the stream to the groundwater. This latter flux, however, can become more important during low flow situations. We therefore further developed the bucket-type hydrological model HBV to simulate low flow situations by allowing for exchange in both directions i.e. also from the stream to the groundwater. The additional HBV exchange box is developed by using a variety of synthetic hydrogeological models as training set that were generated using a fully coupled, physically based hydrogeological model. In this way processes that occur in different spatial settings within the catchment are translated to functional relationships and effective parameter values for the conceptual exchange box can be extracted. Here, we show the development and evaluation of the HBV exchange box. We further show a first application in real catchments and evaluate the model performance by comparing the simulations to benchmark models that do not consider groundwater surface water interaction.

Improved simulation of river water and groundwater exchange in an alluvial plain using the SWAT model

USDA-ARS?s Scientific Manuscript database

Hydrological interaction between surface and subsurface water systems has a significant impact on water quality, ecosystems and biogeochemistry cycling of both systems. Distributed models have been developed to simulate this function, but they require detailed spatial inputs and extensive computati...

Modeling streamflow in a snow-dominated forest watershed using the Water Erosion Prediction Project (WEPP) model

USDA-ARS?s Scientific Manuscript database

The Water Erosion Prediction Project (WEPP) model was originally developed for hillslope and small watershed applications. The model simulates complex interactive processes influencing erosion, such as surface runoff, soil-water changes, vegetation growth and senescence, and snow accumulation and me...

Groundwater and surface-water utilisation using a bank infiltration technique in Malaysia

NASA Astrophysics Data System (ADS)

Shamsuddin, Mohd Khairul Nizar; Sulaiman, Wan Nor Azmin; Suratman, Saim; Zakaria, Mohamad Pauzi; Samuding, Kamarudin

2014-05-01

Bank infiltration (BI) is one of the solutions to providing raw water for public supply in tropical countries. This study in Malaysia explores the use of BI to supplement a polluted surface-water resource with groundwater. Three major factors were investigated: (1) contribution of surface water through BI to the resulting abstraction, (2) input of local groundwater, and (3) water-quality characteristics of the resulting water supply. A geophysical method was employed to define the subsurface geology and hydrogeology, and isotope techniques were performed to identify the source of groundwater recharge and the interaction between surface water and groundwater. The physicochemical and microbiological parameters of the local surface-water bodies and groundwater were analyzed before and during water abstraction. Extracted water revealed a 5-98 % decrease in turbidity, as well as reductions in HCO3 -, Cl-, SO4 2-, NO3 -, Ca2+, Al3+ and As concentrations compared with those of Langat River water. In addition, amounts of E. coli, total coliform and Giardia were significantly reduced (99.9 %). However, water samples from test wells during pumping showed high concentrations of Fe2+ and Mn2+. Pumping test results indicate that the two wells used in the study were able to sustain yields.

Patterns and drivers for wetland connections in the Prairie Pothole Region, United States

USGS Publications Warehouse

Vanderhoof, Melanie; Christensen, Jay R.; Alexander, Laurie C.

2017-01-01

Ecosystem function in rivers, lakes and coastal waters depends on the functioning of upstream aquatic ecosystems, necessitating an improved understanding of watershed-scale interactions including variable surface-water flows between wetlands and streams. As surface water in the Prairie Pothole Region expands in wet years, surface-water connections occur between many depressional wetlands and streams. Minimal research has explored the spatial patterns and drivers for the abundance of these connections, despite their potential to inform resource management and regulatory programs including the U.S. Clean Water Act. In this study, wetlands were identified that did not intersect the stream network, but were shown with Landsat images (1990–2011) to become merged with the stream network as surface water expanded. Wetlands were found to spill into or consolidate with other wetlands within both small (2–10 wetlands) and large (>100 wetlands) wetland clusters, eventually intersecting a stream channel, most often via a riparian wetland. These surface-water connections occurred over a wide range of wetland distances from streams (averaging 90–1400 m in different ecoregions). Differences in the spatial abundance of wetlands that show a variable surface-water connection to a stream were best explained by smaller wetland-to-wetland distances, greater wetland abundance, and maximum surface-water extent. This analysis demonstrated that wetland arrangement and surface water expansion are important mechanisms for depressional wetlands to connect to streams and provides a first step to understanding the frequency and abundance of these surface-water connections across the Prairie Pothole Region.

Groundwater Discharges to Rivers in the Western Canadian Oil Sands Region

NASA Astrophysics Data System (ADS)

Ellis, J.; Jasechko, S.

2016-12-01

Groundwater discharges into rivers impacts the movement and fate of nutrients and contaminants in the environment. Understanding groundwater-surface water interactions is especially important in the western Canadian oil sands, where groundwater contamination risks are elevated and baseline water chemistry data is lacking, leading to substantial uncertainties about anthropogenic influences on local river quality. High salinity groundwater springs sourced from deep aquifers, comprised of Pleistocene-aged glacial meltwater, are known to discharge into many rivers in the oil sands. Understanding connections between deep aquifers and surficial waterways is important in order to determine natural inputs into these rivers and to assess the potential for injected wastewater or oil extraction fluids to enter surface waters. While these springs have been identified, their spatial distribution along rivers has not been fully characterized. Here we present river chemistry data collected along a number of major river corridors in the Canadian oil sands region. We show that saline groundwater springs vary spatially along the course of these rivers and tend to be concentrated where the rivers incise Devonian- or Cretaceous-aged aquifers along an evaporite dissolution front. Our results suggest that water sourced from Devonian aquifers may travel through bitumen-bearing Cretaceous units and discharge into local rivers, implying a strong groundwater-surface water connection in specialized locations. These findings indicate that oil sands process-affected waters that are injected at depth have the potential to move through these aquifers and reach the rivers at the surface at some time in the future. Groundwater-surface water interactions remain key to understanding the risks oil sands activities pose to aquatic ecosystems and downstream communities.

Effect of dimethyl sulfoxide on dentin collagen.

PubMed

Mehtälä, P; Pashley, D H; Tjäderhane, L

2017-08-01

Infiltration of adhesive on dentin matrix depends on interaction of surface and adhesive. Interaction depends on dentin wettability, which can be enhanced either by increasing dentin surface energy or lowering the surface energy of adhesive. The objective was to examine the effect of dimethyl sulfoxide (DMSO) on demineralized dentin wettability and dentin organic matrix expansion. Acid-etched human dentin was used for sessile drop contact angle measurement to test surface wetting on 1-5% DMSO-treated demineralized dentin surface, and linear variable differential transformer (LVDT) to measure expansion/shrinkage of dentinal matrix. DMSO-water binary liquids were examined for surface tension changes through concentrations from 0 to 100% DMSO. Kruskal-Wallis and Mann-Whitney tests were used to test the differences in dentin wettability, expansion and shrinkage, and Spearman test to test the correlation between DMSO concentration and water surface tension. The level of significance was p<0.05. Pretreatment with 1-5% DMSO caused statistically significant concentration-dependent increase in wetting: the immediate contact angles decreased by 11.8% and 46.6% and 60s contact angles by 9.5% and 47.4% with 1% and 5% DMSO, respectively. DMSO-water mixtures concentration-dependently expanded demineralized dentin samples less than pure water, except with high (≥80%) DMSO concentrations which expanded demineralized dentin more than water. Drying times of LVDT samples increased significantly with the use of DMSO. Increased dentin wettability may explain the previously demonstrated increase in adhesive penetration with DMSO-treated dentin, and together with the expansion of collagen matrix after drying may also explain previously observed increase in dentin adhesive bonding. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Adhesion force interactions between cyclopentane hydrate and physically and chemically modified surfaces.

PubMed

Aman, Zachary M; Sloan, E Dendy; Sum, Amadeu K; Koh, Carolyn A

2014-12-07

Interfacial interactions between liquid-solid and solid-solid phases/surfaces are of fundamental importance to the formation of hydrate deposits in oil and gas pipelines. This work establishes the effect of five categories of physical and chemical modification to steel on clathrate hydrate adhesive force: oleamide, graphite, citric acid ester, nonanedithiol, and Rain-X anti-wetting agent. Hydrate adhesive forces were measured using a micromechanical force apparatus, under both dry and water-wet surface conditions. The results show that the graphite coating reduced hydrate-steel adhesion force by 79%, due to an increase in the water wetting angle from 42 ± 8° to 154 ± 7°. Two chemical surface coatings (nonanedithiol and the citric acid ester) induced rapid hydrate growth in the hydrate particles; nonanedithiol increased hydrate adhesive force by 49% from the baseline, while the citric acid ester coating reduced hydrate adhesion force by 98%. This result suggests that crystal growth may enable a strong adhesive pathway between hydrate and other crystalline structures, however this effect may be negated in cases where water-hydrocarbon interfacial tension is minimised. When a liquid water droplet was placed on the modified steel surfaces, the graphite and citric acid ester became less effective at reducing adhesive force. In pipelines containing a free water phase wetting the steel surface, chemical or physical surface modifications alone may be insufficient to eliminate hydrate deposition risk. In further tests, the citric acid ester reduced hydrate cohesive forces by 50%, suggesting mild activity as a hybrid anti-agglomerant suppressing both hydrate deposition and particle agglomeration. These results demonstrate a new capability to develop polyfunctional surfactants, which simultaneously limit the capability for hydrate particles to aggregate and deposit on the pipeline wall.

Relationships between surface free energy, surface texture parameters and controlled drug release in hydrophilic matrices.

PubMed

Saurí, J; Suñé-Negre, J M; Díaz-Marcos, J; Vilana, J; Millán, D; Ticó, J R; Miñarro, M; Pérez-Lozano, P; García-Montoya, E

2015-01-15

The study of controlled release and drug release devices has been dominated by considerations of the bulk or average properties of material or devices. Yet the outermost surface atoms play a central role in their performance. The objective of this article has been to characterize the surface of hydrophilic matrix tablets using the contact angle (CA) method to ascertain the surface free energy, and atomic force microscopy (AFM) and confocal microscopy (CM) for the physical characterization of the surface of the hydrophilic matrix. The surface free energy results obtained show that hydroxypropylmethylcellulose K15M hinders the spreading of water on the surface of the tablet, such that the concentration of HPMC K15M increases the reaction rate of the hydrophobic interactions between the chains of HPMC K15M which increases with respect to the rate of penetration of water into the tablet. In this study, we developed a new method to characterize the swelling of the tablets and established a relationship between the new method based on microswelling and the swelling ratio parameter. The surface texture parameters have been determined and the morphology of the tablets of the different formulations and the evolution of the surface morphology after interacting with the water, swelling and forming a gel layer were characterized. This work represents significant progress in the characterization of matrix tablets. Copyright © 2014 Elsevier B.V. All rights reserved.

The interaction with gold suppresses fiber-like conformations of the amyloid β (16-22) peptide

NASA Astrophysics Data System (ADS)

Bellucci, Luca; Ardèvol, Albert; Parrinello, Michele; Lutz, Helmut; Lu, Hao; Weidner, Tobias; Corni, Stefano

2016-04-01

Inorganic surfaces and nanoparticles can accelerate or inhibit the fibrillation process of proteins and peptides, including the biomedically relevant amyloid β peptide. However, the microscopic mechanisms that determine such an effect are still poorly understood. By means of large-scale, state-of-the-art enhanced sampling molecular dynamics simulations, here we identify an interaction mechanism between the segments 16-22 of the amyloid β peptide, known to be fibrillogenic by itself, and the Au(111) surface in water that leads to the suppression of fiber-like conformations from the peptide conformational ensemble. Moreover, thanks to advanced simulation analysis techniques, we characterize the conformational selection vs. induced fit nature of the gold effect. Our results disclose an inhibition mechanism that is rooted in the details of the microscopic peptide-surface interaction rather than in general phenomena such as peptide sequestration from the solution.Inorganic surfaces and nanoparticles can accelerate or inhibit the fibrillation process of proteins and peptides, including the biomedically relevant amyloid β peptide. However, the microscopic mechanisms that determine such an effect are still poorly understood. By means of large-scale, state-of-the-art enhanced sampling molecular dynamics simulations, here we identify an interaction mechanism between the segments 16-22 of the amyloid β peptide, known to be fibrillogenic by itself, and the Au(111) surface in water that leads to the suppression of fiber-like conformations from the peptide conformational ensemble. Moreover, thanks to advanced simulation analysis techniques, we characterize the conformational selection vs. induced fit nature of the gold effect. Our results disclose an inhibition mechanism that is rooted in the details of the microscopic peptide-surface interaction rather than in general phenomena such as peptide sequestration from the solution. Electronic supplementary information (ESI) available: Representative structures for the most populated conformational structures of Aβ16-22 on bulk and on the metal surface. Normalized distribution of the variable s defined as the sum of internal dihedral angles of the peptide in solution and at the gold/water interface. See DOI: 10.1039/C6NR01539E

INTERACTION OF METHYL-TERT BUTYL ETHER AND WATER STRESS ON SEED GERMINATION AND SEEDLING GROWTH IN SOIL MICROCOSMS

EPA Science Inventory

Methyl tert-butyl ether (MTBE) is a widespread contaminant in surface and ground water in the United States. Frequently irrigation is used to water fields to germinate planted seeds and sustain plant growth. A likely possibility exists that water used may have some MTBE. Our s...

Bacterial Adhesion to Hexadecane (Model NAPL)-Water Interfaces

NASA Astrophysics Data System (ADS)

Ghoshal, S.; Zoueki, C. R.; Tufenkji, N.

2009-05-01

The rates of biodegradation of NAPLs have been shown to be influenced by the adhesion of hydrocarbon- degrading microorganisms as well as their proximity to the NAPL-water interface. Several studies provide evidence for bacterial adhesion or biofilm formation at alkane- or crude oil-water interfaces, but there is a significant knowledge gap in our understanding of the processes that influence initial adhesion of bacteria on to NAPL-water interfaces. In this study bacterial adhesion to hexadecane, and a series of NAPLs comprised of hexadecane amended with toluene, and/or with asphaltenes and resins, which are the surface active fractions of crude oils, were examined using a Microbial Adhesion to Hydrocarbons (MATH) assay. The microorganisms employed were Mycobacterium kubicae, Pseudomonas aeruginosa and Pseudomonas putida, which are hydrocarbon degraders or soil microorganisms. MATH assays as well as electrophoretic mobility measurements of the bacterial cells and the NAPL droplet surfaces in aqueous solutions were conducted at three solution pHs (4, 6 and 7). Asphaltenes and resins were shown to generally decrease microbial adhesion. Results of the MATH assay were not in qualitative agreement with theoretical predictions of bacteria- hydrocarbon interactions based on the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) model of free energy of interaction between the cell and NAPL droplets. In this model the free energy of interaction between two colloidal particles is predicted based on electrical double layer, van der Waals and hydrophobic forces. It is likely that the steric repulsion between bacteria and NAPL surfaces, caused by biopolymers on bacterial surfaces and aphaltenes and resins at the NAPL-water interface contributed to the decreased adhesion compared to that predicted by the XDLVO model.

Sink or Swim: Ions and Organics at the Ice-Air Interface.

PubMed

Hudait, Arpa; Allen, Michael T; Molinero, Valeria

2017-07-26

The ice-air interface is an important locus of environmental chemical reactions. The structure and dynamics of the ice surface impact the uptake of trace gases and kinetics of reactions in the atmosphere and snowpack. At tropospheric temperatures, the ice surface is partially premelted. Experiments indicate that ions increase the liquidity of the ice surface but hydrophilic organics do not. However, it is not yet known the extent of the perturbation solutes induce at the ice surface and what is the role of the disordered liquid-like layer in modulating the interaction between solutes and their mobility and aggregation at the ice surface. Here we use large-scale molecular simulations to investigate the effect of ions and glyoxal, one of the most abundant oxygenated volatile organic compounds in the atmosphere, on the structure, dynamics, and solvation properties of the ice surface. We find that the premelted surface of ice has unique solvation properties, different from those of liquid water. The increase in surface liquidity resulting from the hydration of ions leads to a water-mediated attraction of ions at the ice surface. Glyoxal molecules, on the other hand, perturb only slightly the surface of ice and do not experience water-driven attraction. They nonetheless accumulate as dry agglomerates at the ice surface, driven by direct interactions between the organic molecules. The enhanced attraction and clustering of ions and organics at the ice surface may play a significant role in modulating the mechanism and rate of heterogeneous chemical reactions occurring at the surface of atmospheric ice particles.

Crystalline order of a water/glycine film coadsorbed on the (104) calcite surface.

PubMed

Magdans, Uta; Torrelles, Xavier; Angermund, Klaus; Gies, Hermann; Rius, Jordi

2007-04-24

For biomineralization processes, the interaction of the surface of calcite crystals with organic molecules is of particular importance. Especially, biologically controlled biomineralization as in exoskeletons of mollusks and echinoderms, e.g., sea urchin with single-crystal-like spines and shells,1-3 requires molecular control of seed formation and growth process. So far, experiments showing the obvious influence of organic molecules on the morphology and habit of calcite crystals have demonstrated the molecular dimension of the interaction.4-7 Details of the kinetics of growth and dissolution of mineral surfaces influenced by additives are available,8,9 but other experimental data about the structure of the organic/inorganic interface on the atomic scale are rare. On the other hand, complicated organic macromolecules which are involved in biomineralization are numerous, with only a small fraction solved in structure and function so far.10-13 Therefore, model systems have to be designed to provide a basic understanding for the interaction process.14 Using grazing incidence X-ray diffraction combined with molecular modeling techniques, we show that glycine molecules order periodically on the calcite (104) face in competition with the solvent water when exposed to an aqueous solution of the most simple amino acid. In contrast to the general concept of the charge-matching fit of organic molecules on mineral surfaces,4,14 glycine is not attached to the calcite surface directly but substitutes for water molecules in the second hydration layer.

The environmental applications and implications of nanotechnology in membrane-based separations for water treatment

NASA Astrophysics Data System (ADS)

Shan, Wenqian

This dissertation presents results of three related projects focused on the applications of membrane separation technology to water treatment: 1) Experimental design and evaluation of polyelectrolyte multilayer films as regenerable membrane coatings with controllable surface properties; 2) Modeling of the interactions of nanoscale TiO2 and NOM molecules in aqueous solutions of environmentally relevant compositions; 3) Experimental design and preliminary testing of a membrane-based crossflow filtration hydrocyclone process for the separation of oil-in-water dispersions. Chapter 2 describes the design of polyelectrolyte multilayers as nanoscale membrane coatings and their application in nanofiltration of feed waters that contain suspended colloids and dissolved species. Layer-by-layer deposition of anionic and cationic polyelectrolytes was employed to prepare membrane coatings allowing for a fine control over their surface properties. This approach to membrane design also affords a possibility of regenerating coatings after they are fouled by colloids. This project demonstrated, for first time, the possibility of designing nanofiltration membranes with regenerable skin. Chapter 3 describes a study on the mechanisms of natural organic matter (NOM) adsorption onto the surface of titania nanoparticles. Titainia (TiO 2) is often used in the fabrication of ceramic membranes and understanding how NOM interacts with TiO2 can help to better predict ceramic membrane fouling by NOM-containing waters. The combined effect of pH and calcium on the interactions of nonozonated and ozonated NOM with nanoscale TiO 2 was investigated by applying extended Derjaguin --- Landau --- Verwey - Overbeek (XDLVO) modeling. XDLVO surface energy analysis predicted NOM adsorption onto TiO2 in the ozone-controlled regime but not in the calcium-controlled regime. In both regimes, short range NOM-NOM and NOM-TiO2 interactions were governed by acid-base and van der Waals forces, whereas the role of electrostatic forces was found to be relatively insignificant. Ozonation increased the surface energy of NOM, contributing to the hydrophilic repulsion component of the NOM-NOM and NOM-TiO2 interactions. In the calcium-controlled regime, non-XDLVO interactions such as intermolecular bridging by calcium were hypothesized to be responsible for the observed adsorption behavior. Chapter 4 describes research on the crossflow filtration hydrocyclone separation of oil-in-water dispersions wherein a ceramic tubular membrane was used as the permeable wall of the hydrocyclone. Air sparging was applied to mitigate oil fouling. A dual membrane system consisting of an outer hydrophilic ceramic membrane and an inner hydrophobic polymeric membrane was evaluated to test the possibility of separating the dispersion into two streams: 1) oil with zero or very low concentration of water and 2) water with zero or very low concentration of oil. The performance of the dual membrane system indicated the possibility of using membranes with different chemical affinities to cost-effectively separate the oil-water dispersion into two separate phases. The incorporation of air sparging to membrane filtration was found to be effective in mitigating oil fouling with improved permeate flux.

Relation of streams, lakes, and wetlands to groundwater flow systems

NASA Astrophysics Data System (ADS)

Winter, Thomas C.

Surface-water bodies are integral parts of groundwater flow systems. Groundwater interacts with surface water in nearly all landscapes, ranging from small streams, lakes, and wetlands in headwater areas to major river valleys and seacoasts. Although it generally is assumed that topographically high areas are groundwater recharge areas and topographically low areas are groundwater discharge areas, this is true primarily for regional flow systems. The superposition of local flow systems associated with surface-water bodies on this regional framework results in complex interactions between groundwater and surface water in all landscapes, regardless of regional topographic position. Hydrologic processes associated with the surface-water bodies themselves, such as seasonally high surface-water levels and evaporation and transpiration of groundwater from around the perimeter of surface-water bodies, are a major cause of the complex and seasonally dynamic groundwater flow fields associated with surface water. These processes have been documented at research sites in glacial, dune, coastal, mantled karst, and riverine terrains. Résumé Les eaux de surface sont parties intégrantes des systèmes aquifères. Les eaux souterraines interagissent avec les eaux de surface dans presque tous les types d'environnements, depuis les petits ruisseaux, les lacs et les zones humides jusqu'aux bassins versants des vallées des grands fleuves et aux lignes de côte. Il est en général admis que les zones topographiquement hautes sont des lieux de recharge des aquifères et les zones basses des lieux de décharge, ce qui est le cas des grands systèmes aquifères régionaux. La superposition de systèmes locaux, associés à des eaux de surface, à l'organisation régionale d'écoulements souterrains résulte d'interactions complexes entre les eaux souterraines et les eaux de surface dans tous les environnements, quelle que soit la situation topographique régionale. Les processus hydrologiques associés aux eaux de surface elles-mêmes, tels que des niveaux d'eau de surface saisonnièrement hauts et l'évaporation et la transpiration de l'eau souterraine à la périphérie des eaux de surface, sont les causes essentielles de la dynamique complexe et saisonnière des nappes associées aux eaux de surface. Ces processus ont été mis en évidence sur des sites de recherche dans des formations glaciaires, dunaires, littorales, fluviales et de karst couvert. Resumen Los cuerpos de aguas superficiales son partes integrales de los sistemas de flujo subterráneo. El agua subterránea interactúa con la superficial en prácticamente todo tipo de paisajes, desde pequeños torrentes, lagos y humedales, hasta grandes valles fluviales y costas. Aunque se suele asumir que las áreas topográficamente elevadas son zonas de recarga de aguas subterráneas, mientras las áreas topográficamente más bajas lo son de descarga, esto es cierto básicamente para los sistemas de flujo regional. Al superponer los sistemas de flujo local, asociados a los cuerpos de agua superficial, a las condiciones regionales, resultan interacciones complejas, y esto ocurre independientemente de su posición topográfica. Los procesos hidrológicos asociados con los propios cuerpos de agua superficial, como los niveles superficiales máximos estacionales y la evapotranspiración de agua subterránea en los perímetros de cuerpos superficiales, son una de las principales causas de la complejidad y de las variaciones dinámicas de las interacciones entre aguas subterráneas y superficiales. Estos procesos se han documentado en distintas zonas investigadas, incluyendo depósitos glaciares, dunas, áreas costeras, karsts y terrazas fluviales.

The solvation structures of cellulose microfibrils in ionic liquids.

PubMed

Mostofian, Barmak; Smith, Jeremy C; Cheng, Xiaolin

2011-12-01

The use of ionic liquids for non-derivatized cellulose dissolution promises an alternative method for the thermochemical pretreatment of biomass that may be more efficient and environmentally acceptable than more conventional techniques in aqueous solution. Here, we performed equilibrium MD simulations of a cellulose microfibril in the ionic liquid 1-butyl-3-methylimidazolium chloride (BmimCl) and compared the solute structure and the solute-solvent interactions at the interface with those from corresponding simulations in water. The results indicate a higher occurrence of solvent-exposed orientations of cellulose surface hydroxymethyl groups in BmimCl than in water. Moreover, spatial and radial distribution functions indicate that hydrophilic surfaces are a preferred site of interaction between cellulose and the ionic liquid. In particular, hydroxymethyl groups on the hydrophilic fiber surface adopt a different conformation from their counterparts oriented towards the fiber's core. Furthermore, the glucose units with these solvent-oriented hydroxymethyls are surrounded by the heterocyclic organic cation in a preferred parallel orientation, suggesting a direct and distinct interaction scheme between cellulose and BmimCl.

Mechanisms of protein stabilization and prevention of protein aggregation by glycerol.

PubMed

Vagenende, Vincent; Yap, Miranda G S; Trout, Bernhardt L

2009-11-24

The stability of proteins in aqueous solution is routinely enhanced by cosolvents such as glycerol. Glycerol is known to shift the native protein ensemble to more compact states. Glycerol also inhibits protein aggregation during the refolding of many proteins. However, mechanistic insight into protein stabilization and prevention of protein aggregation by glycerol is still lacking. In this study, we derive mechanisms of glycerol-induced protein stabilization by combining the thermodynamic framework of preferential interactions with molecular-level insight into solvent-protein interactions gained from molecular simulations. Contrary to the common conception that preferential hydration of proteins in polyol/water mixtures is determined by the molecular size of the polyol and the surface area of the protein, we present evidence that preferential hydration of proteins in glycerol/water mixtures mainly originates from electrostatic interactions that induce orientations of glycerol molecules at the protein surface such that glycerol is further excluded. These interactions shift the native protein toward more compact conformations. Moreover, glycerol preferentially interacts with large patches of contiguous hydrophobicity where glycerol acts as an amphiphilic interface between the hydrophobic surface and the polar solvent. Accordingly, we propose that glycerol prevents protein aggregation by inhibiting protein unfolding and by stabilizing aggregation-prone intermediates through preferential interactions with hydrophobic surface regions that favor amphiphilic interface orientations of glycerol. These mechanisms agree well with experimental data available in the literature, and we discuss the extent to which these mechanisms apply to other cosolvents, including polyols, arginine, and urea.

Dynamic molecular oxygen production in cometary comae.

PubMed

Yao, Yunxi; Giapis, Konstantinos P

2017-05-08

Abundant molecular oxygen was discovered in the coma of comet 67P/Churyumov-Gerasimenko. Its origin was ascribed to primordial gaseous O 2 incorporated into the nucleus during the comet's formation. This thesis was put forward after discounting several O 2 production mechanisms in comets, including photolysis and radiolysis of water, solar wind-surface interactions and gas-phase collisions. Here we report an original Eley-Rideal reaction mechanism, which permits direct O 2 formation in single collisions of energetic water ions with oxidized cometary surface analogues. The reaction proceeds by H 2 O + abstracting a surface O-atom, then forming an excited precursor state, which dissociates to produce O 2 - . Subsequent photo-detachment leads to molecular O 2 , whose presence in the coma may thus be linked directly to water molecules and their interaction with the solar wind. This abiotic O 2 production mechanism is consistent with reported trends in the 67P coma and raises awareness of the role of energetic negative ions in comets.

Dynamic molecular oxygen production in cometary comae

NASA Astrophysics Data System (ADS)

Yao, Yunxi; Giapis, Konstantinos P.

2017-05-01

Abundant molecular oxygen was discovered in the coma of comet 67P/Churyumov-Gerasimenko. Its origin was ascribed to primordial gaseous O2 incorporated into the nucleus during the comet's formation. This thesis was put forward after discounting several O2 production mechanisms in comets, including photolysis and radiolysis of water, solar wind-surface interactions and gas-phase collisions. Here we report an original Eley-Rideal reaction mechanism, which permits direct O2 formation in single collisions of energetic water ions with oxidized cometary surface analogues. The reaction proceeds by H2O+ abstracting a surface O-atom, then forming an excited precursor state, which dissociates to produce O2-. Subsequent photo-detachment leads to molecular O2, whose presence in the coma may thus be linked directly to water molecules and their interaction with the solar wind. This abiotic O2 production mechanism is consistent with reported trends in the 67P coma and raises awareness of the role of energetic negative ions in comets.

Automated optimization of water-water interaction parameters for a coarse-grained model.

PubMed

Fogarty, Joseph C; Chiu, See-Wing; Kirby, Peter; Jakobsson, Eric; Pandit, Sagar A

2014-02-13

We have developed an automated parameter optimization software framework (ParOpt) that implements the Nelder-Mead simplex algorithm and applied it to a coarse-grained polarizable water model. The model employs a tabulated, modified Morse potential with decoupled short- and long-range interactions incorporating four water molecules per interaction site. Polarizability is introduced by the addition of a harmonic angle term defined among three charged points within each bead. The target function for parameter optimization was based on the experimental density, surface tension, electric field permittivity, and diffusion coefficient. The model was validated by comparison of statistical quantities with experimental observation. We found very good performance of the optimization procedure and good agreement of the model with experiment.

The Europa Lander Mission Concept and Science Goals — Highlighting Ice Properties and Surface Activity

NASA Astrophysics Data System (ADS)

Hand, K. P.; Murray, A. E.; Garvin, J.; Horst, S.; Brinckerhoff, W.; Edgett, K.; Hoehler, T.; Russell, M.; Rhoden, A.; Yingst, R. A.; German, C.; Schmidt, B.; Paranicas, C.; Smith, D.; Willis, P.; Hayes, A.; Ehlmann, B.; Lunine, J.; Templeton, A.; Nealson, K.; Christner, B.; Cable, M.; Craft, K.; Pappalardo, R.; Hofmann, A.; Nordheim, T.; Phillips, C.

2018-06-01

The Europa Lander mission concept would address key questions regarding ice properties and surface activity, including characterizing any plume deposits, understanding local topography, searching for evidence of interactions with liquid water.

Interaction of water vapor with silicate glass surfaces: Mass-spectrometric investigations

NASA Astrophysics Data System (ADS)

Kudriavtsev, Yu.; Asomoza-Palacio, R.; Manzanilla-Naim, L.

2017-05-01

The secondary ion mass-spectroscopy technique was used to study the results of hydration of borosilicate, aluminosilicate, and soda-lime silicate glasses in 1H2 18O water vapor containing 97% of the isotope 18O. It is shown that hydration of the surface of the soda-lime silicate glass occurs as a result of the ion-exchange reaction with alkali metals. In the case of borosilicate and aluminosilicate glasses, water molecules decompose on the glass surface, with the observed formation of hydrogenated layer in the glass being the result of a solid-state chemical reaction—presumably, with the formation of hydroxides from aluminum and boron oxides.

Exploration of Impinging Water Spray Heat Transfer at System Pressures Near the Triple Point

NASA Technical Reports Server (NTRS)

Golliher, Eric L.; Yao, Shi-Chune

2013-01-01

The heat transfer of a water spray impinging upon a surface in a very low pressure environment is of interest to cooling of space vehicles during launch and re-entry, and to industrial processes where flash evaporation occurs. At very low pressure, the process occurs near the triple point of water, and there exists a transient multiphase transport problem of ice, water and water vapor. At the impingement location, there are three heat transfer mechanisms: evaporation, freezing and sublimation. A preliminary heat transfer model was developed to explore the interaction of these mechanisms at the surface and within the spray.

THE EFFECTS OF CRACKING ON THE SURFACE POTENTIAL OF ICY GRAINS IN SATURN’S E-RING: LABORATORY STUDIES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bu, Caixia; Bahr, David A.; Dukes, Catherine A.

2016-07-10

Within Saturn's E-ring, dust grains are coated by water vapor co-released with ice grains from the geyser-like eruptions of Enceladus. These ice-coated grains have intrinsic surface potential and interact synergistically with the ions and electrons of Saturn's magnetospheric plasmas. We perform laboratory experiments to investigate the effects of water-ice growth on the surface potential, using amorphous solid water (ASW) films. We estimate the growth of the surface potential to be ∼ 2.5 mV (Earth) yr{sup 1} and 112 mV yr{sup 1} for E-ring grains at ∼4.5 R {sub s} and 3.95 R {sub s} outside Enceladus’s plume, respectively. In addition,more » our measurements show that the linear relationship between the surface potential and the film thickness, as described in previous studies, has an upper limit, where the film spontaneously cracks above a porosity-dependent critical thickness. Heating of the cracked films with (and without) deposited charge shows that significant positive (and negative) surface potentials are retained at temperatures above 110 K, contrary to the minimal values (roughly zero) for thin, transparent ASW films. The significant surface potentials observed on micron-scale cracked ice films after thermal cycling, (5–20) V, are consistent with Cassini measurements, which indicate a negative charge of up to 5 V for E-ring dust particles at ∼5 R {sub s}. Therefore, the native grain surface potential resulting from water-vapor coating must be included in modeling studies of interactions between E-ring icy surfaces and Saturn's magnetospheric plasma.« less

Molecular Dynamics Simulations of the Oil-Detachment from the Hydroxylated Silica Surface: Effects of Surfactants, Electrostatic Interactions, and Water Flows on the Water Molecular Channel Formation.

PubMed

Tang, Jian; Qu, Zhou; Luo, Jianhui; He, Lanyan; Wang, Pingmei; Zhang, Ping; Tang, Xianqiong; Pei, Yong; Ding, Bin; Peng, Baoliang; Huang, Yunqing

2018-02-15

The detachment process of an oil molecular layer situated above a horizontal substrate was often described by a three-stage process. In this mechanism, the penetration and diffusion of water molecules between the oil phase and the substrate was proposed to be a crucial step to aid in removal of oil layer/drops from substrate. In this work, the detachment process of a two-dimensional alkane molecule layer from a silica surface in aqueous surfactant solutions is studied by means of molecular dynamics (MD) simulations. By tuning the polarity of model silica surfaces, as well as considering the different types of surfactant molecules and the water flow effects, more details about the formation of water molecular channel and the expansion processes are elucidated. It is found that for both ionic and nonionic type surfactant solutions, the perturbation of surfactant molecules on the two-dimensional oil molecule layer facilitates the injection and diffusion of water molecules between the oil layer and silica substrate. However, the water channel formation and expansion speed is strongly affected by the substrate polarity and properties of surfactant molecules. First, only for the silica surface with relative stronger polarity, the formation of water molecular channel is observed. Second, the expansion speed of the water molecular channel upon the ionic surfactant (dodecyl trimethylammonium bromide, DTAB and sodium dodecyl benzenesulfonate, SDBS) flooding is more rapidly than the nonionic surfactant system (octylphenol polyoxyethylene(10) ether, OP-10). Third, the water flow speed may also affect the injection and diffusion of water molecules. These simulation results indicate that the water molecular channel formation process is affected by multiple factors. The synergistic effects of perturbation of surfactant molecules and the electrostatic interactions between silica substrate and water molecules are two key factors aiding in the injection and diffusion of water molecules and helpful for the oil detachment from silica substrate.

Response surface methodology investigation into the interactions between arsenic and humic acid in water during the coagulation process.

PubMed

Watson, Malcolm Alexander; Tubić, Aleksandra; Agbaba, Jasmina; Nikić, Jasmina; Maletić, Snežana; Molnar Jazić, Jelena; Dalmacija, Božo

2016-07-15

Interactions between arsenic and natural organic matter (NOM) are key limiting factors during the optimisation of drinking water treatment when significant amounts of both must be removed. This work uses Response Surface Methodology (RSM) to investigate how they interact during their simultaneous removal by iron chloride coagulation, using humic acid (HA) as a model NOM substance. Using a three factor Box-Behnken experimental design, As and HA removals were modelled, as well as a combined removal response. ANOVA results showed the significance of the coagulant dose for all three responses. At high initial arsenic concentrations (200μg/l), As removal was significantly hindered by the presence of HA. In contrast, the HA removal response was found to be largely independent of the initial As concentration, with the optimum coagulant dose increasing at increasing HA concentrations. The combined response was similar to the HA removal response, and the interactions evident are most interesting in terms of optimising treatment processes during the preparation of drinking water, highlighting the importance of utilizing RSM for such investigations. The combined response model was successfully validated with two different groundwaters used for drinking water supply in the Republic of Serbia, showing excellent agreement under similar experimental conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Detection of the adsorption of water monolayers through the ion oscillation frequency in the magnesium oxide lattice by means of low energy electron diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guevara-Bertsch, M.; Avendaño, E.; Centro de Investigación en Ciencia e Ingeniería de Materiales, Universidad de Costa Rica, 2060 San Pedro, San José

We investigate the variation of the oscillation frequency of the Mg{sup 2+} and O{sup 2−} ions in the magnesium oxide lattice due to the interactions of the surface with water monolayers by means of Low Energy Electron Diffraction. Our key result is a new technique to determine the adsorbate vibrations produced by the water monolayers on the surface lattice as a consequence of their change in the surface Debye temperature and its chemical shift. The latter was systematically investigated for different annealing times and for a constant external thermal perturbation in the range of 110–300 K in order to accomplish adsorptionmore » or desorption of water monolayers in the surface lattice.« less

Groundwater and surface water interaction in flow-through gravel pit lakes.

NASA Astrophysics Data System (ADS)

Nella Mollema, Pauline; Antonellini, Marco

2015-04-01

Gravel pits are excavated in aquifers to fulfill the need for construction materials. Flow-through lakes form when the gravel pits are below the water table and fill with groundwater. In certain areas there are more than 60 of these lakes close together and their presence changes the drainage patterns and water- and hydrochemical budgets of a watershed. In flow-through gravel pit lakes, groundwater mixes with surface water and interacts with the atmosphere; outflow occurs only via groundwater. The lifespan of gravel pit lakes may be up to thousands of years as their depth to surface ratio is typically large and sedimentation rates are low. We have studied two gravel pit lake systems, a fluvial freshwater system in the Netherlands and a coastal brackish lake system in Italy. One Dutch gravel pit lake studied in detail is in part artificially replenished with Meuse River water for drinking water production that occurs downstream of the lake by water pumps. The Italian gravel pit lakes are fed by brackish groundwater that is a mix of freshwater from precipitation, Apennine Rivers and brackish (Holocene) Adriatic Sea water. Here, the drainage system of the low lying land enhances groundwater flow into the lake. Surface water evaporation is larger in temperate and Mediterranean climates than the actual evapotranspiration of pre-existing grassland and forests. The lakes, therefore, cause a loss of freshwater. The creation of water surfaces allows algae and other flora and fauna to develop. In general, water becomes gradually enriched in certain chemical constituents on its way through the hydrological cycle, especially as groundwater due to water-rock interactions. When groundwater ex-filtrates into gravel pit lakes, the natural flow of solutes towards the sea is interrupted. Hydrochemical analysis of ground- and surface waters, as well as chemical analysis of lake bottom sediments and stable H and O isotope data, show that gravel pit lake water is characterized (among others) by a higher pH, O2 and alkalinity and lower dissolved metal and certain trace concentrations than natural lakes and groundwater. In both settings, groundwater rich in dissolved elements (e.g. Al, As, Fe, Mn, Ni and PO43) flows into the gravel pit lakes where the pH and DO are high, which enhances the (co)precipitation of Fe, Mn and Al oxides that include trace elements. Metal concentrations in the Dutch lake's bottom sediments have increased over a 10 year period. Redox reactions caused by water table lowering and farmland fertilization upstream from the lake explain the metals mobilization and subsequent transport with groundwater towards the lakes. The gravel pit lakes, especially if there are many close together, influence so the cycle of water metals, nutrients as well as other trace elements of a watershed by incorporating them into biomass and bottom sediments or creating an environment where they can remain in concentrated solution.

Molecular dynamics simulations study of nano bubble attachment at hydrophobic surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin, Jiaqi; Dang, Liem X.; Miller, Jan D.

Bubble attachment phenomena are examined using Molecular Dynamics Simulations (MDS) for the first time. The simulation involves a nitrogen nano bubble containing 906 nitrogen molecules in a water phase with 74,000 water molecules at molybdenite surfaces. During a simulation period of 1 ns, film rupture and displacement occurs. The attached nanobubble at the hydrophobic molybdenite face surface results in a contact angle of about 90º. This spontaneous attachment is due to a “water exclusion zone” at the molybdenite face surface and can be explained by a van der Waals (vdW) attractive force, as discussed in the literature. In contrast, themore » film is stable at the hydrophilic quartz (001) surface and the bubble does not attach. Contact angles determined from MD simulations are reported, and these results agree well with experimental and MDS sessile drop results. In this way, film stability and bubble attachment are described with respect to interfacial water structure for surfaces of different polarity. Interfacial water molecules at the hydrophobic molybdenite face surface have relatively weak interactions with the surface when compared to the hydrophilic quartz (001) surface, as revealed by the presence of a 3 Å “water exclusion zone” at the molybdenite/water interface. The molybdenite armchair-edge and zigzag-edge surfaces show a comparably slow process for film rupture and displacement when compared to the molybdenite face surface, which is consistent with their relatively weak hydrophobic character.« less

A statistical examination of Nimbus 7 SMMR data and remote sensing of sea surface temperature, liquid water content in the atmosphere and surfaces wind speed

NASA Technical Reports Server (NTRS)

Prabhakara, C.; Wang, I.; Chang, A. T. C.; Gloersen, P.

1982-01-01

Nimbus 7 Scanning Multichannel Microwave Radiometer (SMMR) brightness temperature measurements over the global oceans have been examined with the help of statistical and empirical techniques. Such analyses show that zonal averages of brightness temperature measured by SMMR, over the oceans, on a large scale are primarily influenced by the water vapor in the atmosphere. Liquid water in the clouds and rain, which has a much smaller spatial and temporal scale, contributes substantially to the variability of the SMMR measurements within the latitudinal zones. The surface wind not only increases the surface emissivity but through its interactions with the atmosphere produces correlations, in the SMMR brightness temperature data, that have significant meteorological implications. It is found that a simple meteorological model can explain the general characteristics of the SMMR data. With the help of this model methods to infer over the global oceans, the surface temperature, liquid water content in the atmosphere, and surface wind speed are developed. Monthly mean estimates of the sea surface temperature and surface winds are compared with the ship measurements. Estimates of liquid water content in the atmosphere are consistent with earlier satellite measurements.

DFT study on the interaction of TiO2 (001) surface with HCHO molecules

NASA Astrophysics Data System (ADS)

Wu, Guofei; Zhao, Cuihua; Guo, Changqing; Chen, Jianhua; Zhang, Yibing; Li, Yuqiong

2018-01-01

The interactions of formaldehyde (HCHO) molecule with TiO2 (001) surface were studied using density functional theory calculations. HCHO molecules are dissociated by the cleavage of Csbnd H bonds after adsorption on TiO2 surface. The strong interactions between HCHO melecules and TiO2 surface are largely attributed to the bonding of hydrogen of HCHO and oxygen of TiO2 surface, which is mainly from the hybridization of the H 1s, O 2p and O 2s. The newly formed Hsbnd O bonds cause the structure changes of TiO2 surface, and lead to the cleavage of Osbnd Ti bond of TiO2 surface. The Csbnd O bond that the dissociated remains of HCHO and newly formed Hsbnd O bond can be oxidized to form carbon dioxide and water in subsequent action by oxygen from the atomosphere. The charges transfer from HCHO to TiO2 surface, and the sum amount of the charges transferred from four HCHO molecules to TiO2 surface is bigger than that from one HCHO molecule to TiO2 surface due to the combined interaction of four HCHO molecules with TiO2 surface.

Hydrogeologic setting, ground-water flow, and ground-water quality at the Lake Wheeler Road research station, 2001-03 : North Carolina Piedmont and Mountains Resource Evaluation Program

USGS Publications Warehouse

Chapman, Melinda J.; Bolich, Richard E.; Huffman, Brad A.

2005-01-01

Results of a 2-year field study of the regolith-fractured bedrock ground-water system at the Lake Wheeler Road research station in Wake County, North Carolina, indicate both disconnection and interaction among components of the ground-water system. The three components of the ground-water system include (1) shallow, porous regolith; (2) a transition zone, including partially weathered rock, having both secondary (fractures) and primary porosity; and (3) deeper, fractured bedrock that has little, if any, primary porosity and is dominated by secondary fractures. The research station includes 15 wells (including a well transect from topographic high to low settings) completed in the three major components of the ground-water-flow system and a surface-water gaging station on an unnamed tributary. The Lake Wheeler Road research station is considered representative of a felsic gneiss hydrogeologic unit having steeply dipping foliation and a relatively thick overlying regolith. Bedrock foliation generally strikes N. 10? E. to N. 30? E. and N. 20? W. to N. 40? W. to a depth of about 400 feet and dips between 70? and 80? SE. and NE., respectively. From 400 to 600 feet, the foliation generally strikes N. 70? E. to N. 80? E., dipping 70? to 80? SE. Depth to bedrock locally ranges from about 67 to 77 feet below land surface. Fractures in the bedrock generally occur in two primary sets: low dip angle, stress relief fractures that cross cut foliation, and steeply dipping fractures parallel to foliation. Findings of this study generally support the conceptual models of ground-water flow from high to low topographic settings developed for the Piedmont and Blue Ridge Provinces in previous investigations, but are considered a refinement of the generalized conceptual model based on a detailed local-scale investigation. Ground water flows toward a surface-water boundary, and hydraulic gradients generally are downward in recharge areas and upward in discharge areas; however, local variations in vertical gradients are apparent. Water-quality sampling and monitoring efforts were conducted to characterize the interaction of components of the ground-water system. Elevated nitrate concentrations as high as 22 milligrams per liter were detected in shallow ground water from the regolith at the study site. These elevated nitrate concentrations likely are related to land use, which includes agricultural practices that involve animal feeding operations and crop fertilization. Continuous ground-water-quality data indicate seasonal fluctuations in field water-quality properties, differences with respect to depth, and fluctuations during recharge events. Water-quality properties recorded in the regolith well following rainfall indicate the upwelling of deeper ground water in the discharge area, likely from ground water in the transition-zone fractures. Additionally, interaction with a surface-water boundary appears likely in the ground-water discharge area, as water levels in all three ground-water zones, including the deep bedrock, mimic the surface-water rise during rainfall.

Direct Measurement of the Surface Energy of Graphene.

PubMed

van Engers, Christian D; Cousens, Nico E A; Babenko, Vitaliy; Britton, Jude; Zappone, Bruno; Grobert, Nicole; Perkin, Susan

2017-06-14

Graphene produced by chemical vapor deposition (CVD) is a promising candidate for implementing graphene in a range of technologies. In most device configurations, one side of the graphene is supported by a solid substrate, wheras the other side is in contact with a medium of interest, such as a liquid or other two-dimensional material within a van der Waals stack. In such devices, graphene interacts on both faces via noncovalent interactions and therefore surface energies are key parameters for device fabrication and operation. In this work, we directly measured adhesive forces and surface energies of CVD-grown graphene in dry nitrogen, water, and sodium cholate using a modified surface force balance. For this, we fabricated large (∼1 cm 2 ) and clean graphene-coated surfaces with smooth topography at both macro- and nanoscales. By bringing two such surfaces into contact and measuring the force required to separate them, we measured the surface energy of single-layer graphene in dry nitrogen to be 115 ± 4 mJ/m 2 , which was similar to that of few-layer graphene (119 ± 3 mJ/m 2 ). In water and sodium cholate, we measured interfacial energies of 83 ± 7 and 29 ± 6 mJ/m 2 , respectively. Our work provides the first direct measurement of graphene surface energy and is expected to have an impact both on the development of graphene-based devices and contribute to the fundamental understanding of surface interactions.

Adsorption of insulin peptide on charged single-walled carbon nanotubes: significant role of ordered water molecules.

PubMed

Shen, Jia-Wei; Wu, Tao; Wang, Qi; Kang, Yu; Chen, Xin

2009-06-02

Ordered hydration shells: The more ordered hydration shells outside the charged CNT surfaces prevent more compact adsorption of the peptide in the charged CNT systems [picture: see text], but peptide binding strengths on the charged CNT surfaces are stronger due to the electrostatic interaction.Studies of adsorption dynamics and stability for peptides/proteins on single-walled carbon nanotubes (SWNTs) are of great importance for a better understanding of the properties and nature of nanotube-based biosystems. Herein, the dynamics and mechanism of the adsorption of the insulin chain B peptide on different charged SWNTs are investigated by explicit solvent molecular dynamics simulations. The results show that all types of surfaces effectively attract the model peptide. Water molecules play a significant role in peptide adsorption on the surfaces of charged carbon nanotubes (CNTs). Compared to peptide adsorption on neutral CNT surfaces, the more ordered hydration shells outside the tube prevent more compact adsorption of the peptide in charged CNT systems. This shield effect leads to a smaller conformational change and van der Waals interaction between the peptide and surfaces, but peptide binding strengths on charged CNT surfaces are stronger than those on the neutral CNT surface due to the strong electrostatic interaction. The result of these simulations implies the possibility of improving the binding strength of peptides/proteins on CNT surfaces, as well as keeping the integrity of the peptide/protein conformation in peptide/protein-CNT complexes by charging the CNTs.

Surface characterization of U(AlxSi1-x)3 alloy and its interaction with O2 and H2O, at room temperature

NASA Astrophysics Data System (ADS)

Matmor, M.; Cohen, S.; Rafailov, G.; Vaknin, M.; Shamir, N.; Gouder, T.; Zalkind, S.

2018-02-01

Surface characterization and the interactions of U(AlxSi1-x)3 alloy (x = 0.57) with oxygen and water vapor were studied, utilizing X-Ray Photoelectron Spectroscopy and Direct Recoil Spectrometry, at room temperature. The U 4f spectrum of U(AlxSi1-x)3 alloy exhibits weak correlation satellites, suggesting an itinerant description of the U 5f states for this compound. The Al and Si 2p lines are chemically shifted to lower binding energies. Exposing the alloy to oxygen and water vapor results in oxidation of mainly the uranium and aluminum components, while silicon is only slightly oxidized. Oxygen was found to be a stronger oxidizer than water vapor and the trend is consistent with the more negative enthalpies of formation of metal oxides produced by the O2 reaction, as compared to H2O. During oxygen exposure, fast oxidation occurs by oxide islands nucleation and lateral growth, followed by oxidation of the sub-surface, up to ∼4 nm, at 1000 L exposure. Water initially reacts with the surface by full dissociation and oxide islands formation, which is then covered by hydroxides. Only a minor increase in the oxide thickness of up to ∼2.5 nm, was observed after coalescence.

Water-wettable polypropylene fibers by facile surface treatment based on soy proteins.

PubMed

Salas, Carlos; Genzer, Jan; Lucia, Lucian A; Hubbe, Martin A; Rojas, Orlando J

2013-07-24

Modification of the wetting behavior of hydrophobic surfaces is essential in a variety of materials, including textiles and membranes that require control of fluid interactions, adhesion, transport processes, sensing, etc. This investigation examines the enhancement of wettability of an important class of textile materials, viz., polypropylene (PP) fibers, by surface adsorption of different proteins from soybeans, including soy flour, isolate,glycinin, and β-conglycinin. Detailed investigations of soy adsorption from aqueous solution (pH 7.4, 25 °C) on polypropylene thin films is carried out using quartz crystal microbalance (QCM) and surface plasmon resonance (SPR). A significant amount of protein adsorbs onto the PP surfaces primarily due to hydrophobic interactions. We establish that adsorption of a cationic surfactant, dioctadecyldimethylammonium bromide (DODA) onto PP surfaces prior to the protein deposition dramatically enhances its adsorption. The adsorption of proteins from native (PBS buffer, pH 7.4, 25 °C) and denatured conditions (PBS buffer, pH 7.4, 95 °C) onto DODA-treated PP leads to a high coverage of the proteins on the PP surface as confirmed by a significant improvement in water wettability. A shift in the contact angle from 128° to completely wettable surfaces (≈0°) is observed and confirmed by imaging experiments conducted with fluorescence tags. Furthermore, the results from wicking tests indicate that hydrophobic PP nonwovens absorb a significant amount of water after protein treatment, i.e., the PP-modified surfaces become completely hydrophilic.

Dynamics of Surface Reorganization of Poly(methyl methacrylate) in Contact with Water

NASA Astrophysics Data System (ADS)

Horinouchi, Ayanobu; Atarashi, Hironori; Fujii, Yoshihisa; Tanaka, Keiji

2013-03-01

New tools for tailor-made diagnostics, such as DNA arrays and tips for micro-total-analysis systems, are generally made from polymers. In these applications, the polymer surface is in contact with a water phase. However, despite the importance of detailed knowledge of the fundamental interactions of polymer interfaces with liquids, such studies are very limited. As an initial benchmark for designing and constructing specialized biomedical surfaces containing polymer, aggregation states and dynamics of chains at the water interface should be systematically examined. We here apply time-resolved contact angle measurement to study the dynamics of the surface reorganization of poly(methyl methacrylate) (PMMA) in contact with water. By doing the measurements at various temperatures, it is possible to discuss the surface dynamics of PMMA based on the apparent activation energy. Also, sum-frequency generation spectroscopy revealed that the surface reorganization involves the conformational changes in the main chain part as well as the side chains. Hence, the dynamics observed here may reflect the segmental motion at the outermost region of the PMMA film, in which water plays as a plasticizer.

Adsorption and structure of water on kaolinite surfaces: possible insight into ice nucleation from grand canonical monte carlo calculations.

PubMed

Croteau, T; Bertram, A K; Patey, G N

2008-10-30

Grand canonical Monte Carlo calculations are used to determine water adsorption and structure on defect-free kaolinite surfaces as a function of relative humidity at 235 K. This information is then used to gain insight into ice nucleation on kaolinite surfaces. Results for both the SPC/E and TIP5P-E water models are compared and demonstrate that the Al-surface [(001) plane] and both protonated and unprotonated edges [(100) plane] strongly adsorb at atmospherically relevant relative humidities. Adsorption on the Al-surface exhibits properties of a first-order process with evidence of collective behavior, whereas adsorption on the edges is essentially continuous and appears dominated by strong water lattice interactions. For the protonated and unprotonated edges no structure that matches hexagonal ice is observed. For the Al-surface some of the water molecules formed hexagonal rings. However, the a o lattice parameter for these rings is significantly different from the corresponding constant for hexagonal ice ( Ih). A misfit strain of 14.0% is calculated between the hexagonal pattern of water adsorbed on the Al-surface and the basal plane of ice Ih. Hence, the ring structures that form on the Al-surface are not expected to be good building-blocks for ice nucleation due to the large misfit strain.

Designed cellulose nanocrystal surface properties for improving barrier properties in polylactide nanocomposites.

PubMed

Espino-Pérez, Etzael; Bras, Julien; Almeida, Giana; Plessis, Cédric; Belgacem, Naceur; Perré, Patrick; Domenek, Sandra

2018-03-01

Nanocomposites are an opportunity to increase the performance of polymer membranes by fine-tuning their morphology. In particular, the understanding of the contribution of the polymer matrix/nanofiller interface to the overall transport properties is key to design membranes with tailored selective and adsorptive properties. In that aim, cellulose nanocrystals (CNC)/polylactide (PLA) nanocomposites were fabricated with chemically designed interfaces, which were ensuring the compatibility between the constituents and impacting the mass transport mechanism. A detailed analysis of the mass transport behaviour of different permeants in CNC/PLA nanocomposites was carried out as a function of their chemical affinity to grafted CNC surfaces. Penetrants (O 2 and cyclohexane), which were found to slightly interact with the constituents of the nanocomposites, provided information on the small tortuosity effect of CNC on diffusive mass transport. The mass transport of water (highly interacting with CNC) and anisole (interacting only with designed CNC surfaces) exhibited non-Fickian, Case II behaviour. The water vapour caused significant swelling of the CNC, which created a preferential pathway for mass transport. CNC surface grafting could attenuate this phenomenon and decrease the water transport rate. Anisole, an aromatic organic vapour, became reversibly trapped at the specifically designed CNC/PLA interface, but without any swelling or creation of an accelerated pathway. This caused the decrease of the overall mass transport rate. The latter finding could open a way to the creation of materials with specifically designed barrier properties by designing nanocomposites interfaces with specific interactions towards permeants. Copyright © 2017 Elsevier Ltd. All rights reserved.

Modeling Adsorption-Desorption Processes at the Intermolecular Interactions Level

NASA Astrophysics Data System (ADS)

Varfolomeeva, Vera V.; Terentev, Alexey V.

2018-01-01

Modeling of the surface adsorption and desorption processes, as well as the diffusion, are of considerable interest for the physical phenomenon under study in ground tests conditions. When imitating physical processes and phenomena, it is important to choose the correct parameters to describe the adsorption of gases and the formation of films on the structural materials surface. In the present research the adsorption-desorption processes on the gas-solid interface are modeled with allowance for diffusion. Approaches are proposed to describe the adsorbate distribution on the solid body surface at the intermolecular interactions level. The potentials of the intermolecular interaction of water-water, water-methane and methane-methane were used to adequately modeling the real physical and chemical processes. The energies calculated by the B3LYP/aug-cc-pVDZ method. Computational algorithms for determining the average molecule area in a dense monolayer, are considered here. Differences in modeling approaches are also given: that of the proposed in this work and the previously approved probabilistic cellular automaton (PCA) method. It has been shown that the main difference is due to certain limitations of the PCA method. The importance of accounting the intermolecular interactions via hydrogen bonding has been indicated. Further development of the adsorption-desorption processes modeling will allow to find the conditions for of surface processes regulation by means of quantity adsorbed molecules control. The proposed approach to representing the molecular system significantly shortens the calculation time in comparison with the use of atom-atom potentials. In the future, this will allow to modeling the multilayer adsorption at a reasonable computational cost.

Delineation of spatial-temporal patterns of groundwater/surface-water interaction along a river reach (Aa River, Belgium) with transient thermal modeling

NASA Astrophysics Data System (ADS)

Anibas, Christian; Tolche, Abebe Debele; Ghysels, Gert; Nossent, Jiri; Schneidewind, Uwe; Huysmans, Marijke; Batelaan, Okke

2018-05-01

Among the advances made in analytical and numerical analysis methods to quantify groundwater/surface-water interaction, one methodology that stands out is the use of heat as an environmental tracer. A large data set of river and riverbed temperature profiles from the Aa River in Belgium has been used to examine the spatial-temporal variations of groundwater/surface-water interaction. Exchange fluxes were calculated with the numerical heat-transport code STRIVE. The code was applied in transient mode to overcome previous limitations of steady-state analysis, and allowed for the calculation of model quality. In autumn and winter the mean exchange fluxes reached -90 mm d-1, while in spring and early summer fluxes were -42 mm d-1. Predominantly gaining conditions occurred along the river reach; however, in a few areas the direction of flow changed in time. The river banks showed elevated fluxes up to a factor of 3 compared to the center of the river. Higher fluxes were detected in the upstream section of the reach. Due to the influence of exchange fluxes along the river banks, larger temporal variations were found in the downstream section. The exchange fluxes at the river banks seemed more driven by variable local exchange flows, while the center of the river was dominated by deep and steady regional groundwater flows. These spatial and temporal differences in groundwater/surface-water exchange show the importance of long-term investigations on the driving forces of hyporheic processes across different scales.

Characterizing groundwater/surface-water interactions in the interior of Jianghan Plain, central China

NASA Astrophysics Data System (ADS)

Du, Yao; Ma, Teng; Deng, Yamin; Shen, Shuai; Lu, Zongjie

2018-06-01

Quantifying groundwater/surface-water interactions is essential for managing water resources and revealing contaminant fate. There has been little concern on the exchange between streams and aquifers through an extensive aquitard thus far. In this study, hydrogeologic calculation and tritium modeling were jointly applied to characterize such interactions through an extensive aquitard in the interior of Jianghan Plain, an alluvial plain of Yangtze River, China. One groundwater simulation suggested that the lateral distance of influence from the river was about 1,000 m; vertical flow in the aquitard followed by lateral flow in the aquifer contributed significantly more ( 90%) to the aquifer head change near the river than lateral bank storage in the aquitard followed by infiltration. The hydrogeologic calculation produced vertical fluxes of the order 0.01 m/day both near and farther from the river, suggesting that similar shorter-lived (half-monthly) vertical fluxes occur between the river and aquitard near the river, and between the surface end members and aquitard farther from the river. Tritium simulation based on the OTIS model produced an average groundwater residence time of about 15 years near the river and a resulting vertical flux of the order 0.001 m/day. Another tritium simulation based on a dispersion model produced a vertical flux of the order 0.0001 m/day away from the river, coupled with an average residence time of around 90 years. These results suggest an order of magnitude difference for the longer-lived (decadal) vertical fluxes between surface waters and the aquifer near and away from the river.

Characterizing groundwater/surface-water interactions in the interior of Jianghan Plain, central China

NASA Astrophysics Data System (ADS)

Du, Yao; Ma, Teng; Deng, Yamin; Shen, Shuai; Lu, Zongjie

2018-01-01

Quantifying groundwater/surface-water interactions is essential for managing water resources and revealing contaminant fate. There has been little concern on the exchange between streams and aquifers through an extensive aquitard thus far. In this study, hydrogeologic calculation and tritium modeling were jointly applied to characterize such interactions through an extensive aquitard in the interior of Jianghan Plain, an alluvial plain of Yangtze River, China. One groundwater simulation suggested that the lateral distance of influence from the river was about 1,000 m; vertical flow in the aquitard followed by lateral flow in the aquifer contributed significantly more ( 90%) to the aquifer head change near the river than lateral bank storage in the aquitard followed by infiltration. The hydrogeologic calculation produced vertical fluxes of the order 0.01 m/day both near and farther from the river, suggesting that similar shorter-lived (half-monthly) vertical fluxes occur between the river and aquitard near the river, and between the surface end members and aquitard farther from the river. Tritium simulation based on the OTIS model produced an average groundwater residence time of about 15 years near the river and a resulting vertical flux of the order 0.001 m/day. Another tritium simulation based on a dispersion model produced a vertical flux of the order 0.0001 m/day away from the river, coupled with an average residence time of around 90 years. These results suggest an order of magnitude difference for the longer-lived (decadal) vertical fluxes between surface waters and the aquifer near and away from the river.

Solvent/co-solvent effects on the electronic properties and adsorption mechanism of anticancer drug Thioguanine on Graphene oxide surface as a nanocarrier: Density functional theory investigation and a molecular dynamics

NASA Astrophysics Data System (ADS)

Hasanzade, Zohre; Raissi, Heidar

2017-11-01

In this work, the adsorption of Thioguanine (TG) anticancer drug on the surface of Graphene oxide (GO) nanosheet has investigated using density functional theory (DFT) and molecular dynamics simulation (MDs). Quantum mechanics calculations by two methods including M06-2X/6-31G**and ωB97X-D/6-31G** have been employed to calculate the details of energetic, geometric, and electronic properties of the TG molecule interacting with Graphene oxide nanosheet (GONS). DFT calculations confirmed that the strongest adsorption is observed when hydrogen bond interactions between TG molecule and the functional groups of Graphene oxide nanosheet are predominate. In all calculations, solvent effects have been considered in water using the PCM method. It is found that TG molecule can be adsorbed on Graphene oxide with negative solvation energy, indicating the TG adsorption on Graphene oxide surfaces is thermodynamically favored. Moreover, MD simulations are examined to understand the solvent/co-solvent effect (water, ethanol, nicotine) on the Thioguanine drug delivery through Graphene oxide. The results of RDF patterns and the van der Waals energy calculations show that interaction between TG drugs and the Graphene oxide surface is stronger in water solvent compared to the other co-solvent. The obtained MD results illustrate that when nicotine and ethanol exist in the system, the drug takes longer time to bind with GO nanosheet and the system becomes unstable. It can be concluded that Graphene oxide can be a promising candidate in water media for delivery the TG molecule.

Hydration of a Large Anionic Charge Distribution - Naphthalene-Water Cluster Anions

NASA Astrophysics Data System (ADS)

Weber, J. Mathias; Adams, Christopher L.

2010-06-01

We report the infrared spectra of anionic clusters of naphthalene with up to three water molecules. Comparison of the experimental infrared spectra with theoretically predicted spectra from quantum chemistry calculations allow conclusions regarding the structures of the clusters under study. The first water molecule forms two hydrogen bonds with the π electron system of the naphthalene moiety. Subsequent water ligands interact with both the naphthalene and the other water ligands to form hydrogen bonded networks, similar to other hydrated anion clusters. Naphthalene-water anion clusters illustrate how water interacts with negative charge delocalized over a large π electron system. The clusters are interesting model systems that are discussed in the context of wetting of graphene surfaces and polyaromatic hydrocarbons.

THE IMPACT OF GROUND WATER-SURFACE WATER INTERACTIONS ON CONTAMINANT TRANSPORT AT CONTAMINATED SITES

EPA Science Inventory

The purpose of this document is to provide an overview of the dynamics of chemical processes that govern contaminant transport and speciation during water exchange across the GW/SW transition zone. A conceptual model of the GW/SW transition zone is defined to serve as a starting...

ASSESSMENT OF NEAR-STREAM GROUND WATER-SURFACE WATER INTERACTION (GSI) OF A DEGRADED STREAM BEFORE RESTORATION

EPA Science Inventory

In Fall 2001, EPA undertook an intensive collaborative research effort with the USGS and the Institute of Ecosystem Studies (IES) to evaluate the impact of restoration on water quality at a degraded stream in an urban watershed using a before/after stream restoration study design...

Effects of Potamogeton crispus L.-bacteria interactions on the removal of phthalate acid esters from surface water.

PubMed

Chi, Jie; Gao, Jing

2015-01-01

To investigate the mechanism of submerged macrophyte-bacteria interactions on the removal of phthalic acid esters from surface water, experiments with and without Potamogeton crispus L. were performed. A two-compartment (i.e., water and plant) kinetic model was developed. The model adequately described the variation of dibutyl phthalate (DBP) and di-2-ethylhexyl phthalate (DEHP) in the plant-water system by providing the first-order rate constants of plant uptake (k1) and release (k2), microbial degradation in water (k3) and plant degradation (k4). During 10-d incubation, the presence of P. crispus enhanced the removal of DBP and DEHP from water by 6.3% and 22.4%. Compared with the experiment without P. crispus, biodegradation of DBP in water with P. crispus decreased by 8.3% because of plant uptake even though k3 increased by 30%. 21.4% of DBP transferred from water to plants, of which only small amount (5.1%) retained in the plant and the rest (94.9%) was degraded. Different from DBP, biodegradation of DEHP in water with P. crispus was a slightly higher than that without P. crispus. 25.5% of DEHP transferred from water to plants, of which a large portion (73.3%) retained in the plant and the rest (26.7%) was degraded. This finding reveals that the enhancement of DBP removal from surface water is mainly related to faster degradation in the plant, whereas it is mainly related to higher plant accumulation for DEHP. Copyright © 2014 Elsevier Ltd. All rights reserved.

Protein Adsorption in Three Dimensions

PubMed Central

Vogler, Erwin A.

2011-01-01

Recent experimental and theoretical work clarifying the physical chemistry of blood-protein adsorption from aqueous-buffer solution to various kinds of surfaces is reviewed and interpreted within the context of biomaterial applications, especially toward development of cardiovascular biomaterials. The importance of this subject in biomaterials surface science is emphasized by reducing the “protein-adsorption problem” to three core questions that require quantitative answer. An overview of the protein-adsorption literature identifies some of the sources of inconsistency among many investigators participating in more than five decades of focused research. A tutorial on the fundamental biophysical chemistry of protein adsorption sets the stage for a detailed discussion of the kinetics and thermodynamics of protein adsorption, including adsorption competition between two proteins for the same adsorbent immersed in a binary-protein mixture. Both kinetics and steady-state adsorption can be rationalized using a single interpretive paradigm asserting that protein molecules partition from solution into a three-dimensional (3D) interphase separating bulk solution from the physical-adsorbent surface. Adsorbed protein collects in one-or-more adsorbed layers, depending on protein size, solution concentration, and adsorbent surface energy (water wettability). The adsorption process begins with the hydration of an adsorbent surface brought into contact with an aqueous-protein solution. Surface hydration reactions instantaneously form a thin, pseudo-2D interface between the adsorbent and protein solution. Protein molecules rapidly diffuse into this newly-formed interface, creating a truly 3D interphase that inflates with arriving proteins and fills to capacity within milliseconds at mg/mL bulk-solution concentrations CB. This inflated interphase subsequently undergoes time-dependent (minutes-to-hours) decrease in volume VI by expulsion of either-or-both interphase water and initially-adsorbed protein. Interphase protein concentration CI increases as VI decreases, resulting in slow reduction in interfacial energetics. Steady-state is governed by a net partition coefficient P=(/CBCI). In the process of occupying space within the interphase, adsorbing protein molecules must displace an equivalent volume of interphase water. Interphase water is itself associated with surface-bound water through a network of transient hydrogen bonds. Displacement of interphase water thus requires an amount of energy that depends on the adsorbent surface chemistry/energy. This “adsorption-dehydration” step is the significant free-energy cost of adsorption that controls the maximum amount of protein that can be adsorbed at steady state to a unit adsorbent-surface area (the adsorbent capacity). As adsorbent hydrophilicity increases, protein adsorption monotonically decreases because the energetic cost of surface dehydration increases, ultimately leading to no protein adsorption near an adsorbent water wettability (surface energy) characterized by a water contact angle θ → 65°. Consequently, protein does not adsorb (accumulate at interphase concentrations greater than bulk solution) to more hydrophilic adsorbents exhibiting θ < 65° . For adsorbents bearing strong Lewis acid/base chemistry such as ion-exchange resins, protein/surface interactions can be highly favorable, causing protein to adsorb in multilayers in a relatively thick interphase. A straightforward, three-component free energy relationship captures salient features of protein adsorption to all surfaces predicting that the overall free energy of protein adsorption ΔGadso is a relatively small multiple of thermal energy for any surface chemistry (except perhaps for bioengineered surfaces bearing specific ligands for adsorbing protein) because a surface chemistry that interacts chemically with proteins must also interact with water through hydrogen bonding. In this way, water moderates protein adsorption to any surface by competing with adsorbing protein molecules. This Leading Opinion ends by proposing several changes to the protein-adsorption paradigm that might advance answers to the three core questions that frame the “protein-adsorption problem” that is so fundamental to biomaterials surface science. PMID:22088888

Water Hydrogen-Bonding Network Structure and Dynamics at Phospholipid Multibilayer Surface: Femtosecond Mid-IR Pump-Probe Spectroscopy.

PubMed

Kundu, Achintya; Błasiak, Bartosz; Lim, Joon-Hyung; Kwak, Kyungwon; Cho, Minhaeng

2016-03-03

The water hydrogen-bonding network at a lipid bilayer surface is crucial to understanding membrane structures and its functional activities. With a phospholipid multibilayer mimicking a biological membrane, we study the temperature dependence of water hydrogen-bonding structure, distribution, and dynamics at a lipid multibilayer surface using femtosecond mid-IR pump-probe spectroscopy. We observe two distinguished vibrational lifetime components. The fast component (0.6 ps) is associated with water interacting with a phosphate part, whereas the slow component (1.9 ps) is with bulk-like choline-associated water. With increasing temperature, the vibrational lifetime of phosphate-associated water remains constant though its relative fraction dramatically increases. The OD stretch vibrational lifetime of choline-bound water slows down in a sigmoidal fashion with respect to temperature, indicating a noticeable change of the water environment upon the phase transition. The water structure and dynamics are thus shown to be in quantitative correlation with the structural change of liquid multibilayer upon the gel-to-liquid crystal phase transition.

New methods for the analysis of the protein-solvent interface

NASA Astrophysics Data System (ADS)

Goodfellow, Julia M.; Pitt, William R.; Smart, Oliver S.; Williams, Mark A.

1995-09-01

The protein-solvent interface is complex and may include solvent channels and cavities as well as the normal surface water molecules. We describe several algorithms for investigating the intra- and inter-molecular interactions of proteins in general but with the aim of developing methods to accurately and definitively characterise the interactions of water and other small ligands with proteins. Specifically, we present the methods which underlie three programs (AQUARIUS2, HOLE and PRO_ACT) which can be used to to look at different aspects of these interactions.

Clay Minerals as Solid Acids and Their Catalytic Properties.

ERIC Educational Resources Information Center

Helsen, J.

1982-01-01

Discusses catalytic properties of clays, attributed to acidity of the clay surface. The formation of carbonium ions on montmorillonite is used as a demonstration of the presence of surface acidity, the enhanced dissociation of water molecules when polarized by cations, and the way the surface can interact with organic substances. (Author/JN)

Use of the Nitrogen Index to assess nitrate leaching and water drainage from plastic-mulched horticultural cropping systems of Florida

USDA-ARS?s Scientific Manuscript database

Water quality in Florida is significantly impacted by nitrogen (N) losses from agriculture in a large part of the state, where there is a close interaction between surface water and groundwater that has a high water table. Horticultural crops are planted across large areas of Florida, including area...

Interactions of woody biofuel feedstock production systems with water resources: Considerations for sustainability

Treesearch

Carl C. Trettin; Devendra Amatya; Mark Coleman

2008-01-01

Water resources are important for the production of woody biofuel feedstocks. It is necessary to ensure that production systems do not adversely affect the quantity or quality of surface and ground water. The effects of woody biomass plantations on water resources are largely dependent on the prior land use and the management regime. Experience from both irrigated and...

Interactions of woody biofuel feedstock production systems with water resources: considerations for sustainability

Treesearch

Carl C. Trettin; Devendra Amatya; Mark Coleman

2008-01-01

Water resources are important for the production of woody biofuel feedstocks. It is necessary to ensure that production systems do not adversely affect the quantity or quality of surface and ground water. The effects of woody biomass plantations on water resources are largely dependent on the prior land use and the management regime. Experience from both irrigated and...

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. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Preliminary Water-Table Map and Water-Quality Data for Part of the Matanuska-Susitna Valley, Alaska, 2005

USGS Publications Warehouse

Moran, Edward H.; Solin, Gary L.

2006-01-01

The Matanuska-Susitna Valley is in the northeastern part of the Cook Inlet Basin, Alaska, an area experiencing rapid population growth and development proximal to many lakes. Here water commonly flows between lakes and ground water, indicating interrelation between water quantity and quality. Thus concerns exist that poorer quality ground water may degrade local lake ecosystems. This concern has led to water-quality sampling in cooperation with the Alaska Department of Environmental Conservation and the Matanuska-Susitna Borough. A map showing the estimated altitude of the water table illustrates potential ground-water flow directions and areas where ground- and surface-water exchanges and interactions might occur. Water quality measured in selected wells and lakes indicates some differences between ground water and surface water. 'The temporal and spatial scarcity of ground-water-level and water-quality data limits the analysis of flow direction and water quality. Regionally, the water-table map indicates that ground water in the eastern and southern parts of the study area flows southerly. In the northcentral area, ground water flows predominately westerly then southerly. Although ground and surface water in most areas of the Matanuska-Susitna Valley are interconnected, they are chemically different. Analyses of the few water-quality samples collected in the area indicate that dissolved nitrite plus nitrate and orthophosphorus concentrations are higher in ground water than in surface water.'

A coupled surface-water and ground-water flow model (MODBRANCH) for simulation of stream-aquifer interaction

USGS Publications Warehouse

Swain, Eric D.; Wexler, Eliezer J.

1996-01-01

Ground-water and surface-water flow models traditionally have been developed separately, with interaction between subsurface flow and streamflow either not simulated at all or accounted for by simple formulations. In areas with dynamic and hydraulically well-connected ground-water and surface-water systems, stream-aquifer interaction should be simulated using deterministic responses of both systems coupled at the stream-aquifer interface. Accordingly, a new coupled ground-water and surface-water model was developed by combining the U.S. Geological Survey models MODFLOW and BRANCH; the interfacing code is referred to as MODBRANCH. MODFLOW is the widely used modular three-dimensional, finite-difference ground-water model, and BRANCH is a one-dimensional numerical model commonly used to simulate unsteady flow in open- channel networks. MODFLOW was originally written with the River package, which calculates leakage between the aquifer and stream, assuming that the stream's stage remains constant during one model stress period. A simple streamflow routing model has been added to MODFLOW, but is limited to steady flow in rectangular, prismatic channels. To overcome these limitations, the BRANCH model, which simulates unsteady, nonuniform flow by solving the St. Venant equations, was restructured and incorporated into MODFLOW. Terms that describe leakage between stream and aquifer as a function of streambed conductance and differences in aquifer and stream stage were added to the continuity equation in BRANCH. Thus, leakage between the aquifer and stream can be calculated separately in each model, or leakages calculated in BRANCH can be used in MODFLOW. Total mass in the coupled models is accounted for and conserved. The BRANCH model calculates new stream stages for each time interval in a transient simulation based on upstream boundary conditions, stream properties, and initial estimates of aquifer heads. Next, aquifer heads are calculated in MODFLOW based on stream stages calculated by BRANCH, aquifer properties, and stresses. This process is repeated until convergence criteria are met for head and stage. Because time steps used in ground-water modeling can be much longer than time intervals used in surface- water simulations, provision has been made for handling multiple BRANCH time intervals within one MODFLOW time step. An option was also added to BRANCH to allow the simulation of channel drying and rewetting. Testing of the coupled model was verified by using data from previous studies; by comparing results with output from a simpler, four-point implicit, open-channel flow model linked with MODFLOW; and by comparison to field studies of L-31N canal in southern Florida.

Oceanographic, Air-sea Interaction, and Environmental Aspects of Artificial Upwelling Produced by Wave-Inertia Pumps for Potential Hurricane Intensity Mitigation

NASA Astrophysics Data System (ADS)

Soloviev, A.; Dean, C.

2017-12-01

The artificial upwelling system consisting of the wave-inertia pumps driven by surface waves can produce flow of cold deep water to the surface. One of the recently proposed potential applications of the artificial upwelling system is the hurricane intensity mitigation. Even relatively small reduction of intensity may provide significant benefits. The ocean heat content (OHC) is the "fuel" for hurricanes. The OHC can be reduced by mixing of the surface layer with the cold water produced by wave-inertia pumps. Implementation of this system for hurricane mitigation has several oceanographic and air-sea interaction aspects. The cold water brought to the surface from a deeper layer has higher density than the surface water and, therefore, tends to sink back down. The mixing of the cold water produced by artificial upwelling depends on environmental conditions such as stratification, regional ocean circulation, and vertical shear. Another aspect is that as the sea surface temperature drops below the air temperature, the stable stratification develops in the atmospheric boundary layer. The stable atmospheric stratification suppresses sensible and latent heat air-sea fluxes and reduces the net longwave irradiance from the sea surface. As a result, the artificial upwelling may start increasing the OHC (though still reducing the sea surface temperature). In this work, the fate of the cold water in the stratified environment with vertical shear has been studied using computational fluid dynamics (CFD) tools. A 3D large eddy simulation model is initialized with observational temperature, salinity, and current velocity data from a sample location in the Straits of Florida. A periodic boundary condition is set along the direction of the current, which allows us to simulate infinite fetch. The model results indicate that the cold water brought to the sea surface by a wave-inertia pump forms a convective jet. This jet plunges into the upper ocean mixed layer and penetrates the thermocline. On the way down, the jet partially mixes with the surrounding water reducing the temperature of the upper ocean. The OHC thus can either reduce or increase, depending on the wave-inertia pump parameters. Based on the model results, we discuss feasibility of the implementation of the artificial upwelling system for hurricane intensity mitigation.

Land use, water and Mediterranean landscapes: modelling long-term dynamics of complex socio-ecological systems.

PubMed

Barton, C Michael; Ullah, Isaac I; Bergin, Sean

2010-11-28

The evolution of Mediterranean landscapes during the Holocene has been increasingly governed by the complex interactions of water and human land use. Different land-use practices change the amount of water flowing across the surface and infiltrating the soil, and change water's ability to move surface sediments. Conversely, water amplifies the impacts of human land use and extends the ecological footprint of human activities far beyond the borders of towns and fields. Advances in computational modelling offer new tools to study the complex feedbacks between land use, land cover, topography and surface water. The Mediterranean Landscape Dynamics project (MedLand) is building a modelling laboratory where experiments can be carried out on the long-term impacts of agropastoral land use, and whose results can be tested against the archaeological record. These computational experiments are providing new insights into the socio-ecological consequences of human decisions at varying temporal and spatial scales.

Characterization of the adsorption of water vapor and chlorine on microcrystalline silica

NASA Technical Reports Server (NTRS)

Skiles, J. A.; Wightman, J. P.

1979-01-01

The characterization of water adsorption on silica is necessary to an understanding of how hydrogen chloride interacts with silica. The adsorption as a function of outgas temperatures of silica and as a function of the isotherm temperature was studied. Characterization of the silica structure by infrared analysis, X-ray diffraction and differential scanning calorimetry, surface area determinations, characterization of the sample surface by electron spectroscopy for chemical analysis (ESCA), and determinations of the heat of immersion in water of silica were investigated. The silica with a scanning electron microscope was examined.

Jumping on water

NASA Astrophysics Data System (ADS)

Kim, Ho-Young

2016-11-01

Water striders can jump on water as high as they can jump on land. Quick jumps allow them to avoid sudden dangers such as predators' attacks, and therefore understanding how they make such a dramatic motion for survival can shed light on the ultimate level of semi-aquatic motility achievable through evolution. However, the mechanism of their vertical jumping from a water surface has eluded hydrodynamic explanations so far. By observing movements of water strider legs and theoretically analyzing their dynamic interactions with deforming liquid-air interface, we have recently found that different species of jumping striders always tune their leg rotation speed with a force just below that required to break the water surface to reach the maximum take-off velocity. Here, we start with discussing the fundamental theories of dynamics of floating and sinking of small objects. The theories then enable us to analyze forces acting on a water strider while it presses down the water surface to fully exploit the capillary force. We further introduce a 68-milligram at-scale robotic insect capable of jumping on water without splash, strikingly similar to the real strider, by utilizing the water surface just as a trampoline.

Application of Tracer-Injection Techniques to Demonstrate Surface-Water and Ground-Water Interactions Between an Alpine Stream and the North Star Mine, Upper Animas River Watershed, Southwestern Colorado

USGS Publications Warehouse

Wright, Winfield G.; Moore, Bryan

2003-01-01

Tracer-injection studies were done in Belcher Gulch in the upper Animas River watershed, southwestern Colorado, to determine whether the alpine stream infiltrates into underground mine workings of the North Star Mine and other nearby mines in the area. The tracer-injection studies were designed to determine if and where along Belcher Gulch the stream infiltrates into the mine. Four separate tracer-injec-tion tests were done using lithium bromide (LiBr), optical brightener dye, and sodium chloride (NaCl) as tracer solu-tions. Two of the tracers (LiBr and dye) were injected con-tinuously for 24 hours, one of the NaCl tracers was injected continuously for 12 hours, and one of the NaCl tracers was injected over a period of 1 hour. Concentration increases of tracer constituents were detected in water discharging from the North Star Mine, substantiating a surface-water and ground-water connection between Belcher Gulch and the North Star Mine. Different timing and magnitude of tracer breakthroughs indicated multiple flow paths with different residence times from the stream to the mine. The Pittsburgh and Sultan Mines were thought to physically connect to the North Star Mine, but tracer breakthroughs were inconclusive in water from these mines. From the tracer-injection tests and synoptic measure-ments of streamflow discharge, a conceptual model was devel-oped for surface-water and ground-water interactions between Belcher Gulch and the North Star Mine. This information, combined with previous surface geophysical surveys indicat-ing the presence of subsurface voids, may assist with decision-making process for preventing infiltration and for the remedia-tion of mine drainage from these mines.

Soliton interactions, Bäcklund transformations, Lax pair for a variable-coefficient generalized dispersive water-wave system

NASA Astrophysics Data System (ADS)

Liu, Lei; Tian, Bo; Zhen, Hui-Ling; Liu, De-Yin; Xie, Xi-Yang

2018-04-01

Under investigation in this paper is a variable-coefficient generalized dispersive water-wave system, which can simulate the propagation of the long weakly non-linear and weakly dispersive surface waves of variable depth in the shallow water. Under certain variable-coefficient constraints, by virtue of the Bell polynomials, Hirota method and symbolic computation, the bilinear forms, one- and two-soliton solutions are obtained. Bäcklund transformations and new Lax pair are also obtained. Our Lax pair is different from that previously reported. Based on the asymptotic and graphic analysis, with different forms of the variable coefficients, we find that there exist the elastic interactions for u, while either the elastic or inelastic interactions for v, with u and v as the horizontal velocity field and deviation height from the equilibrium position of the water, respectively. When the interactions are inelastic, we see the fission and fusion phenomena.

Platinum-catalyzed hydrolysis etching of SiC in water: A density functional theory study

NASA Astrophysics Data System (ADS)

Van Bui, Pho; Toh, Daisetsu; Isohashi, Ai; Matsuyama, Satoshi; Inagaki, Kouji; Sano, Yasuhisa; Yamauchi, Kazuto; Morikawa, Yoshitada

2018-05-01

A comprehensive study of the physicochemical interactions and the reaction mechanism of SiC etching with water by Pt catalysts can reveal key details about the surface treatment and catalytic phenomena at interfaces. Therefore, density functional theory simulations were performed to study the kinetics of Pt-assisted water dissociation and breaking of a Si–C bond compared to the HF-assisted mechanism. These calculations carefully considered the elastic and chemical interaction energies at the Pt–SiC interface, activation barriers of Si–C bond dissociation, and the catalytic role of Pt. It was found that the Pt-catalyzed etching of SiC in water is initiated via hydrolysis reactions that break the topmost Si–C bonds. The activation barrier strongly depends on the elastic and chemical interactions. However, chemical interactions are a dominant factor and mainly contribute to the lowering of the activation barrier, resulting in an increased rate of reaction.

Exploring the spatio-temporal interrelation between groundwater and surface water by using the self-organizing maps

NASA Astrophysics Data System (ADS)

Chen, I.-Ting; Chang, Li-Chiu; Chang, Fi-John

2018-01-01

In this study, we propose a soft-computing methodology to visibly explore the spatio-temporal groundwater variations of the Kuoping River basin in southern Taiwan. The self-organizing map (SOM) is implemented to investigate the interactive mechanism between surface water and groundwater over the river basin based on large high-dimensional data sets coupled with their occurrence times. We find that extracting the occurrence time from each 30-day moving average data set in the clustered neurons of the SOM is a crucial step to learn the spatio-temporal interaction between surface water and groundwater. We design 2-D Topological Bubble Map to summarize all the groundwater values of four aquifers in a neuron, which can visibly explore the major features of the groundwater in the vertical direction. The constructed SOM topological maps nicely display that: (1) the groundwater movement, in general, extends from the eastern area to the western, where groundwater in the eastern area can be easily recharged from precipitation in wet seasons and discharged into streams during dry seasons due to the high permeability in this area; (2) the water movements in the four aquifers of the study area are quite different, and the seasonal variations of groundwater in the second and third aquifers are larger than those of the others; and (3) the spatial distribution and seasonal variations of groundwater and surface water are comprehensively linked together over the constructed maps to present groundwater characteristics and the interrelation between groundwater and surface water. The proposed modeling methodology not only can classify the large complex high-dimensional data sets into visible topological maps to effectively facilitate the quantitative status of regional groundwater resources but can also provide useful elaboration for future groundwater management.

Field Techniques for Estimating Water Fluxes Between Surface Water and Ground Water

USGS Publications Warehouse

Rosenberry, Donald O.; LaBaugh, James W.

2008-01-01

This report focuses on measuring the flow of water across the interface between surface water and ground water, rather than the hydrogeological or geochemical processes that occur at or near this interface. The methods, however, that use hydrogeological and geochemical evidence to quantify water fluxes are described herein. This material is presented as a guide for those who have to examine the interaction of surface water and ground water. The intent here is that both the overview of the many available methods and the in-depth presentation of specific methods will enable the reader to choose those study approaches that will best meet the requirements of the environments and processes they are investigating, as well as to recognize the merits of using more than one approach. This report is designed to make the reader aware of the breadth of approaches available for the study of the exchange between surface and ground water. To accomplish this, the report is divided into four chapters. Chapter 1 describes many well-documented approaches for defining the flow between surface and ground waters. Subsequent chapters provide an in-depth presentation of particular methods. Chapter 2 focuses on three of the most commonly used methods to either calculate or directly measure flow of water between surface-water bodies and the ground-water domain: (1) measurement of water levels in well networks in combination with measurement of water level in nearby surface water to determine water-level gradients and flow; (2) use of portable piezometers (wells) or hydraulic potentiomanometers to measure hydraulic gradients; and (3) use of seepage meters to measure flow directly. Chapter 3 focuses on describing the techniques involved in conducting water-tracer tests using fluorescent dyes, a method commonly used in the hydrogeologic investigation and characterization of karst aquifers, and in the study of water fluxes in karst terranes. Chapter 4 focuses on heat as a tracer in hydrological investigations of the near-surface environment.

Experimental observation of standing interfacial waves induced by surface waves in muddy water

NASA Astrophysics Data System (ADS)

Maxeiner, Eric; Dalrymple, Robert A.

2011-09-01

A striking feature has been observed in a laboratory wave tank with a thin layer of clear water overlying a layer of mud. A piston-type wave maker is used to generate long monochromatic surface waves in a tank with a layer of kaolinite clay at the bottom. The wave action on the mud causes the clay particles to rise from the bottom into the water column, forming a lutocline. As the lutocline approaches the water surface, a set of standing interfacial waves form on the lutocline. The interfacial wave directions are oriented nearly orthogonal to the surface wave direction. The interfacial waves, which sometimes cover the entire length and width of the tank, are also temporally subharmonic as the phase of the interfacial wave alternates with each passing surface wave crest. These interfacial waves are the result of a resonant three-wave interaction involving the surface wave train and the two interfacial wave trains. The interfacial waves are only present when the lutocline is about 3 cm of the water surface and they can be sufficiently nonlinear as to exhibit superharmonics and a breaking-type of instability.

Inference of Stream Network Fragmentation Patterns from Ground Water - Surface Water Interactions on the High Plains Aquifer

NASA Astrophysics Data System (ADS)

Chandler, D. G.; Yang, X.; Steward, D. R.; Gido, K.

2007-12-01

Stream networks in the Great Plains integrate fluxes from precipitation as surface runoff in discrete events and groundwater as base flow. Changes in land cover and agronomic practices and development of ground water resources to support irrigated agriculture have resulted in profound changes in the occurrence and magnitude of stream flows, especially near the Ogallala aquifer, where precipitation is low. These changes have demonstrably altered the aquatic habitat of western Kansas, with documented changes in fish populations, riparian communities and groundwater quality due to stream transmission losses. Forecasting future changes in aquatic and riparian ecology and groundwater quality requires a large scale spatially explicit model of groundwater- surface water interaction. In this study, we combine historical data on land use, stream flow, production well development and groundwater level observations with groundwater elevation modeling to support a geospatial framework for assessing changes in refugia for aquatic species in four rivers in western Kansas between 1965 and 2005. Decreased frequency and duration of streamflow occurred in all rivers, but the extent of change depended on the geomorphology of the river basin and the extent of groundwater development. In the absence of streamflow, refugia for aquatic species were defined as the stream reaches below the phreatic surface of the regional aquifer. Changes in extent, location and degree of fragmentation of gaining reaches was found to be a strong predictor of surface water occurrence during drought and a robust hydrological template for the analysis of changes in recharge to alluvial and regional aquifers and riparian and aquatic habitat.

Groundwater/surface-water interactions in the Tunk, Bonaparte, Antoine, and Tonasket Creek Subbasins, Okanogan River Basin, North-Central Washington, 2008

USGS Publications Warehouse

Sumioka, S.S.; Dinicola, R.S.

2009-01-01

An investigation into groundwater/surface-water interactions in four tributary subbasins of the Okanogan River determined that streamflows and shallow groundwater levels beneath the streams varied seasonally and by location. Streamflows measured in June 2008 indicated net losses of streamflow along 10 of 17 reaches, and hydraulic gradients measured between streams and shallow groundwater indicated potential recharge of surface water to groundwater at 11 of 21 measurement sites. In September 2008, net losses of streamflow were indicated along 9 of 17 reaches, and potential recharge of surface water to groundwater was indicated at 18 of 21 measurement sites. The greatest losses of streamflow occurred near the confluences with the Okanogan River, likely due to the presence of thick layers of unconsolidated deposits in the flood plain of the Okanogan River. Based on available geologic information compiled from drillers' logs, a surficial geologic map, and streamflow records, the extensive and thick deposits of unconsolidated material in the Tunk and Bonaparte Creek subbasins are factors in sustaining the almost perennial streamflow in those creeks. The less extensive and generally thinner unconsolidated deposits in the Tonasket and Antoine subbasins are contributing factors to the occasional extended periods of zero flow (a dry stream channel) in those creeks. Even though groundwater withdrawals would affect streamflows, relatively low precipitation in the area, along with limited groundwater storage capacity and the presence of permeable, unconsolidated deposits underlying the stream channels, would likely lead to loss of surface water to the groundwater system without any withdrawals.

ISOTOPIC EVIDENCE FOR NATURALLY OCCURRING SULFATE PONDS IN THE KANKAKEE RIVER BASIN, ILLINOIS-INDIANA

EPA Science Inventory

Design of constructed wetlands in the Kankakee watershed, Indiana, include pumping and distribution ditches leaving former channelized river levees intact. Resultant changes in shallow ground water - surface water interactions may be contributing elevated sulfate to wetland ponds...

Numerical studies of the KP line-solitons

NASA Astrophysics Data System (ADS)

Chakravarty, S.; McDowell, T.; Osborne, M.

2017-03-01

The Kadomtsev-Petviashvili (KP) equation admits a class of solitary wave solutions localized along distinct rays in the xy-plane, called the line-solitons, which describe the interaction of shallow water waves on a flat surface. These wave interactions have been observed on long, flat beaches, as well as have been recreated in laboratory experiments. In this paper, the line-solitons are investigated via direct numerical simulations of the KP equation, and the interactions of the evolved solitary wave patterns are studied. The objective is to obtain greater insight into solitary wave interactions in shallow water and to determine the extent the KP equation is a good model in describing these nonlinear interactions.

Effects of surface wettability and contact time on protein adhesion to biomaterial surfaces

PubMed Central

Xu, Li-Chong; Siedlecki, Christopher A.

2013-01-01

Atomic force microscopy (AFM) was used to directly measure the adhesion forces between three test proteins and low density polyethylene (LDPE) surfaces treated by glow discharge plasma to yield various levels of water wettability. The adhesion of proteins to the LDPE substrates showed a step dependence on the wettability of surfaces as measured by the water contact angle (θ). For LDPE surfaces with θ > ∼60–65°, stronger adhesion forces were observed for bovine serum albumin, fibrinogen and human FXII than for the surfaces with θ < 60°. Smaller adhesion forces were observed for FXII than for the other two proteins on all surfaces although trends were identical. Increasing the contact time from 0 to 50 s for each protein–surface combination increased the adhesion force regardless of surface wettability. Time varying adhesion data was fit to an exponential model and free energies of protein unfolding were calculated. This data, viewed in light of previously published studies, suggests a 2-step model of protein denaturation, an early stage on the order of seconds to minutes where the outer surface of the protein interacts with the substrate and a second stage involving movement of hydrophobic amino acids from the protein core to the protein/surface interface. Impact statement The work described in this manuscript shows a stark transition between protein adherent and protein non-adherent materials in the range of water contact angles 60–65°, consistent with known changes in protein adsorption and activity. Time-dependent changes in adhesion force were used to calculate unfolding energies relating to protein–surface interactions. This analysis provides justification for a 2-step model of protein denaturation on surfaces. PMID:17466368

Comparison of a Conceptual Groundwater Model and Physically Based Groundwater Mode

NASA Astrophysics Data System (ADS)

Yang, J.; Zammit, C.; Griffiths, J.; Moore, C.; Woods, R. A.

2017-12-01

Groundwater is a vital resource for human activities including agricultural practice and urban water demand. Hydrologic modelling is an important way to study groundwater recharge, movement and discharge, and its response to both human activity and climate change. To understand the groundwater hydrologic processes nationally in New Zealand, we have developed a conceptually based groundwater flow model, which is fully integrated into a national surface-water model (TopNet), and able to simulate groundwater recharge, movement, and interaction with surface water. To demonstrate the capability of this groundwater model (TopNet-GW), we applied the model to an irrigated area with water shortage and pollution problems in the upper Ruamahanga catchment in Great Wellington Region, New Zealand, and compared its performance with a physically-based groundwater model (MODFLOW). The comparison includes river flow at flow gauging sites, and interaction between groundwater and river. Results showed that the TopNet-GW produced similar flow and groundwater interaction patterns as the MODFLOW model, but took less computation time. This shows the conceptually-based groundwater model has the potential to simulate national groundwater process, and could be used as a surrogate for the more physically based model.

Hyporheic flow and transport processes: mechanisms, models, and biogeochemical implications

USGS Publications Warehouse

Boano, Fulvio; Harvey, Judson W.; Marion, Andrea; Packman, Aaron I.; Revelli, Roberto; Ridolfi, Luca; Anders, Wörman

2014-01-01

Fifty years of hyporheic zone research have shown the important role played by the hyporheic zone as an interface between groundwater and surface waters. However, it is only in the last two decades that what began as an empirical science has become a mechanistic science devoted to modeling studies of the complex fluid dynamical and biogeochemical mechanisms occurring in the hyporheic zone. These efforts have led to the picture of surface-subsurface water interactions as regulators of the form and function of fluvial ecosystems. Rather than being isolated systems, surface water bodies continuously interact with the subsurface. Exploration of hyporheic zone processes has led to a new appreciation of their wide reaching consequences for water quality and stream ecology. Modern research aims toward a unified approach, in which processes occurring in the hyporheic zone are key elements for the appreciation, management, and restoration of the whole river environment. In this unifying context, this review summarizes results from modeling studies and field observations about flow and transport processes in the hyporheic zone and describes the theories proposed in hydrology and fluid dynamics developed to quantitatively model and predict the hyporheic transport of water, heat, and dissolved and suspended compounds from sediment grain scale up to the watershed scale. The implications of these processes for stream biogeochemistry and ecology are also discussed."

Hyporheic flow and transport processes: Mechanisms, models, and biogeochemical implications

NASA Astrophysics Data System (ADS)

Boano, F.; Harvey, J. W.; Marion, A.; Packman, A. I.; Revelli, R.; Ridolfi, L.; Wörman, A.

2014-12-01

Fifty years of hyporheic zone research have shown the important role played by the hyporheic zone as an interface between groundwater and surface waters. However, it is only in the last two decades that what began as an empirical science has become a mechanistic science devoted to modeling studies of the complex fluid dynamical and biogeochemical mechanisms occurring in the hyporheic zone. These efforts have led to the picture of surface-subsurface water interactions as regulators of the form and function of fluvial ecosystems. Rather than being isolated systems, surface water bodies continuously interact with the subsurface. Exploration of hyporheic zone processes has led to a new appreciation of their wide reaching consequences for water quality and stream ecology. Modern research aims toward a unified approach, in which processes occurring in the hyporheic zone are key elements for the appreciation, management, and restoration of the whole river environment. In this unifying context, this review summarizes results from modeling studies and field observations about flow and transport processes in the hyporheic zone and describes the theories proposed in hydrology and fluid dynamics developed to quantitatively model and predict the hyporheic transport of water, heat, and dissolved and suspended compounds from sediment grain scale up to the watershed scale. The implications of these processes for stream biogeochemistry and ecology are also discussed.

Endurance of larch forest ecosystems in eastern Siberia under warming trends

NASA Astrophysics Data System (ADS)

Sato, H.; Iwahana, G.; Ohta, T.

2015-12-01

The larch (Larix spp.) forest in eastern Siberia is the world's largest coniferous forest. However, its existence depends on near-surface permafrost, which increases water availability for trees, and the boundary of the forest closely follows the permafrost zone. Therefore, the degradation of near-surface permafrost due to forecasted warming trends during the 21st century is expected to affect the larch forest in Siberia. However, predictions of how warming trends will affect this forest vary greatly, and many uncertainties remain about land-atmospheric interactions within the ecosystem. We developed an integrated land surface model to analyze how the Siberian larch forest will react to current warming trends. This model analyzed interactions between vegetation dynamics and thermo-hydrology and showed that, under climatic conditions predicted by the Intergovernmental Panel on Climate Change (IPCC) Representative Concentration Pathway (RCP) scenarios 2.6 and 8.5, annual larch net primary production (NPP) increased about 2 and 3 times, respectively, by the end of 21st century compared with that in the 20th century. Soil water content during larch growing season showed no obvious trend, even after decay of surface permafrost and accompanying sub-surface runoff. A sensitivity test showed that the forecasted warming and pluvial trends extended leafing days of larches and reduced water shortages during the growing season, thereby increasing productivity.

Microplastics in Arctic polar waters: the first reported values of particles in surface and sub-surface samples

PubMed Central

Lusher, Amy L.; Tirelli, Valentina; O’Connor, Ian; Officer, Rick

2015-01-01

Plastic, as a form of marine litter, is found in varying quantities and sizes around the globe from surface waters to deep-sea sediments. Identifying patterns of microplastic distribution will benefit an understanding of the scale of their potential effect on the environment and organisms. As sea ice extent is reducing in the Arctic, heightened shipping and fishing activity may increase marine pollution in the area. Microplastics may enter the region following ocean transport and local input, although baseline contamination measurements are still required. Here we present the first study of microplastics in Arctic waters, south and southwest of Svalbard, Norway. Microplastics were found in surface (top 16 cm) and sub-surface (6 m depth) samples using two independent techniques. Origins and pathways bringing microplastic to the Arctic remain unclear. Particle composition (95% fibres) suggests they may either result from the breakdown of larger items (transported over large distances by prevailing currents, or derived from local vessel activity), or input in sewage and wastewater from coastal areas. Concurrent observations of high zooplankton abundance suggest a high probability for marine biota to encounter microplastics and a potential for trophic interactions. Further research is required to understand the effects of microplastic-biota interaction within this productive environment. PMID:26446348

Microplastics in Arctic polar waters: the first reported values of particles in surface and sub-surface samples

NASA Astrophysics Data System (ADS)

Lusher, Amy L.; Tirelli, Valentina; O'Connor, Ian; Officer, Rick

2015-10-01

Plastic, as a form of marine litter, is found in varying quantities and sizes around the globe from surface waters to deep-sea sediments. Identifying patterns of microplastic distribution will benefit an understanding of the scale of their potential effect on the environment and organisms. As sea ice extent is reducing in the Arctic, heightened shipping and fishing activity may increase marine pollution in the area. Microplastics may enter the region following ocean transport and local input, although baseline contamination measurements are still required. Here we present the first study of microplastics in Arctic waters, south and southwest of Svalbard, Norway. Microplastics were found in surface (top 16 cm) and sub-surface (6 m depth) samples using two independent techniques. Origins and pathways bringing microplastic to the Arctic remain unclear. Particle composition (95% fibres) suggests they may either result from the breakdown of larger items (transported over large distances by prevailing currents, or derived from local vessel activity), or input in sewage and wastewater from coastal areas. Concurrent observations of high zooplankton abundance suggest a high probability for marine biota to encounter microplastics and a potential for trophic interactions. Further research is required to understand the effects of microplastic-biota interaction within this productive environment.

Microplastics in Arctic polar waters: the first reported values of particles in surface and sub-surface samples.

PubMed

Lusher, Amy L; Tirelli, Valentina; O'Connor, Ian; Officer, Rick

2015-10-08

Plastic, as a form of marine litter, is found in varying quantities and sizes around the globe from surface waters to deep-sea sediments. Identifying patterns of microplastic distribution will benefit an understanding of the scale of their potential effect on the environment and organisms. As sea ice extent is reducing in the Arctic, heightened shipping and fishing activity may increase marine pollution in the area. Microplastics may enter the region following ocean transport and local input, although baseline contamination measurements are still required. Here we present the first study of microplastics in Arctic waters, south and southwest of Svalbard, Norway. Microplastics were found in surface (top 16 cm) and sub-surface (6 m depth) samples using two independent techniques. Origins and pathways bringing microplastic to the Arctic remain unclear. Particle composition (95% fibres) suggests they may either result from the breakdown of larger items (transported over large distances by prevailing currents, or derived from local vessel activity), or input in sewage and wastewater from coastal areas. Concurrent observations of high zooplankton abundance suggest a high probability for marine biota to encounter microplastics and a potential for trophic interactions. Further research is required to understand the effects of microplastic-biota interaction within this productive environment.

Ab initio study on the dynamics of furfural at the liquid-solid interfaces

NASA Astrophysics Data System (ADS)

Dang, Hongli; Xue, Wenhua; Shields, Darwin; Liu, Yingdi; Jentoft, Friederike; Resasco, Daniel; Wang, Sanwu

2013-03-01

Catalytic biomass conversion sometimes occurs at the liquid-solid interfaces. We report ab initio molecular dynamics simulations at finite temperatures for the catalytic reactions involving furfural at the water-Pd and water-Cu interfaces. We found that, during the dynamic process, the furan ring of furfural prefers to be parallel to the Pd surface and the aldehyde group tends to be away from the Pd surface. On the other hand, at the water-Cu(111) interface, furfural prefers to be tilted to the Cu surface while the aldehyde group is bonded to the surface. In both cases, interaction of liquid water and furfural is identified. The difference of dynamic process of furfural at the two interfaces suggests different catalytic reaction mechanisms for the conversion of furfural, consistent with the experimental investigations. Supported by DOE (DE-SC0004600). Simulations and calculations were performed on XSED's and NERSC's supercomputers

Two-dimensional wetting: the role of atomic steps on the nucleation of thin water films on BaF2(111) at ambient conditions.

PubMed

Cardellach, M; Verdaguer, A; Santiso, J; Fraxedas, J

2010-06-21

The interaction of water with freshly cleaved BaF(2)(111) surfaces at ambient conditions (room temperature and under controlled humidity) has been studied using scanning force microscopy in different operation modes. The images strongly suggest a high surface diffusion of water molecules on the surface indicated by the accumulation of water at step edges forming two-dimensional bilayered structures. Steps running along the 110 crystallographic directions show a high degree of hydrophilicity, as evidenced by small step-film contact angles, while steps running along other directions exhibiting a higher degree of kinks surprisingly behave in a quite opposite way. Our results prove that morphological defects such as steps can be crucial in improving two-dimensional monolayer wetting and stabilization of multilayer grown on surfaces that show good lattice mismatch with hexagonal ice.

Molecular simulations of heterogeneous ice nucleation. II. Peeling back the layers.

PubMed

Cox, Stephen J; Kathmann, Shawn M; Slater, Ben; Michaelides, Angelos

2015-05-14

Coarse grained molecular dynamics simulations are presented in which the sensitivity of the ice nucleation rate to the hydrophilicity of a graphene nanoflake is investigated. We find that an optimal interaction strength for promoting ice nucleation exists, which coincides with that found previously for a face centered cubic (111) surface. We further investigate the role that the layering of interfacial water plays in heterogeneous ice nucleation and demonstrate that the extent of layering is not a good indicator of ice nucleating ability for all surfaces. Our results suggest that to be an efficient ice nucleating agent, a surface should not bind water too strongly if it is able to accommodate high coverages of water.

Movement of fine particles on an air bubble surface studied using high-speed video microscopy.

PubMed

Nguyen, Anh V; Evans, Geoffrey M

2004-05-01

A CCD high-speed video microscopy system operating at 1000 frames per second was used to obtain direct quantitative measurements of the trajectories of fine glass spheres on the surface of air bubbles. The glass spheres were rendered hydrophobic by a methylation process. Rupture of the intervening water film between a hydrophobic particle and an air bubble with the consequent formation of a three-phase contact was observed. The bubble-particle sliding attachment interaction is not satisfactorily described by the available theories. Surface forces had little effect on the particle sliding with a water film, which ruptured probably due to the submicrometer-sized gas bubbles existing at the hydrophobic particle-water interface.

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

Many times the start up of granular activated carbon adsorption systems for the control of organic contaminants in wastewater cm exhibit unacceptable increases in the adscurber effluent pH. Experience shows that the duration of the pH increase ranges from several hours to several days, during which time several hundred bed volumes of water can be discharged with a pH in excess of 9. Laboratory studies have identified the cause of the pH rise as an interaction between the naturally occurring anions and protons ar the water and the carbon surface. The interaction can be described as an ion exchange typemore » of phenomenon, in which the carbon surface sorbs the anions and corresponding hydronium ions from the water. Capacities of the carbon for the anions range from 2 to 9 mg/g GAC, depending upon the water characteristics, the carbon type, the nature of the anion and its influent concentration. These studies have shown de the anion sorption and resulting pH increase is independent of the raw material used for die activated carbon production, e.g. bituminous or sub-bituminous coal, peat, wood or coconut. Also, the pH excursions occur with virgin, reactivated, and acid washed granular carbons. Current pH control technologies focus on adjustment of wastewater pH prior to discharge or recycle of the initial effluent water until the pH increase abates. However, improved water pH control options have been realized by altering the carbon surface rather than the water chemistry. The change to the carbon surface is accomplished through a controlled oxidation process. This process provides a more acidic carbon surface with a reduced affinity for the anions in the waste water. As a result, the pH excursions above 9 are eliminated and the initial effluent from the adsorption system can be discharged without further treatment.« less

Modification of land-atmosphere interactions by CO2 effects

NASA Astrophysics Data System (ADS)

Lemordant, Leo; Gentine, Pierre

2017-04-01

Plant stomata couple the energy, water and carbon cycles. Increased CO2 modifies the seasonality of the water cycle through stomatal regulation and increased leaf area. As a result, the water saved during the growing season through higher water use efficiency mitigates summer dryness and the impact of potential heat waves. Land-atmosphere interactions and CO2 fertilization together synergistically contribute to increased summer transpiration. This, in turn, alters the surface energy budget and decreases sensible heat flux, mitigating air temperature rise. Accurate representation of the response to higher CO2 levels, and of the coupling between the carbon and water cycles are therefore critical to forecasting seasonal climate, water cycle dynamics and to enhance the accuracy of extreme event prediction under future climate.

78 FR 52148 - Takes of Marine Mammals Incidental to Specified Activities; Taking Marine Mammals Incidental to a...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-08-22

... (Richardson et al., 1995): Wind and waves: The complex interactions between wind and water surface, including... interaction with these species is likely to be within the narrow sliver of ensonified area expected to extend... greater potential for interaction during the calving season we considered available density information...

Assessing the influence of climate change and inter-basin water diversion on Haihe River basin, eastern China: a coupled model approach

NASA Astrophysics Data System (ADS)

Xia, Jun; Wang, Qiang; Zhang, Xiang; Wang, Rui; She, Dunxian

2018-04-01

The modeling of changes in surface water and groundwater in the areas of inter-basin water diversion projects is quite difficult because surface water and groundwater models are run separately most of the time and the lack of sufficient data limits the application of complex surface-water/groundwater coupling models based on physical laws, especially for developing countries. In this study, a distributed surface-water and groundwater coupling model, named the distributed time variant gain model-groundwater model (DTVGM-GWM), was used to assess the influence of climate change and inter-basin water diversion on a watershed hydrological cycle. The DTVGM-GWM model can reflect the interaction processes of surface water and groundwater at basin scale. The model was applied to the Haihe River Basin (HRB) in eastern China. The possible influences of climate change and the South-to-North Water Diversion Project (SNWDP) on surface water and groundwater in the HRB were analyzed under various scenarios. The results showed that the newly constructed model DTVGM-GWM can reasonably simulate the surface and river runoff, and describe the spatiotemporal distribution characteristics of groundwater level, groundwater storage and phreatic recharge. The prediction results under different scenarios showed a decline in annual groundwater exploitation and also runoff in the HRB, while an increase of groundwater storage and groundwater level after the SNWDP's operation. Additionally, as the project also addresses future scenarios, a slight increase is predicted in the actual evapotranspiration, soil water content and phreatic recharge. This study provides valuable insights for developing sustainable groundwater management options for the HRB.

The interfacial energetics of the oil molecules interactions with shale media using molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Zhang, Z.; Wang, J.

2017-12-01

Characterizing the behavior of oil molecules in nanopore is vital to the understanding of geochemistry of hydrocarbon-bearing fluid in ultra-tight source rocks, such as shale. The heterogeneous nature of hydrocarbon system of nanoscale complicates experimental studies of oil / shale interfacial interaction. Therefore, to gain mechanistic understanding of the interplay of oil molecules in rock nanopore, molecular dynamics simulations have been applied to study the interactions of polar and non-polar oil on both calcite and kerogen surfaces. The effect of surface wetting, oil polarity, and temperature on the Gibbs free energy of adsorption have been investigated. The free energy, entropy, and enthalpy profiles have been calculated using advanced molecular dynamics method: umbrella sampling. In agreement with experiment, 1) surface with adsorbed water layer significantly reduces the oil adsorption energy on kerogen and turns the calcite surface to highly oil-repellent; 2) polar oil has overall stronger adsorption free energy than that of non-polar oil on both non-wetted calcite and kerogen surface; 3) organic interface (e.g. kerogen) exhibits stronger adsorption of oil molecules compared to inorganic one (e.g. calcite). The finding of this study indicates that oil displacement in nanopores can be enhanced by promoting the water adsorption on surface and reducing the polarity of oil on both inorganic and organic interfaces.

Coupled land surface/hydrologic/atmospheric models

NASA Technical Reports Server (NTRS)

Pielke, Roger; Steyaert, Lou; Arritt, Ray; Lahtakia, Mercedes; Smith, Chris; Ziegler, Conrad; Soong, Su Tzai; Avissar, Roni; Wetzel, Peter; Sellers, Piers

1993-01-01

The topics covered include the following: prototype land cover characteristics data base for the conterminous United States; surface evapotranspiration effects on cumulus convection and implications for mesoscale models; the use of complex treatment of surface hydrology and thermodynamics within a mesoscale model and some related issues; initialization of soil-water content for regional-scale atmospheric prediction models; impact of surface properties on dryline and MCS evolution; a numerical simulation of heavy precipitation over the complex topography of California; representing mesoscale fluxes induced by landscape discontinuities in global climate models; emphasizing the role of subgrid-scale heterogeneity in surface-air interaction; and problems with modeling and measuring biosphere-atmosphere exchanges of energy, water, and carbon on large scales.

Defect-induced wetting on BaF 2(111) and CaF 2(111) at ambient conditions

NASA Astrophysics Data System (ADS)

Cardellach, M.; Verdaguer, A.; Fraxedas, J.

2011-12-01

The interaction of water with freshly cleaved (111) surfaces of isostructural BaF2 and CaF2 single crystals at ambient conditions (room temperature and under controlled humidity) has been studied using scanning force microscopy in different operation modes and optical microscopy. Such surfaces exhibit contrasting behaviors for both materials: while on BaF2(111) two-dimensional water layers are formed after accumulation at step edges, CaF2(111) does not promote the formation of such layers. We attribute such opposed behavior to lattice match (mismatch) between hexagonal water ice and the hexagonal (111) surfaces of BaF2(CaF2). Optical microscope images reveal that this behavior also determines the way the surfaces become wetted at a macroscopic level.

Effects of salinity and the extent of water on supercritical CO2-induced phlogopite dissolution and secondary mineral formation.

PubMed

Shao, Hongbo; Ray, Jessica R; Jun, Young-Shin

2011-02-15

To ensure the viability of geologic CO2 sequestration (GCS), we need a holistic understanding of reactions at supercritical CO2 (scCO2)-saline water-rock interfaces and the environmental factors affecting these interactions. This research investigated the effects of salinity and the extent of water on the dissolution and surface morphological changes of phlogopite [KMg2.87Si3.07Al1.23O10(F,OH)2], a model clay mineral in potential GCS sites. Salinity enhanced the dissolution of phlogopite and affected the location, shape, size, and phase of secondary minerals. In low salinity solutions, nanoscale particles of secondary minerals formed much faster, and there were more nanoparticles than in high salinity solutions. The effect of water extent was investigated by comparing scCO2-H2O(g)-phlogopite and scCO2-H2O(l)-phlogopite interactions. Experimental results suggested that the presence of a thin water film adsorbed on the phlogopite surface caused the formation of dissolution pits and a surface coating of secondary mineral phases that could change the physical properties of rocks. These results provide new information for understanding reactions at scCO2-saline water-rock interfaces in deep saline aquifers and will help design secure and environmentally sustainable CO2 sequestration projects.

Accelerated evaporation of water on graphene oxide.

PubMed

Wan, Rongzheng; Shi, Guosheng

2017-03-29

Using molecular dynamics simulations, we show that the evaporation of nanoscale volumes of water on patterned graphene oxide is faster than that on homogeneous graphene oxide. The evaporation rate of water is insensitive to variation in the oxidation degree of the oxidized regions, so long as the water film is only distributed on the oxidized regions. The evaporation rate drops when the water film spreads onto the unoxidized regions. Further analysis showed that varying the oxidation degree observably changed the interaction between the outmost water molecules and the solid surface, but the total interaction for the outmost water molecules only changed a very limited amount due to the correspondingly regulated water-water interaction when the water film is only distributed on the oxidized regions. When the oxidation degree is too low and some unoxidized regions are also covered by the water film, the thickness of the water film decreases, which extends the lifetime of the hydrogen bonds for the outmost water molecules and lowers the evaporation rate of the water. The insensitivity of water evaporation to the oxidation degree indicates that we only need to control the scale of the unoxidized and oxidized regions for graphene oxide to regulate the evaporation of nanoscale volumes of water.

HYDRAULIC ANALYSIS ON STREAM-AQUIFER INTERACTION BY STORAGE FUNCTION MODELS

EPA Science Inventory

In the natural hydrologic cycle, surface and subsurface water in a watershed are closely related and interact with each other. However, their relatrionships are affected by human activities. For instance, as the impervious area of a basin spreads due to urbanization, rainfall r...

Contributions of nanoscale roughness to anomalous colloid retention and stability behavior

USDA-ARS?s Scientific Manuscript database

Expressions were presented to determine the mean interaction energy between a colloid and a solid-water interface (SWI), as well as for colloid-colloid interactions, when both surfaces contain binary nanoscale roughness and chemical heterogeneity. The influence of heterogeneity type, roughness para...

Molecular insight into nanoscale water films dewetting on modified silica surfaces.

PubMed

Zhang, Jun; Li, Wen; Yan, Youguo; Wang, Yefei; Liu, Bing; Shen, Yue; Chen, Haixiang; Liu, Liang

2015-01-07

In this work, molecular dynamics simulations are adopted to investigate the microscopic dewetting mechanism of nanoscale water films on methylated silica surfaces. The simulation results show that the dewetting process is divided into two stages: the appearance of dry patches and the quick contraction of the water film. First, the appearance of dry patches is due to the fluctuation in the film thickness originating from capillary wave instability. Second, for the fast contraction of water film, the unsaturated electrostatic and hydrogen bond interactions among water molecules are the driving forces, which induce the quick contraction of the water film. Finally, the effect of film thickness on water films dewetting is studied. Research results suggest that upon increasing the water film thickness from 6 to 8 Å, the final dewetting patterns experience separate droplets and striation-shaped structures, respectively. But upon further increasing the water film thickness, the water film is stable and there are no dry patches. The microscopic dewetting behaviors of water films on methylated silica surfaces discussed here are helpful in understanding many phenomena in scientific and industrial processes better.

Prediction of Protein-Protein Interaction Sites Using Electrostatic Desolvation Profiles

PubMed Central

Fiorucci, Sébastien; Zacharias, Martin

2010-01-01

Abstract Protein-protein complex formation involves removal of water from the interface region. Surface regions with a small free energy penalty for water removal or desolvation may correspond to preferred interaction sites. A method to calculate the electrostatic free energy of placing a neutral low-dielectric probe at various protein surface positions has been designed and applied to characterize putative interaction sites. Based on solutions of the finite-difference Poisson equation, this method also includes long-range electrostatic contributions and the protein solvent boundary shape in contrast to accessible-surface-area-based solvation energies. Calculations on a large set of proteins indicate that in many cases (>90%), the known binding site overlaps with one of the six regions of lowest electrostatic desolvation penalty (overlap with the lowest desolvation region for 48% of proteins). Since the onset of electrostatic desolvation occurs even before direct protein-protein contact formation, it may help guide proteins toward the binding region in the final stage of complex formation. It is interesting that the probe desolvation properties associated with residue types were found to depend to some degree on whether the residue was outside of or part of a binding site. The probe desolvation penalty was on average smaller if the residue was part of a binding site compared to other surface locations. Applications to several antigen-antibody complexes demonstrated that the approach might be useful not only to predict protein interaction sites in general but to map potential antigenic epitopes on protein surfaces. PMID:20441756

Global modeling of withdrawal, allocation and consumptive use of surface water and groundwater resources

NASA Astrophysics Data System (ADS)

Wada, Y.; Wisser, D.; Bierkens, M. F. P.

2014-01-01

To sustain growing food demand and increasing standard of living, global water withdrawal and consumptive water use have been increasing rapidly. To analyze the human perturbation on water resources consistently over large scales, a number of macro-scale hydrological models (MHMs) have been developed in recent decades. However, few models consider the interaction between terrestrial water fluxes, and human activities and associated water use, and even fewer models distinguish water use from surface water and groundwater resources. Here, we couple a global water demand model with a global hydrological model and dynamically simulate daily water withdrawal and consumptive water use over the period 1979-2010, using two re-analysis products: ERA-Interim and MERRA. We explicitly take into account the mutual feedback between supply and demand, and implement a newly developed water allocation scheme to distinguish surface water and groundwater use. Moreover, we include a new irrigation scheme, which works dynamically with a daily surface and soil water balance, and incorporate the newly available extensive Global Reservoir and Dams data set (GRanD). Simulated surface water and groundwater withdrawals generally show good agreement with reported national and subnational statistics. The results show a consistent increase in both surface water and groundwater use worldwide, with a more rapid increase in groundwater use since the 1990s. Human impacts on terrestrial water storage (TWS) signals are evident, altering the seasonal and interannual variability. This alteration is particularly large over heavily regulated basins such as the Colorado and the Columbia, and over the major irrigated basins such as the Mississippi, the Indus, and the Ganges. Including human water use and associated reservoir operations generally improves the correlation of simulated TWS anomalies with those of the GRACE observations.

Global Modeling of Withdrawal, Allocation and Consumptive Use of Surface Water and Groundwater Resources

NASA Astrophysics Data System (ADS)

Wada, Y.; Wisser, D.; Bierkens, M. F.

2014-12-01

To sustain growing food demand and increasing standard of living, global water withdrawal and consumptive water use have been increasing rapidly. To analyze the human perturbation on water resources consistently over large scales, a number of macro-scale hydrological models (MHMs) have been developed in recent decades. However, few models consider the interaction between terrestrial water fluxes, and human activities and associated water use, and even fewer models distinguish water use from surface water and groundwater resources. Here, we couple a global water demand model with a global hydrological model and dynamically simulate daily water withdrawal and consumptive water use over the period 1979-2010, using two re-analysis products: ERA-Interim and MERRA. We explicitly take into account the mutual feedback between supply and demand, and implement a newly developed water allocation scheme to distinguish surface water and groundwater use. Moreover, we include a new irrigation scheme, which works dynamically with a daily surface and soil water balance, and incorporate the newly available extensive global reservoir data set (GRanD). Simulated surface water and groundwater withdrawals generally show good agreement with reported national and sub-national statistics. The results show a consistent increase in both surface water and groundwater use worldwide, with a more rapid increase in groundwater use since the 1990s. Human impacts on terrestrial water storage (TWS) signals are evident, altering the seasonal and inter-annual variability. This alteration is particularly large over heavily regulated basins such as the Colorado and the Columbia, and over the major irrigated basins such as the Mississippi, the Indus, and the Ganges. Including human water use and associated reservoir operations generally improves the correlation of simulated TWS anomalies with those of the GRACE observations.

Variations in surface water-ground water interactions along a headwater mountain stream: comparisons between transient storage and water balance analyses

Treesearch

Adam S. Ward; Robert A. Payn; Michael N. Gooseff; Brian L. McGlynn; Kenneth E. Bencala; Christa A. Kellecher; Steven M. Wondzell; Thorsten Wagener

2013-01-01

The accumulation of discharge along a stream valley is frequently assumed to be the primary control on solute transport processes. Relationships of both increasing and decreasing transient storage, and decreased gross losses of stream water have been reported with increasing discharge; however, we have yet to validate these relationships with extensive field study. We...

Non-interacting surface solvation and dynamics in protein-protein interactions.

PubMed

Visscher, Koen M; Kastritis, Panagiotis L; Bonvin, Alexandre M J J

2015-03-01

Protein-protein interactions control a plethora of cellular processes, including cell proliferation, differentiation, apoptosis, and signal transduction. Understanding how and why proteins interact will inevitably lead to novel structure-based drug design methods, as well as design of de novo binders with preferred interaction properties. At a structural and molecular level, interface and rim regions are not enough to fully account for the energetics of protein-protein binding, even for simple lock-and-key rigid binders. As we have recently shown, properties of the global surface might also play a role in protein-protein interactions. Here, we report on molecular dynamics simulations performed to understand solvent effects on protein-protein surfaces. We compare properties of the interface, rim, and non-interacting surface regions for five different complexes and their free components. Interface and rim residues become, as expected, less mobile upon complexation. However, non-interacting surface appears more flexible in the complex. Fluctuations of polar residues are always lower compared with charged ones, independent of the protein state. Further, stable water molecules are often observed around polar residues, in contrast to charged ones. Our analysis reveals that (a) upon complexation, the non-interacting surface can have a direct entropic compensation for the lower interface and rim entropy and (b) the mobility of the first hydration layer, which is linked to the stability of the protein-protein complex, is influenced by the local chemical properties of the surface. These findings corroborate previous hypotheses on the role of the hydration layer in shielding protein-protein complexes from unintended protein-protein interactions. © 2014 Wiley Periodicals, Inc.

Copper-silver ionization at a US hospital: interaction of treated drinking water with plumbing materials, aesthetics and other considerations

EPA Science Inventory

Tap water sampling and surface analysis of copper pipe/bathroom porcelain were performed to explore the fate of copper and silver during the first nine months of copper-silver ionization (CSI) applied to cold and hot water at a hospital in Cincinnati, Ohio. Ions dosed by CSI into...

The Amateur Scientist: Funny Things Happen When Drops of Oil or Other Substances Are Placed on Water.

ERIC Educational Resources Information Center

Walker, Jearl

1983-01-01

Discusses solubility interactions of various oils placed on the surface of water and other liquids, explained using the basic forces of gravity, electrical attraction, and quantum mechanics (non-mathematical). Hydrogen and ionic bonding between oleic acid/water is analyzed. An experiment to determine physical properties of the oleic acid molecule…

Spatially variable stage-driven groundwater-surface water interaction inferred from time-frequency analysis of distributed temperature sensing data

USGS Publications Warehouse

Mwakanyamale, Kisa; Slater, Lee; Day-Lewis, Frederick D.; Elwaseif, Mehrez; Johnson, Carole D.

2012-01-01

Characterization of groundwater-surface water exchange is essential for improving understanding of contaminant transport between aquifers and rivers. Fiber-optic distributed temperature sensing (FODTS) provides rich spatiotemporal datasets for quantitative and qualitative analysis of groundwater-surface water exchange. We demonstrate how time-frequency analysis of FODTS and synchronous river stage time series from the Columbia River adjacent to the Hanford 300-Area, Richland, Washington, provides spatial information on the strength of stage-driven exchange of uranium contaminated groundwater in response to subsurface heterogeneity. Although used in previous studies, the stage-temperature correlation coefficient proved an unreliable indicator of the stage-driven forcing on groundwater discharge in the presence of other factors influencing river water temperature. In contrast, S-transform analysis of the stage and FODTS data definitively identifies the spatial distribution of discharge zones and provided information on the dominant forcing periods (≥2 d) of the complex dam operations driving stage fluctuations and hence groundwater-surface water exchange at the 300-Area.

Interaction of monovalent ions with the water liquid-vapor interface - A molecular dynamics study

NASA Technical Reports Server (NTRS)

Wilson, Michael A.; Pohorille, Andrew

1991-01-01

Results of molecular dynamics calculations are presented for a series of ions at infinite dilution near the water liquid-vapor interface. The free energies of ion transfer from the bulk to the interface are discussed, as are the accompanying changes of water structure at the surface and ion mobilities as a function of their proximity to the interface. It is shown that simple dielectric models do not provide an accurate description of ions at the water surface. The results of the study should be useful in the development of better models incorporating the shape and molecular structure of the interface.

Self-assembly of silica nanoparticles by tuning substrate-adsorbate interaction

NASA Astrophysics Data System (ADS)

Utsav, Khanna, Sakshum; Mukhopadhayay, Indrajit; Banerjee, Rupak

2018-05-01

We report on self-assembled nanodisc formations of silica nanoparticles on a surface modified silicon substrate using modified Langmuir-Schafer deposition technique (stamping). The size, inter-particle separation as well as the packing of the silica nanoparticles within the nanodiscs formed spontaneously can be tuned by the surface pressure applied on the water surface. We obtain self-assembled nanodiscs of silica nanoparticle arranged in a hexagonal symmetry. We also observe that by varying the surface pressure of deposition at the water-molecule-air interface we obtain such 2D disc-shaped structure with varying sizes and a packing ratio of the silica nanoparticle.

Comparison of the fouling release properties of hydrophobic fluorinated and hydrophilic PEGylated block copolymer surfaces: attachment strength of the diatom Navicula and the green alga Ulva.

PubMed

Krishnan, Sitaraman; Wang, Nick; Ober, Christopher K; Finlay, John A; Callow, Maureen E; Callow, James A; Hexemer, Alexander; Sohn, Karen E; Kramer, Edward J; Fischer, Daniel A

2006-05-01

To understand the role of surface wettability in adhesion of cells, the attachment of two different marine algae was studied on hydrophobic and hydrophilic polymer surfaces. Adhesion of cells of the diatom Navicula and sporelings (young plants) of the green macroalga Ulva to an underwater surface is mainly by interactions between the surface and the adhesive exopolymers, which the cells secrete upon settlement and during subsequent colonization and growth. Two types of block copolymers, one with poly(ethylene glycol) side-chains and the other with liquid crystalline, fluorinated side-chains, were used to prepare the hydrophilic and hydrophobic surfaces, respectively. The formation of a liquid crystalline smectic phase in the latter inhibited molecular reorganization at the surface, which is generally an issue when a highly hydrophobic surface is in contact with water. The adhesion strength was assessed by the fraction of settled cells (Navicula) or biomass (Ulva) that detached from the surface in a water flow channel with a wall shear stress of 53 Pa. The two species exhibited opposite adhesion behavior on the same sets of surfaces. While Navicula cells released more easily from hydrophilic surfaces, Ulva sporelings showed higher removal from hydrophobic surfaces. This highlights the importance of differences in cell-surface interactions in determining the strength of adhesion of cells to substrates.

Molecular dynamics simulations of low-ordered alzheimer β-amyloid oligomers from dimer to hexamer on self-assembled monolayers.

PubMed

Zhao, Jun; Wang, Qiuming; Liang, Guizhao; Zheng, Jie

2011-12-20

Accumulation of small soluble oligomers of amyloid-β (Aβ) in the human brain is thought to play an important pathological role in Alzheimer's disease. The interaction of these Aβ oligomers with cell membrane and other artificial surfaces is important for the understanding of Aβ aggregation and toxicity mechanisms. Here, we present a series of exploratory molecular dynamics (MD) simulations to study the early adsorption and conformational change of Aβ oligomers from dimer to hexamer on three different self-assembled monolayers (SAMs) terminated with CH(3), OH, and COOH groups. Within the time scale of MD simulations, the conformation, orientation, and adsorption of Aβ oligomers on the SAMs is determined by complex interplay among the size of Aβ oligomers, the surface chemistry of the SAMs, and the structure and dynamics of interfacial waters. Energetic analysis of Aβ adsorption on the SAMs reveals that Aβ adsorption on the SAMs is a net outcome of different competitions between dominant hydrophobic Aβ-CH(3)-SAM interactions and weak CH(3)-SAM-water interactions, between dominant electrostatic Aβ-COOH-SAM interactions and strong COOH-SAM-water interactions, and between comparable hydrophobic and electrostatic Aβ-OH-SAM interactions and strong OH-SAM-water interactions. Atomic force microscopy images also confirm that all of three SAMs can induce the adsorption and polymerization of Aβ oligomers. Structural analysis of Aβ oligomers on the SAMs shows a dramatic increase in structural stability and β-sheet content from dimer to trimer, suggesting that Aβ trimer could act as seeds for Aβ polymerization on the SAMs. This work provides atomic-level understanding of Aβ peptides at interface. © 2011 American Chemical Society

Hydrological modeling of upper Indus Basin and assessment of deltaic ecology

USDA-ARS?s Scientific Manuscript database

Managing water resources is mostly required at watershed scale where the complex hydrology processes and interactions linking land surface, climatic factors and human activities can be studied. Geographical Information System based watershed model; Soil and Water Assessment Tool (SWAT) is applied f...

Oxygen isotope fractionation effects in soil water via interaction with cations (Mg, Ca, K, Na) adsorbed to phyllosilicate clay minerals

NASA Astrophysics Data System (ADS)

Oerter, Erik; Finstad, Kari; Schaefer, Justin; Goldsmith, Gregory R.; Dawson, Todd; Amundson, Ronald

2014-07-01

In isotope-enabled hydrology, soil and vadose zone sediments have been generally considered to be isotopically inert with respect to the water they host. This is inconsistent with knowledge that clay particles possessing an electronegative surface charge and resulting cation exchange capacity (CEC) interact with a wide range of solutes which, in the absence of clays, have been shown to exhibit δ18O isotope effects that vary in relation to the ionic strength of the solutions. To investigate the isotope effects caused by high CEC clays in mineral-water systems, we created a series of monominerallic-water mixtures at gravimetric water contents ranging from 5% to 32%, consisting of pure deionized water of known isotopic composition with homoionic (Mg, Ca, Na, K) montmorillonite. Similar mixtures were also created with quartz to determine the isotope effect of non-, or very minimally-, charged mineral surfaces. The δ18O value of the water in these monominerallic soil analogs was then measured by isotope ratio mass spectrometry (IRMS) after direct headspace CO2 equilibration. Mg- and Ca-exchanged homoionic montmorillonite depleted measured δ18O values up to 1.55‰ relative to pure water at 5% water content, declining to 0.49‰ depletion at 30% water content. K-montmorillonite enriched measured δ18O values up to 0.86‰ at 5% water content, declining to 0.11‰ enrichment at 30% water. Na-montmorillonite produces no measureable isotope effect. The isotope effects observed in these experiments may be present in natural, high-clay soils and sediments. These findings have relevance to the interpretation of results of direct CO2-water equilibration approaches to the measurement of the δ18O value of soil water. The adsorbed cation isotope effect may bear consideration in studies of pedogenic carbonate, plant-soil water use and soil-atmosphere interaction. Finally, the observed isotope effects may prove useful as molecular scale probes of the nature of mineral-water interactions.

Dynamic interaction of CO/H 2O mixtures with gold nanocrystals: Real-time imaging and local chemical probing

NASA Astrophysics Data System (ADS)

Visart de Bocarmé, Thierry; Chau, Thoi-Dai; Kruse, Norbert

2006-09-01

The dynamic interaction of pure gold nanocrystals ("tips") with H 2O/CO gas mixtures was studied by means of video-field ion microscopy (FIM). While imaging with nano-scale resolution selected areas of the equivalent of ˜200 atomic Au sites were analysed for their chemical composition using short field pulses and injecting respective ions into a time-of-flight mass spectrometer (pulsed field desorption mass spectrometry, PFDMS). At room temperature the exposure of a clean Au sample to water gas at 10 -4 Pa, in the presence of an electric field of ˜10 V/nm, led to water adsorption and formation of bright patterns in FIM. Additional exposure to CO gas at 5 × 10 -3 Pa led to the removal of the water layer. This was associated with the occurrence of bright wave fronts which ignited simultaneously in several regions of the Au surface with no preference for a certain crystallographic surface plane. In some cases wave fronts were seen to collide resulting in more complicated patterns such as concentric rings. Surface areas free of water appeared with low brightness. The phenomena were completely reversible. PFDMS demonstrated water ions to be responsible for image formation. Surface hydroxyl was also detected mass spectrometrically and respective ion intensities decreased during the titration with CO. The results suggest that gold nanocrystals, in the absence of oxidic support materials, may be active in the reaction between water and CO at temperatures as low as 300 K and in the presence of an electric field of ˜10 V/nm.

A Stochastic Multi-Media Model of Microbial Transport in Watersheds

NASA Astrophysics Data System (ADS)

Yeghiazarian, L.; Safwat, A.; Whiteaker, T.; Teklitz, A.; Nietch, C.; Maidment, D. R.; Best, E. P.

2012-12-01

Fecal contamination is the leading cause of surface-water impairment in the US, and fecal pathogens are capable of triggering massive outbreaks of gastrointestinal disease. The difficulty in prediction of water contamination has its roots in the stochastic variability of fecal pathogens in the environment, and in the complexity of microbial dynamics and interactions on the soil surface and in water. To address these challenges, we have developed a stochastic model whereby the transport of microorganisms in watersheds is considered in two broad categories: microorganisms that are attached to mineral or organic substrates in suspended sediment; and unattached microorganisms suspended in overland flow. The interactions of microorganisms with soil particles on the soil surface and in the overland flow lead to transitions of microorganisms between solid and aqueous media. The strength of attachment of microorganisms to soil particles is determined by the chemical characteristics of soils which are highly correlated with the particle size. The particle size class distribution in the suspended sediment is predicted by the Water Erosion Prediction Project (WEPP). The model is integrated with ArcGIS, resulting in a general transport-modeling framework applicable to a variety of biological and chemical surface water contaminants. Simulations are carried out for a case study of contaminant transport in the East Fork Little Miami River Watershed in Ohio. Model results include the spatial probability distribution of microbes in the watershed and can be used for assessment of (1) mechanisms dominating microbial transport, and (2) time and location of highest likelihood of microbial occurrence, thus yielding information on best water sampling strategies.

Dynamic Kinetics of Nitrogen Cycle in Groundwater-Surface Water Interaction Zone at Hanford Site

NASA Astrophysics Data System (ADS)

Liu, Y.; Liu, C.; Liu, Y.; Xu, F.; Yan, A.; Shi, L.; Zachara, J. M.; Gao, Y.; Qian, W.; Nelson, W.; Fredrickson, J.; Zhong, L.; Thompson, C.

2015-12-01

Nitrogen cycle carried out by microbes is an important geobiological process that has global implications for carbon and nitrogen cycling and climate change. This presentation describes a study of nitrogen cycle in groundwater-surface water interaction zone (GSIZ) at the US Department of Energy's Hanford Site. Groundwater at Hanford sites has long been documented with nitrate contamination. Nearby Columbia River stage changes of up to 3 m every day because of daily discharge fluctuation from upstream Priest Rapids Dam; resulting an exchange of groundwater and surface water in a short time period. Yet, nitrogen cycle in the GSIZ at Hanford Site remains unclear. Column studies have been used to identify nitrogen metabolism pathways and investigate kinetics of nitrogen cycle in groundwater saturated zone, surface water saturated zone, and GSIZ. Functional gene and protein abundances were determined by qPCR and PRISM-SRM (high-pressure, high-resolution separations coupled with intelligent selection and multiplexing for sensitive selected reaction monitoring) to identify key enzymatic reactions and metabolic pathways of nitrogen cycle. The results showed that dissimilatory nitrate reduction to ammonium (DNRA) competed with denitrification under anaerobic conditions, reducing 30% of NO3- to NH4+, a cation strongly retained on the sediments. As dissolved oxygen intruded the anaerobic zone with river water, NH4+ was oxidized to NO3-, increasing the mobility of NO3-. Multiplicative Monod models were established to describe nitrogen cycle in columns fed with O2 depleted synthetic groundwater and O2 saturated synthetic river water, respectively. The two models were then coupled to predict the dynamic kinetics of nitrogen cycle in GSIZ.

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

2016-07-07

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.

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

DOE PAGES

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

2016-07-23

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. In this paper, 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 localmore » 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 Mo 132-based SEPs are more polar than Mo 72V 30 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 Mo 132 and Mo 72V 30 SEPs, respectively, indicating a strong propensity for the fluid surface. Finally, the influence of intermolecular interactions on the surface adsorption energies is discussed.« less

Contamination risk and drinking water protection for a large-scale managed aquifer recharge site in a semi-arid karst region, Jordan

NASA Astrophysics Data System (ADS)

Xanke, Julian; Liesch, Tanja; Goeppert, Nadine; Klinger, Jochen; Gassen, Niklas; Goldscheider, Nico

2017-09-01

Karst aquifers in semi-arid regions are particularly threatened by surface contamination, especially during winter seasons when extremely variable rainfall of high intensities prevails. An additional challenge is posed when managed recharge of storm water is applied, since karst aquifers display a high spatial variability of hydraulic properties. In these cases, adapted protection concepts are required to address the interaction of surface water and groundwater. In this study a combined protection approach for the surface catchment of the managed aquifer recharge site at the Wala reservoir in Jordan and the downstream Hidan wellfield, which are both subject to frequent bacteriological contamination, is developed. The variability of groundwater quality was evaluated by correlating contamination events to rainfall, and to recharge from the reservoir. Both trigger increased wadi flow downstream of the reservoir by surface runoff generation and groundwater seepage, respectively. A tracer test verified the major pathway of the surface flow into the underground by infiltrating from pools along Wadi Wala. An intrinsic karst vulnerability and risk map was adapted to the regional characteristics and developed to account for the catchment separation by the Wala Dam and the interaction of surface water and groundwater. Implementation of the proposed protection zones for the wellfield and the reservoir is highly recommended, since the results suggest an extreme contamination risk resulting from livestock farming, arable agriculture and human occupation along the wadi. The applied methods can be transferred to other managed aquifer recharge sites in similar karstic environments of semi-arid regions.

Quantifying groundwater dependency of riparian surface hydrologic features using the exit gradient

EPA Science Inventory

This study examines groundwater exit gradients as a way to quantify groundwater interactions with surface water. We calibrated high resolution groundwater models for the basin fill sediments in the lower Calapooia watershed, Oregon, using data collected between 1928--2000. The e...

Structure and dynamics of protein waters revealed by radiolysis and mass spectrometry

PubMed Central

Gupta, Sayan; D’Mello, Rhijuta; Chance, Mark R.

2012-01-01

Water is critical for the structure, stability, and functions of macromolecules. Diffraction and NMR studies have revealed structure and dynamics of bound waters at atomic resolution. However, localizing the sites and measuring the dynamics of bound waters, particularly on timescales relevant to catalysis and macromolecular assembly, is quite challenging. Here we demonstrate two techniques: first, temperature-dependent radiolytic hydroxyl radical labeling with a mass spectrometry (MS)-based readout to identify sites of bulk and bound water interactions with surface and internal residue side chains, and second, H218O radiolytic exchange coupled MS to measure the millisecond dynamics of bound water interactions with various internal residue side chains. Through an application of the methods to cytochrome c and ubiquitin, we identify sites of water binding and measure the millisecond dynamics of bound waters in protein crevices. As these MS-based techniques are very sensitive and not protein size limited, they promise to provide unique insights into protein–water interactions and water dynamics for both small and large proteins and their complexes. PMID:22927377

Effect of colloidal particleson the foamability and stabilization of aqueous foams by cationic surfactant CTAB

NASA Astrophysics Data System (ADS)

Cao, Huiying; Chen, Jiayi; Cai, Jie; Li, Yapin

2017-12-01

Colloidal particles can influence the foamability and stabilization of aqueous foam by addition of surfactant at the air-water interface. This occurs because particles are activated via the interaction with surfactant and are adsorbed onto the surfaces of foams. This phenomenon has been applied extensively to the development of new materials and techniques. Whether particle surface can be activated or not is decided by the interaction between the surfactant and the particle. In this work, we studied the effects of cationic surfactant CTAB (cetyltrimethylammonium bromide) on PS (polystyrene), SiO2, and TiO2 particles in aqueous solution, and compared the difference in their surface activation according to foam volume of the particles/CTAB/water system, and the degrees of foamability and foam stabilization. In addition, the influence of anionic surfactant SDS (sodium dodecyl sulfate) on the surface activation of PS in aqueous solution was also analyzed and compared with that of CTAB.

Morphology and the Strength of Intermolecular Contact in Protein Crystals

NASA Technical Reports Server (NTRS)

Matsuura, Yoshiki; Chernov, Alexander A.

2002-01-01

The strengths of intermolecular contacts (macrobonds) in four lysozyme crystals were estimated based on the strengths of individual intermolecular interatomic interaction pairs. The periodic bond chain of these macrobonds accounts for the morphology of protein crystals as shown previously. Further in this paper, the surface area of contact, polar coordinate representation of contact site, Coulombic contribution on the macrobond strength, and the surface energy of the crystal have been evaluated. Comparing location of intermolecular contacts in different polymorphic crystal modifications, we show that these contacts can form a wide variety of patches on the molecular surface. The patches are located practically everywhere on this surface except for the concave active site. The contacts frequently include water molecules, with specific intermolecular hydrogen-bonds on the background of non-specific attractive interactions. The strengths of macrobonds are also compared to those of other protein complex systems. Making use of the contact strengths and taking into account bond hydration we also estimated crystal-water interfacial energies for different crystal faces.

Theoretical study of adsorption of nitrogen-containing environmental contaminants on kaolinite surfaces.

PubMed

Scott, Andrea Michalkova; Burns, Elizabeth A; Hill, Frances C

2014-08-01

The adsorption of nitrogen-containing compounds (NCCs) including 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), 2,4-dinitroanisole (DNAN), and 3-nitro-1,2,4-triazol-5-one (NTO) on kaolinite surfaces was investigated. The M06-2X and M06-2X-D3 density functionals were applied with the cluster approximation. Several different positions of NCCs relative to the adsorption sites of kaolinite were examined, including NCCs in perpendicular and parallel orientation toward both surface models of kaolinite. The binding between the target molecules and kaolinite surfaces was analyzed and bond energies were calculated applying the atoms in molecules (AIM) method. All NCCs were found to prefer a parallel orientation toward both kaolinite surfaces, and were bound more strongly to the octahedral than to the tetrahedral site. TNT exhibited the strongest interaction with the octahedral surface and DNAN with the tetrahedral surface of kaolinite. Hydrogen bonding was shown to be the dominant non-covalent interaction for NCCs interacting with the octahedral surface of kaolinite with a small stabilizing effect of dispersion interactions. In the case of adsorption on the tetrahedral surface, kaolonite-NCC binding was shown to be governed by the balance between hydrogen bonds and dispersion forces. The presence of water as a solvent leads to a significant decrease in the adsorption strength for all studied NCCs interacting with both kaolinite surfaces.

Kinetic modeling of streamer penetration into de-ionized water

NASA Astrophysics Data System (ADS)

Levko, Dmitry; Sharma, Ashish; Raja, Laxminarayan L.

2018-03-01

Interest in plasma-liquid interaction phenomena has grown in recent years due to applications in plasma medicine, water purification, and plasma-hydrocarbon reforming. The plasma in contact with liquid is generated, for example, using the plasma jets or streamer discharges. The interaction between the streamer and water can cause both physical and chemical modifications of the liquid. In this paper, the interaction between an anode-directed streamer and the de-ionized water is studied using one-dimensional particle-in-cell Monte Carlo collisions model. In this model, plasma species in both gas and liquid phase are considered as the macro-particles. We find that the penetration of the streamer head into the liquid causes ionization of water molecules by electron impact, a process which is usually ignored in the fluid models. The main charge carriers in the liquid phase are negative water ions which agree with earlier experimental and computational modeling studies. Additionally, we observe an ion-rich sheath in the vicinity of the water surface on the gas side.

Changing Groundwater-Surface Water Interactions Impact Stream Chemistry and Ecology at the Arctic-Boreal Transition in Western Alaska

NASA Astrophysics Data System (ADS)

Koch, J. C.; Carey, M.; O'Donnell, J.; Sjoberg, Y.; Zimmerman, C. E.

2016-12-01

The arctic-boreal transition zone of Alaska is experiencing rapid change related to unprecedented warming and subsequent loss of permafrost. These changes in turn may affect groundwater-surface water (GW-SW) interactions, biogeochemical cycling, and ecosystem processes. While recent field and modeling studies have improved our understanding of hydrology in watersheds underlain by thawing permafrost, little is known about how these hydrologic shifts will impact bottom-up controls on stream food webs. To address this uncertainty, we are using an integrative experimental design to link GW-SW interactions to stream biogeochemistry and biota in 10 first-order streams in northwest Alaska. These study streams drain watersheds that span several gradients, including elevation, aspect, and vegetation (tundra vs. forest). We have developed a robust, multi-disciplinary data set to characterize GW-SW interactions and to mechanistically link GW-SW dynamics to water quality and the stream ecosystem. Data includes soil hydrology and chemistry; stream discharge, temperature, and inflow rates; water chemistry (including water isotopes, major ions, carbon concentration and isotopes, nutrients and chlorophyll-a), and invertebrate and fish communities. Stream recession curves indicate a decreasing rate later in the summer in some streams, consistent with seasonal thaw in lower elevation and south-facing catchments. Base cation and water isotope chemistry display similar impacts of seasonal thaw and also suggest the dominance of groundwater in many streams. Coupled with estimates of GW-SW exchange at point, reach, and catchment scales, these results will be used to predict how hydrology and water quality are likely to impact fish habitat and growth given continued warming at the arctic-boreal transition.

Surface water and groundwater interactions in coastal wetlands

NASA Astrophysics Data System (ADS)

Li, Ling; Xin, Pei; Shen, Chengji

2014-05-01

Salt marshes are an important wetland system in the upper intertidal zone, interfacing the land and coastal water. Dominated by salt-tolerant plants, these wetlands provide essential eco-environmental services for maintaining coastal biodiversity. They also act as sediment traps and help stabilize the coastline. While they play an active role in moderating greenhouse gas emissions, these wetlands have become increasingly vulnerable to the impact of global climate change. Salt marshes are a complex hydrological system characterized by strong, dynamic interactions between surface water and groundwater, which underpin the wetland's eco-functionality. Bordered with coastal water, the marsh system undergoes cycles of inundation and exposure driven by the tide. This leads to dynamic, complex pore-water flow and solute transport in the marsh soil. Pore-water circulations occur at different spatial and temporal scales with strong link to the marsh topography. These circulations control solute transport between the marsh soil and the tidal creek, and ultimately affect the overall nutrient exchange between the marsh and coastal water. The pore-water flows also dictate the soil aeration conditions, which in turn affect marsh plant growth. This talk presents results and findings from recent numerical and experimental studies, focusing on the pore-water flow behaviour in the marsh soil under the influence of tides and density-gradients.

Micropollutant sorption to membrane polymers: a review of mechanisms for estrogens.

PubMed

Schäfer, Andrea I; Akanyeti, Ime; Semião, Andrea J C

2011-05-11

Organic micropollutants such as estrogens occur in water in increasing quantities from predominantly anthropogenic sources. In water such micropollutants partition not only to surfaces such as membrane polymers but also to any other natural or treatment related surfaces. Such interactions are often observed as sorption in treatment processes and this phenomenon is exploited in activated carbon filtration, for example. Sorption is important for polymeric materials and this is used for the concentration of such micropollutants for analytical purposes in solid phase extraction. In membrane filtration the mechanism of micropollutant sorption is a relatively new discovery that was facilitated through new analytical techniques. This sorption plays an important role in micropollutant retention by membranes although mechanisms of interaction are to date not understood. This review is focused on sorption of estrogens on polymeric surfaces, specifically membrane polymers. Such sorption has been observed to a large extent with values of up to 1.2 ng/cm(2) measured. Sorption is dependent on the type of polymer, micropollutant characteristics, solution chemistry, membrane operating conditions as well as membrane morphology. Likely contributors to sorption are the surface roughness as well as the microporosity of such polymers. While retention-and/or reflection coefficient as well as solute to effective pore size ratio-controls the access of such micropollutants to the inner surface, pore size, porosity and thickness as well as morphology or shape of inner voids determines the available area for sorption. The interaction mechanisms are governed, most likely, by hydrophobic as well as solvation effects and interplay of molecular and supramolecular interactions such as hydrogen bonding, π-cation/anion interactions, π-π stacking, ion-dipole and dipole-dipole interactions, the extent of which is naturally dependent on micropollutant and polymer characteristics. Systematic investigations are required to identify and quantify both relative contributions and strength of such interactions and develop suitable surface characterisation tools. This is a difficult endeavour given the complexity of systems, the possibility of several interactions taking place simultaneously and the generally weaker forces involved. Copyright © 2010 Elsevier B.V. All rights reserved.

The influence of trehalose on hydrophobic interactions of small nonpolar solute: A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Paul, Subrata; Paul, Sandip

2013-07-01

Molecular dynamics simulations were carried out to investigate the influences of aqueous trehalose solution on the hydrophobic interactions between neopentane molecules. In this study, we consider six different trehalose concentrations ranging from 0% to 56%. We observe that with increasing trehalose concentration the dispersion of solute neopentane takes place. The neopentane-neopentane association constant value decreases with addition of trehalose. Our preferential interaction calculations suggest that with increasing trehalose concentration neopentane interacts preferentially with water over trehalose. Site-site neopentane-trehalose rdfs indicate that trehalose molecules are expelled out from the neopentane surface. Also observed are (i) trehalose induced second shell collapse of water network (ii) decrease in average number of water-water and water-trehalose hydrogen bonds with increasing trehalose concentration. We also find that addition of trehalose decreases the translational motion of all the solution species. The decrease in diffusion coefficient value is more pronounced for trehalose. We, further, observe that the ratio of the diffusion coefficient values of water and trehalose increases with increasing trehalose concentration.

Sticky ions in biological systems.

PubMed Central

Collins, K D

1995-01-01

Aqueous gel sieving chromatography on Sephadex G-10 of the Group IA cations (Li+, Na+, K+, Rb+, Cs+) plus NH4+ as the Cl- salts, in combination with previous results for the halide anions (F-, Cl-, Br-, I-) as the Na+ salts [Washabaugh, M.W. & Collins, K.D. (1986) J. Biol. Chem. 261, 12477-12485], leads to the following conclusions. (i) The small monovalent ions (Li+, Na+, F-) flow through the gel with water molecules attached, whereas the large monovalent ions (K+, Rb+, Cs+, Cl-, Br-, I-) adsorb to the nonpolar surface of the gel, a process requiring partial dehydration of the ion and implying that these ions bind the immediately adjacent water molecules weakly. (ii) The transition from strong to weak hydration occurs at a radius of about 1.78 A for the monovalent anions, compared with a radius of about 1.06 A for the monovalent cations (using ionic radii), indicating that the anions are more strongly hydrated than the cations for a given charge density. (iii) The anions show larger deviations from ideal behavior (an elution position corresponding to the anhydrous molecular weight) than do the cations and dominate the chromatographic behavior of the neutral salts. These results are interpreted to mean that weakly hydrated ions (chaotropes) are "pushed" onto weakly hydrated surfaces by strong water-water interactions and that the transition from strong ionic hydration to weak ionic hydration occurs where the strength of ion-water interactions approximately equals the strength of water-water interactions in bulk solution. PMID:7539920