Dissertations / Theses on the topic 'Surface Water'

Surface-water and groundwater are two resources both requiring careful management and protection. Computer modelling of both has long been used as an aid to their management. Historically they have been modelled separately, as their behaviour is represented by different mathematical equations. However, in reality, they are a linked resource each affects the other. DIVAST is a two-dimensional hydrodynamic and water quality numerical model developed for estuarine and coastal modelling. The original model enables the simulation of problems such as pollution and flooding in surface waters. In this study the existing model is extended to allow the modelling of groundwater as well as surface water in the same model. Chapters 1-5 introduce the problem, review some existing models, and then derive, discretise, and implement the equations for surface water and groundwater flow into the new model. Chapters 6-10 test the new model against analytical solutions, laboratory data, field data, and an existing groundwater model (MODFLOW). The outcome is a new version of the DIVAST model, known as DIVAST-SG (Depth Integrated Velocities And Solute Transport in Surface water and Groundwater). It simulates interactions between two-dimensional surface water and groundwater, in addition to the facilities of the original code. The equations are solved within one model, avoiding coupling problems. It is successfully tested against analytical solutions, laboratory studies and field data, and compared to an existing groundwater code, where it successfully models a gravel aquifer adjacent to tidal surface water. A framework is laid for continuing this work to produce a pseudo 3-D surface- water / groundwater code. In addition, novel techniques are pioneered in the laboratory, where open cell foam is used in a tidal flume to represent a porous aquifer adjacent to a river, and a highly detailed dataset of groundwater field data is compiled in the course of the work.

From the Proceedings of the 1991 Meetings of the Arizona Section - American Water Resources Association and the Hydrology Section - Arizona-Nevada Academy of Science - April 20, 1991, Northern Arizona University, Flagstaff, Arizona
Since the spring of 1988 the University of Arizona has conducted nanofiltration research. The major emphasis has been the treatment of both Colorado River Water and municipal effluent. The work has been sponsored by the John F. Long Foundation Inc. and the Consolidated Water Utilities, Phoenix Az. Nanofiltration is a low pressure form of reverse osmosis. It operates at about 1/3 the pressure and 3 times the flux rate of older brackish water reverse osmosis systems. This reduces both the cost as well as the operating costs to approximately 1 /10 of the older reverse osmosis systems. The City of Ft Myers is projecting costs as low as $0.50-0.60/1000 gallons for their 20 MGD plant. Nanofiltration treats water the way it needs to be treated to meet the Environmental Protection Agency's (EPA) present minimum contamination levels (MCL) as well as projected future levels. Nanofiltration removes most of the bivalent inorganic molecules such as calcium and magnesium as well as some monovalent molecules such as sodium and chloride. It also removes pathogens and dissolved organics, thus reducing the trihalomethane formation potential (THMFP). The research on recharged effluent municipal effluent below the 91st Avenue Plant in Phoenix has shown the value of nanofiltration for reclaiming municipal wastewater to potable standards. A 20,000 GPD slowsand /nanofiltration pilot plant at Apache Junction has shown the effectiveness of the treatment on Colorado River Water at a 95% recovery over the past 2 years.

Several methods for simulating a body of water and a water surface has been investigated. A method by Layton & van de Panne based on a simplification of the Navier-Stokes equations was selected. A number of simplifications was made to increase the performance of the method, and it was implemented on the programmable graphical processing unit (GPU) using the Jacobi method to solve the linear equations. A conjugate gradient solver was also implemented on the GPU. The performance of the methods were measured and recorded.

Thesis (M.S.)--University of North Carolina at Chapel Hill, 2006.
Title from electronic title page (viewed Oct. 10, 2007). "... in partial fulfillment of the requirements for the degree of Masters of Science in the Department of Environmental Sciences and Engineering." Discipline: Environmental Sciences and Engineering; Department/School: Public Health.

Paper presented at "Membranes For Drinking Water Treatment Conference", Environmental Protection Agency, Cincinnati, OH, August 6, 1990.
Introduction: Through the studies published in Drinking Water and Health (1977) the nation has become more aware of the carcinogenic nature of the byproducts of disinfection such as trihalomethanes. Trihalomethanes are formed when the disinfectant chlorine reacts with the precursors, humic and fluvic acids that are naturally occuring in all surface water. The Environmental Protection Agency (EPA) has set a minimum contaminent level of 100 ppb on THM's that many in the health agencies feel need to be lowered. The problem is that when the MCL's are lowered utilities will be enclined to chlorimines and chloride dioxide which have been found to be mutagenic. Drinking Water and Health (1987) found the Suggested No-Adverse Response Levels (SNARLs) for chioramines for a child is 0.166 ppm, for an adult it is 0.581. The SNARL for chlorine dioxide is 0.06 ppm for a child and 0.210 ppm for an adult. These levels for utilities are virtually impossible to maintain and still have a residual at the end of the system.

Thesis: S.M., Massachusetts Institute of Technology, Department of Mechanical Engineering, 2018.
Cataloged from PDF version of thesis.
Includes bibliographical references (pages 55-57).
Condensation is a ubiquitous process often observed in nature and our daily lives. The large amount of latent heat released during the condensation process has been harnessed in many industrial processes such as power generation, building heating and cooling, desalination, dew harvesting, thermal management, and refrigeration. Condensation has two modes: dropwise mode and filmwise mode. Although it has been known for decades that dropwise condensation outperforms filmwise condensation in heat transfer owing to the droplet shedding effects which can efficiently reduce thermal resistance, filmwise condensation still dominates industrial applications currently due to the high costs, low robustness and technical challenges of manufacturing dropwise coatings. During water condensation, dropwise mode can be readily promoted with thin hydrophobic coatings. Superhydrophobic surfaces made out of hydrophobic coatings on micro-or-nano-engineered surfaces have shown further heat transfer enhancement in dropwise condensation of water; however, the applications of these micro- or nanoscale structured surface designs have been restricted by the high manufacturing expenses and short range of subcooling limit. Recent studies have shown that the combination of millimeter sized geometric features and plain hydrophobic coatings can effectively manipulate droplet distribution of water condensate, which provides opportunities to locally facilitate dropwise condensation at relatively low manufacturing expenses as compared to those delicate micro- and nano-structured hydrophobic surfaces. Low surface tension fluids such as hydrocarbons pose a unique challenge to achieving dropwise condensation, because common hydrophobic coatings are not capable of repelling low surface tension fluids. Recent development in lubricant infused surfaces (LIS) offers promising solutions to achieving dropwise condensation of low surface tension fluids by replacing the solid-condensate interface in conventional hydrophobic coatings with a smooth lubricant-condensate interface. However, only a few experimental studies have applied LIS to promoting dropwise condensation of low surface tension fluids (y as low as 15 mN/m). In this work, we investigated dropwise condensation of both water (y ~ 72 mN/m) and a low surface tension fluid, namely butane (y - 13 mN/m) on structured surfaces. For water condensation, we studied the effects of millimeter sized geometric structures on dropwise condensation heat transfer under two different environments: pure vapor and an air-vapor mixture. Our experimental results show that, although convex structures enable faster droplet growth in an air-vapor mixture, the same structures impose the opposite effect during pure vapor condensation, hindering droplet growth. We developed a numerical model for each case to predict the heat flux distribution along the structured surface, and the model shows good agreement with experimental results. This work demonstrates that the effects of geometric features on dropwise condensation are not invariable but rather dependent on the scenario of resistances to heat and mass transfer in the system. For butane condensation, based on a design guideline we recently developed for lubricant infused surfaces, we successfully designed an energy-favorable combination of lubricant and structured solid substrate, which was further demonstrated to promote dropwise condensation of butane. The fundamental understanding of dropwise condensation of water and low surface tension fluids on structured surfaces developed in this study provides useful guidelines for condensation applications including power generation, desalination, dew harvesting, and thermal management.
by Yajing Zhao.
S.M.

Thesis (MEng)--Stellenbosch University, 2015.
ENGLISH ABSTRACT: The purpose of this study is to construct and test a surface tension driven water pump. The surface tension driven water pump is a passive water pump which uses a similar mechanism to that of trees to pump water. This study was conducted at the Department of Mechanical and Mechatronic Engineering at the University of Stellenbosch. For the study an extensive literature survey was done encompassing aspects such as water properties, surface tension (basic principles, capillary forces, temperature and contaminant effects, wettability), bubble formation (nucleation theory and tensile strength of water) and, finally water and mineral transport in trees (plant structures and mechanisms, limiting factors, misconceptions and organic substance transport). Previous work by botanists who demonstrate the transpiration mechanism needed for water transport in trees was also considered. The study further required the development of a theoretical thermal-hydraulic model to simulate the pumping performance for the surface tension driven water pump. The developed water pump was also experimentally tested with particular focus on design improvement, pumping performance, pump behaviour, potential pumping head as well as water collection capability. The experimental data was statistically analysed by multi-linear regression. Both the experimental data and statically generated predictions were compared to the theoretical thermal-hydraulic model. The results show that a working surface tension driven pump was constructed. Evaporation rates of up to 400 mL/hr.m2 were obtained, with pumping head heights reaching up to 1.8 m and a maximum pump functional lifespan of 13 days. The results further suggest that there is a good correlation between the various statistical fits and the experimental data. The developed theoretical thermal-hydraulic model was also found to be in good agreement with the experimental results. A sensitivity analysis of the theoretical and statistical models showed that the statistical models fairs poorly under extrapolation. Additionally, the mechanistic causes of pump failure as well as the effect of heat and pumping head on water pumping performance were identified. Thereafter, the water collection efficiency was established to be 98% on average. Further testing revealed that the pumping performance of larger area or multiple grouped “leaves” are less accurately predicted with the theoretical model than a single “leaf”. In conclusion, the results provide some support that the surface tension driven pump may be used as a water transport system in an artificial photosynthesis project, if the functional lifespan of the pump can be greatly improved. It is recommended that a more rigid hydrophilic material be used in the “leaf” interface and that multiple narrower conduits be used instead of a single larger pipe. Additional future work may include the development of pit-like structures to prevent air spreading throughout the system as well as a simple mechanism for evaporative control.
AFRIKAANSE OPSOMMING: Die doel van hierdie ondersoek is om 'n oppervlakspanning-aangedrewe waterpomp te bou en te toets. Die oppervlakspanning-aangedrewe waterpomp is ‘n passiewe waterpomp wat gebruik maak van ‘n meganisme soortgelyke aan dié van bome om water te pomp. Hierdie ondersoek is by die Departement Meganiese en Megatroniese Ingenieurswese by die Universiteit van Stellenbosch uitgevoer. Vir die ondersoek is 'n uitgebreide literatuurstudie gedoen wat aspekte soos water eienskappe, oppervlakspanning (basiese beginsels, kapillêre kragte, die uitwerking van temperatuur, onsuiwerhede asook benatbaarheid), lugborrelvorming (kernvormingsteorie en die treksterkte van water) en uiteindelik water- en mineraalvervoer in bome (plantstrukture en -meganismes, beperkende faktore, wanpersepsies en die vervoer van organiese stowwe) insluit. Vorige navoring deur plantkundiges, wat die watervervoermeganismes in bome demonstreer, is ook in ag geneem. Die ondersoek het die ontwikkeling van 'n teoretiese termies-hidrouliese model ingesluit, wat gebruik is om die oppervlakspanning-aangedrewe waterpomp se werking te voorspel. Die waterpomp is ook eksperimenteel getoets met die fokus op ontwerpverbetering, pompwerkverrigting, pompwerking, potensiële pompopvoerdrukhoogte sowel as die waterversamelingsvermoë. Die eksperimentele data is statisties ontleed deur middel van meervoudige liniêre regressie. Beide die eksperimentele data en statisties-gegenereerde voorspellings is vergelyk met die teoretiese termies-hidrouliese-model. Die resultate toon dat 'n werkende oppervlakspanning-aangedrewe pomp gebou is. ‘n Verdampingstempo van tot 400 mL/hr.m2, pompopvoerdrukhoogte van tot 1.8m en 'n maksimum funksionele pompleeftyd van 13 dae is bereik. Die resultate dui verder daarop dat daar 'n goeie korrelasie tussen die verskillende statistiese lynpassings en die eksperimentele data is. Die teoretiese termies-hidrouliese-model wat ontwikkel is, toon 'n goeie ooreenkoms met die eksperimentele resultate. 'n Sensitiwiteitsanalise van die teoretiese en statistiese modelle het getoon dat die statistiese modelle swak voorspellings maak as geëkstrapoleerde data gebruik word. Verder is die meganismes wat pompweiering veroorsaak, die effek van hitte asook die effek van pompopvoerdrukhoogte op die pomp se werkverrigting geïdentifiseer. Daarna is die doeltreffendheid van waterversamelingsvermoë vir die waterpomp vasgestel op gemiddeld 98%. Verdere toetse het getoon dat die pompwerkverrigting van groter gegroepeerde "blare" minder akkuraat met die teoretiese model voorspel word as vir 'n enkele "blaar". Ten slotte: Die resultate toon dat die oppervlakspanning-aangedrewe waterpomp as 'n water vervoer stelsel gebruik kan word in 'n kunsmatige fotosinteseprojek, indien die funksionele leeftyd van die pomp verbeter kan word. Dit word aanbeveel dat 'n sterker hidrofiliese materiaal in die "blaar"-koppelvlak gebruik word en dat verskeie nouer leipype gebruik word in plaas van 'n enkele groter pyp. Bykomende toekomstige werk kan die ontwikkeling van put-agtige strukture insluit wat die verspeiding van lug deur die hele stelsel voorkom, sowel as 'n eenvoudige meganisme wat die verdampingstempo beheer.

In this research water dispersed epoxy varnishes were produced by reacting solid epoxy resin with ethylene diamine (EDA) and maleinized fatty acids of linseed oil. Maleinized fatty acid (MFA) was produced by the maleinization process, in which, fatty acid and maleic anhydride were reacted under nitrogen atmosphere. Maleinization was performed in order to insert hydrophilic groups to the fatty acid chains, which were then inserted to the backbone of the epoxy resin. This was done to give water dispersibility to the hydrophobic epoxy resin. Solid epoxy resin was dissolved in 1,4-dioxane. Ethylene diamine was then added to the solution at 50°
C, and stirred for 4 hours. Then the temperature was increased to 80oC and kept for 2 hours. Maleinized fatty acids were then introduced, and the reaction was carried out at 90oC for 10 hours. 1,4-dioxane was used for the removal of the water, which forms as the byproduct. Then the driers were added. The carboxylic groups of the maleinized fatty acid were neutralized by morpholine and the product was dispersed in water. The varnish was applied on test panels and left for air-drying for 24 hours and then baked at 140°
C for 5 hours. The free epoxy content was determined by pyridinium-chloride titration and it was seen that all the epoxy groups reacted. Also, produced fatty acid was characterized by FTIR spectroscopy and maleinized fatty acid was characterized by H-NMR and FTIR spectroscopy. Hardness, bending, impact resistance, gloss, and abrasion resistance tests were carried out on hardened varnish specimens. The samples generally showed good mechanical and physical properties. While the baking time was increased the hardness of product increased. Samples showed superior impact resistance, gloss, and flexibility.

Nowadays, organic pollutants occurring in surface waters have raised substantial concern in public. Triclosan (TCS) is one of the antimicrobial agents which are utilized in both domestic and industrial application. In this study nanofiltration (NF) of TCS in surface water was investigated. Laboratory scale cross-flow device is operated in total recycle mode and DK-NF and DL-NF membranes were used. Kesikkö
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Reservoir (Ankara) water was used as raw water. Effect of natural organic matter (NOM) content of raw water on TCS removal is searched through addition of humic acid (HA) into the raw water as to represent for NOM. Steady state permeate fluxes are monitored throughout the experiments to explore the flux behavior of the membranes. During the experiments, performance of the membranes is assessed by monitoring TCS, as well as other water quality parameters, such as UVA254 and total organic carbon (TOC) in the feed and permeates waters. Results obtained put forward that TCS removal by NF membrane is not as same as reported in the literature. In the literature, membrane removal efficiency is reported as above 90%. However, this study proved that this would be true if and only if one does not considers the adsorption of TCS by the system itself, in the absence of membrane. It is now clear that, because of adsorption of the TCS onto the experimental set up (feed tank, pipings etc.)
the real TCS removal efficiency of the nanofiltration is around 60-70%.

Surface freezing transitions in mixed monolayers of a homologous series of cationic surfactants, the alkyltrimethyl ammonium bromides (CnTAB where n = 12, 14, 16, 18), as well as a range of non-ionic, zwitterionic and biological surfactants, have been investigated ellipsometrically with a range of n-alkanes (Cm where m = 12 – 20, 28). Two distinct solid phases are observed depending upon the chain length difference between surfactant and n-alkane. Type I solid phases consist of a surface frozen mixed monolayer and are formed when this difference is small. Type II solid phases are bilayer structures with a frozen layer of neat n-alkane above a liquid-like mixed monolayer. Type II freezing was thought to occur via wetting of surface frozen n-alkane, as previously reported type II transitions took place in the presence of surface frozen n-alkanes. Thermodynamically stable type II solid phases have now been found in the presence of n-alkanes that do not show surface freezing at the air/alkane interface, however, and so this picture is incomplete. In the presence of pentadecane, for example, the biological surfactant lyso-OPC forms a stable type II solid phase 6.5 °C above the n-alkane bulk melting point. Such a large surface freezing range is unprecedented for a type II system. Studies using external reflection FTIR (ER-FTIRS) and vibrational sum-frequency spectroscopies (VSFS) have been used to probe these novel behaviours. Results were fully consistent with the proposed structures of both type I and type II surface frozen layers. 2D correlation analysis of ER-FTIR spectra as a function of temperature showed that type II frozen layer formation does not proceed via a simple wetting transition, with the formation of a transient intermediate implied. Evidence for such an intermediate was provided by dynamic ellipsometry measurements on the type II C18TAB/n-eicosane system.

The main objective of this work, which was the synthesis of water-soluble polymers for scale formation inhibition on stainless steel surfaces, has been achieved. Following an introduction and discussion of the background of the work (Chapter 1), the synthesis and characterisation of various monomers, norbomenes with alkylene ether side chains terminated by trialkyl ammonium salts, is described (Chapter 2). These monomers were polymerised to give water-soluble materials, as described in Chapter 3. The nature of the polymers involved and the development of special techniques for their characterisation is explained in Chapter 4. The amphiphilic water-soluble polymers prepared were used as additives in a detergent solution for scale inhibition tests. The variation in the structures of the polymers prepared allowed the study of the effects of different factors on scale inhibition, including the molecular weights of the polymers, the lengths of the alkylene ether side chains, and the nature of the trialkyl ammonium salt functionality. Most of the materials synthesised had an inhibiting effect on scale formation on the stainless steel substrate, in that treated surfaces allowed an easier cleaning of the samples. This study allowed the identification of a polymer structure showing good properties for scale inhibition, which may provide a lead for future development.

COORDENAÇÃO DE APERFEIÇOAMENTO DO PESSOAL DE ENSINO SUPERIOR
CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO
A relação entre os processos hidrológicos de escoamento superficial e subterrâneo apresenta uma grande variabilidade espacial e temporal. Podendo ser representado de forma qualitativa como parte sequêncial do ciclo hidrológico, estes processos, demostram sua grande dependência e importância nos estudos de balanços hídricos. Visando uma representação quantitativa, este trabalho faz o acoplamento, entre os modelos numéricos de escoamento superficial e de fluxo em meios porosos. Para o meio poroso adotou-se o modelo numérico SWMS_3D (Simunek et al, 1995), o qual resolve a equação de Richards, para fluxo em meios porosos saturados e não saturados nas três dimensões. Na simulação da dinâmica superficial, foram desenvolvidos dois modelos derivados das equações de Saint- Venant: o modelo da Onda Cinemática e o modelo de Difusão. Para a solução numérica foi empregado o método dos elementos finitos através da formulaçao de Galerkin, adotando uma malha tridimensional de elementos tetraédricos, formando uma sub-malha de elementos triangulares na superfície. O modelo de escoamento superficial emprega a malha triangular e interage com o programa SWMS_3D modificado (que utiliza a malha de tetraédros) através das imposições das condições de contorno transientes. Este, responderá com uma parcela de fluxo correspondente à recarga ou descarga no contorno a cada passo de tempo. Com isso, o modelo gerado é capaz de quantificar espacialmente e temporalmente as cargas de pressão em todos os pontos do domínio de estudo.
While analyzing the interaction between the hydrological processes of surface and groundwater flow, it is seen that there is a big difference in its interaction in the space and time. These processes can be represented in a qualitative form as part of the hydrological cycle, demonstrating its dependences and importance in the hydrological balance. This work does the numerical coupling of the surface and groundwater flow. This work adopted the SWMS_3D numerical model (Simunek et. al., 1995), which resolves the Richards equation for saturated and non saturated porous media flow in 3D. In order to simulate the superficial dynamic flow, two models from Saint-Vennat equation were developed, these models are: the cinematic wave model and the diffusion model. These two models consider the average outflow in sections in a 2D scenario. For the numerical solution the finite element method was adopted through the Galerkin formulation. Adopting a 3D domain mesh of tetrahedral elements, seen from above, in 2D, we can see a triangular element mesh. The superficial flow model uses the triangular mesh and iterates with the SWMS_3D modified software, which uses the tetrahedral elements mesh. This was done by changes in the boundary conditions to the models. The SWMS_3D will answer with a flow portion corresponding to a sink or source action in the surface, in each time step. Finally the generated model is able to quantify in space and in time the pressure head in the study domain.

The thesis presents the development, implementation and results of two series of experiments, at large and small scale, for the study of surface gravity waves. A number of measurement techniques are developed and implemented to capture space and time evolution of waves on a water surface in gravity, gravity-capillary and capillary ranges with the purpose to study the statistics of wave turbulence in terms of frequency and wave number spectra. The first series of experiments was conducted in a large wave tank of size 12 m x 6 m x 1.6 m filled with water to a depth of 0.9 m. A wave maker comprised of eight panels is controlled by a computer to generate waves at typically two frequencies; these waves are directed at different angles. Surface elevation of the resulting turbulent wave field is measured via capacitance wire probes and a fluorescent laser technique that is capable of capturing wave profiles at sufficient frame rate to access both wavenumber and frequency statistics. Following the processing of these data a comprehensive set of results describe characteristics of the life cycle of the experiment including the rise of the wave field to its statistically stationary state and the decay of the regime after energy pumped into the system from the wave maker has ceased. The first series of experiments was conducted in a large wave tank of size 12 m x 6 m x 1.6 m filled with water to a depth of 0.9 m. A wave maker comprised of eight panels is controlled by a computer to generate waves at typically two frequencies; these waves are directed at different angles. Surface elevation of the resulting turbulent wave field is measured via capacitance wire probes and a fluorescent laser technique that is capable of capturing wave profiles at sufficient frame rate to access both wavenumber and frequency statistics. Following the processing of these data a comprehensive set of results describe characteristics of the life cycle of the experiment including the rise of the wave field to its statistically stationary state and the decay of the regime after energy pumped into the system from the wave maker has ceased. Across both series of experiments the implementation of data acquisition techniques forms a significant contribution to the work undertaken and a comprehensive set of tools for measurement and analysis of data from surface waves is developed.

Surface reactions occurring at solid-water interfaces in calcium mineral-ligands systems have been studied. Both hydrous apatite and fluorite surfaces show clear amphoteric properties. An ion exchange process between lattice ions of F- on fluorite and OH- ions in bulk solution is discovered. The surface adsorption of Alizarin Red S and sodium oleate are determined. Surface chemical reaction models are established based on acidbase potentiometric titrations, solubility, adsorption and zeta-potential measurements in 0. 1 mol dm-3 ionic media at 25'C. Experimental data are evaluated using the computer program FITEQL assuming a constance capacitance model for the electric double layer. Surface complexes identities are obtained from FT-IR, FT-Raman, and UV/visible spectroscopy studies. A series of surface equilibrium constants in the system are presented. The correlation between surface complex formation and mineral flotation is discussed.
Godkänd; 1994; 20070429 (ysko)

Implementation of quality of surface waters is important stage on which priorities are determined by water protection activities, the Organization of monitoring networks and water-planning activities. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/30169

High extraction mining techniques have produced the need to mitigate and understand ground movements associated with this technology.  Tools such as the Surface Deformation Prediction System (SDPS) facilitate sound scientific decision making in the industry and has continually improved since its inception in 1987.  The capabilities of SDPS have expanded on an as-needed basis.  Currently, the regulatory climate has emphasized the need to understand the impact of underground mining on surface waters, physically and chemically.

The SDPS program is used to conduct an analysis of ground movements to assess optimal barrier pillar size for stream protection.  Typical analytical and empirical methods used in mine planning were compared against SDPS methods to ensure the validity and advantage to the use of SDPS for this purpose.

Finally, underground mining effects on stream chemistry and health were explored by studying the heavily mined and industrialized watershed of Dumps Creek located in Russell County, Virginia.  This watershed has been identified as being impaired since the Virginia 303(d) List of Impaired Waters was created in 1994.  Currently, there are two pumps staged in the headwaters region of Dumps Creek that help to maintain water levels in an inactive underground mine.  The pumping is necessary to control methane levels that rising water could force into an active underground mine that lies stratigraphically above the inactive mine.  Water is pumped on an as-needed basis and discharges directly into Dumps Creek.  Historic measurements of stream conductivity and benthic health scores were compared to assess whether a correlation exists between the two measurements.  These measurements were compared based on regulatory decisions that emphasized that conductivity is a direct indicator of stream health in all watersheds.

Scientific contributions associated with this research include: Further developments in the use of SDPS programming in order to account for stream protection on a case by case basis for both mine panel and surface water protection by optimizing barrier pillar size in relation to a nearby stream; the analysis of available and currently obtained water chemistry data in a mining impacted watershed in attempt to further research to appropriately characterize and mitigate specific problems in order to improve stream health; and, assessment of the complexity of water chemistry impacts from underground mining as related to stream health indicators in different chemically dominated watersheds.

Master of Science

The town of Mosier, Oregon, is located near the east, dry end of the Columbia River Gorge, and the local area is known for cherry orchards that rely heavily on groundwater for irrigation. The CRBG groundwater system in Mosier has experienced groundwater declines of up to 60 meters due to over-pumping and or commingling. Declining groundwater levels have led to concerns over the sustainability of the resource, as it is the principle water source for irrigation and domestic use. Despite numerous previous studies of groundwater flow in CRBG aquifers here and elsewhere in the Columbia River basin, an aspect that has received relatively little attention is the interaction between groundwater and surface waters at locations where interflow zones are intersected by the surface waters. The objective of my research is to investigate how CRBG interflow zone exposures in Mosier Creek may be controlling groundwater elevations in the area. The methods used include: (1) geochemical analysis of well cuttings and detailed geologic mapping along area streams to identify interflow zones of individual CRBG flows, (2) analysis of stream discharge data and groundwater elevation data to confirm exchange of groundwater and surface waters, and (3) collection and analyses of 31 water samples from area wells, streams, and springs, to determine if waters from individual CRBG aquifers can be hydrochemically identified and to further constrain understanding of surface and groundwater interactions. My study confirms that the general elevation of the Pomona Member and Basalt of Lolo interflow zone creek exposure is coincident with the elevation where a change in slope of the decline trend in 2004 is seen in Mosier area well hydrographs. Furthermore, the results of stream discharge data indicated a close connection between drawdown from groundwater pumping during irrigation season and groundwater- surface water interaction. At the time of drawdown in the upper-most CRBG aquifer (Pomona), the stream transitions from gaining to losing water into the groundwater system. Elemental chemistry data indicates the Frenchman Springs Sentinel Gap aquifer waters are the most evolved waters in this study. Stable isotopic data reinforced this determination as the Sentinel Gap waters are the lightest, or most negative, with regard to δD and δ18O. Sentinel Gap samples were more depleted than other aquifer samples by 4.38 to 6.89 0/100 for δD and 0.39 to 0.59 0/100 for δ18O. The results of the general chemistry and isotope data reveal a more evolved chemical signature in lower watershed groundwater versus a less evolved signature for waters from wells located higher up on the Columbia Hills anticline. This was interpreted to be the result of the major structural features in the area providing for a more regional pathway of recharge in lower watershed groundwaters, versus a more local source of recharge for upper watershed groundwaters. There was also a pronounced commingled signature in the elemental ratios of lower watershed aquifer waters. The suspected mechanism of recharge to lower watershed wells is through younger Cascadian deposits upslope from the local watershed. The findings of this study reveal the importance of a detailed understanding of CRBG stratigraphy and its relation to surface waters, especially for other areas within the Yakima Fold Belt or Oregon and Washington. Studies that do not consider the influence that individual CRBG flows can have on groundwater-surface water interactions, and the groundwater system as a whole, run the risk of improperly assessing the groundwater resource for a region.

L'evidenza riconosciuta del riscaldamento globale richiede una valutazione del ciclo dell'acqua presente e futuro in Europa e nel mondo. Recentemente, è stata documentata l'evidenza di un regime idrologico modificato nelle Alpi sotto il cambiamento climatico. Tuttavia, secondo il quinto rapporto di valutazione dell'IPCC, è ancora necessario approfondire la nostra comprensione dell'impatto del cambiamento climatico e dell'uso del suolo sullo stoccaggio delle acque sotterranee nei bacini idrografici alpini. Una delle maggiori limitazioni all'analisi dell'interazione tra acque superficiali e sotterranee nei terreni alpini è la difficoltà di acquisizione dei dati e la limitata presenza di stazioni meteorologiche. Questi due fattori aumentano considerevolmente l'incertezza di una rappresentazione olistica dei processi idrologici e una stima affidabile della ricarica delle acque sotterranee. Lo scopo di questo lavoro di ricerca è quello di migliorare le attuali conoscenze sull'interazione tra le acque superficiali e gli acquiferi poco profondi e di definire un metodo per una modellazione integrata delle principali componenti del ciclo dell'acqua a scala di bacino da utilizzare come input per la modellazione delle acque sotterranee. La raccolta e l'uso di dati e metodi che permettono la massima discretizzazione dell'eterogeneità degli elementi coinvolti è il filo conduttore di questo lavoro. L'approccio scientifico è dimostrato per un caso di studio complesso, la valle della Valtellina (Italia settentrionale), per indagare l'interazione tra le componenti del ciclo idrogeologico e le loro proiezioni future secondo le dinamiche climatiche. Questa valle potrebbe essere considerata un perfetto caso di studio perché è caratterizzata da un sistema attivo che reagisce rapidamente alle variazioni meteorologiche e climatiche. Ciò è visibile dalla fluttuazione delle acque sotterranee e del fiume principale, l'Adda, durante eventi estremi di precipitazione e con lo scioglimento della neve durante i periodi di primavera/estate. La tesi è divisa in tre sezioni principali. La prima fornisce una descrizione dell'idrostratigrafia della pianura alluvionale della Valtellina. Questa sezione include il modello di flusso delle acque sotterranee in condizione stazionaria, sviluppato utilizzando FeFlow 7.2, e il relativo processo di calibrazione automatica della parametrizzazione idrogeologica. La seconda mostra la quantificazione del volume di stoccaggio stagionale delle acque sotterranee secondo il metodo del bilancio idrico residuo per due anni idrologici. Per la stima delle componenti principali (Precipitazione, Evapotraspirazione e Snow Water Equivalent), vengono testati nuovi promettenti database e metodi satellitari. L'ultimo capitolo descrive il modello di flusso transitorio delle acque sotterranee sviluppato con condizioni limite dinamiche ottenute dai metodi satellitari. Infine, il modello di flusso è stato utilizzato per valutare l'impatto sulle acque sotterranee di possibili scenari di cambiamento climatico.
The recognized evidence of global warming demands assessment of the present and future water cycle in Europe and worldwide. Recently, evidence of modified hydrological regime in the Alps under climate change has been documented. However, according to the IPCC Fifth Assessment Report, it is still necessary to deepen our understanding of the impact of climate change and land use on groundwater storage in the alpine catchment areas. A major limitation to the analysis of the surface water-groundwater interaction in alpine terrain are the difficultly of data acquisition as well as the limited presence of meteorological stations. These two factors considerably increase the uncertainty of a holistic representation of the hydrological processes and a reliable estimation of groundwater recharge. The aim of this research work is to improve the current knowledge on the interaction between surface water and shallow aquifers and to define a method for an integrated modelling of the main components of the water cycle at the catchment scale to be used as input for groundwater modelling. The collection and use of data and methods that allow for the maximum discretisation of the heterogeneity of the elements involved is the guiding thread of this work. The scientific approach is demonstrated for a complex case study, the Valtellina valley (northern Italy), to investigate the interaction among the components of hydrogeologic cycle and their future projections according to climate dynamics. This valley could be considered a perfect case study because it is characterized by an active system that rapidly reacts to meteorological and climatic variations. This is visible by the fluctuation of the groundwater and of the main river, Adda River, during extreme precipitation events and with snow melts during the spring/summer periods. The thesis is divided into three main sections. The first provides a description of hydro-stratigraphy of the Valtellina valley floodplain. This section includes the groundwater flow model in a steady state condition, developed by using FeFlow 7.2, and the relative automatic calibration process for the hydrogeologic parametrization. 5 The second shows the quantification of seasonal groundwater storage volume according to the residual water budget method for two hydrologic years. For the estimation of the main components (Precipitation, Evapotranspiration and Snow water equivalent), new promising satellite-based database and methods are tested. The last one describes the tranFinally, the flow model has been used to evaluate the impact on groundwater of possible climate change scenarios.sient groundwater flow model developed with dynamic boundary conditions obtained from satellite-based methods.

Thesis (M.S.)--Worcester Polytechnic Institute.
Keywords: Conductivity, pH, Dissolved Oxygen, UV absorbance, Source Water, Surface Water, Dissolved Organic Carbon, Total Organic Carbon, Particle Counts, Turbidity, E. coli, Fecal Coliforms, West Boylston Brook, Wachusett Reservoir, source water protection, surface water protection Includes bibliographical references (p.73-77).

Two of the most important environmental challenges in the 21st century are to protect the quality of fresh water resources and to utilize renewable energy sources to lower greenhouse gas emissions. This study contributes to the solution of the first challenge by providing methodologies for optimal design of real-time water quality monitoring systems and interpretation of data supplied by the monitoring system to identify potential pollution sources in river networks. In this study, the optimal river water quality monitoring network design aspect of the overall monitoring program is addressed by a novel methodology for the analysis of this problem. In this analysis, the locations of sampling sites are determined such that the contaminant detection time is minimized for the river network while achieving maximum reliability for the monitoring system performance. The data collected from these monitoring stations can be used to identify contamination source locations. This study suggests a methodology that utilizes a classification routine which associates the observations on a contaminant spill with one or more of the candidate spill locations in the river network. This approach consists of a training step followed by a sequential elimination of the candidate spill locations which lead to the identification of potential spill locations. In order to contribute the solution of the second environmental challenge, this study suggests utilizing available excess energy in water distribution systems by providing a methodology for optimal design of energy recovery systems. The energy recovery in water distribution systems is possible by using micro hydroelectric turbines to harvest available excess energy inevitably produced to satisfy consumer demands and to maintain adequate pressures. In this study, an optimization approach for the design of energy recovery systems in water distribution networks is proposed. This methodology is based on finding the best locations for micro hydroelectric plants in the network to recover the excess energy. Due to the unsteady nature of flow in water distribution networks, the proposed methodology also determines optimum operation schedules for the micro turbines.

Thesis advisor: Rudolph Hon
The application of road de-icers has lead to increasing solute concentrations in surface and ground water across the northern US, Canada, and northern Europe. In a public water supply well field in southeastern Massachusetts, USA, chloride concentrations in ground water from an unconfined aquifer have steadily risen for the past twenty years. The objectives of this study are to understand spatial and temporal trends in road salt concentrations in order to identify contamination sources and fate. To this end, the methods of this project include field and lab work. Water samples were collected from surface, near-surface, and ground water from March 2012 to March 2013. The other major field data are specific conductance measurements from probes located in three piezometers. In the lab, all samples were analyzed for major ions with ion chromatography analysis. Additionally, trace elements were measured by inductively coupled plasma analysis on a subset of samples. The results of these hydrogeochemical procedures showed several important trends. First, the highest concentrations of sodium and chloride from near-surface samples were located near to roadways. Second, ground water samples taken from glacial sediments contained relatively high concentrations throughout the water column, whereas ground water samples from wetlands had high concentrations only near the surface. Third, there was no clear relationship between pH and cation concentrations. Finally, specific conductance data showed strong seasonal trends near to the surface, whereas values taken from deeper in the aquifer were steadily increasing. Based on these results, it is highly probable that road salt application is the dominate contamination source. The pathways of road salt in the watershed include runoff into surface water and infiltration into the vadose zone and ground water. Road salt appears to preferentially travel through glacial features rather than floodplain features. It is possible that sodium from road salt is sorbed to aquifer sediment and displaces other cations. However, the low values of trace metals suggest that cation exchange is not mobilizing heavy metals. Finally, the increasing specific conductance values deep in the aquifer suggest that road salt is retained within the aquifer and concentrations will likely increase in the future if the current road salt application procedures are continued
Thesis (MS) — Boston College, 2013
Submitted to: Boston College. Graduate School of Arts and Sciences
Discipline: Earth and Environmental Sciences

Surface waters are increasingly polluted by the industries in Colombo, Sri Lanka. Among these the food and drink industries are prominent in urban Colombo. To understand the extent of pollution of the inland surface waters a project was undertaken in the San Sebastian canal, which runs through the heart of Colombo, and the connecting waterways. It entailed the chemical and physical monitoring of the surface waters and the waste water discharges of the industries. The results indicated that the San Sebastian canal was a highly polluted canal with a very low dissolved oxygen level. The oxygen sag was very marked at the industrial discharges. Most of the industries, by nature of the highly organic waste waters in addition to being untreated failed to meet the specified standards of discharges into inland surface waters. The rainfall-pollutant and the rainfall-lag analysis indicated the poor dilution of these strong waste waters, and the low assimilative capacity of the highly polluted canal system. Hence, the San Sebastian canal polluted the receiving river Kelani, into which it discharges in the east, and the Beira lake in the west, where the polluted waters are pumped from the canal to maintain the level of the lake.

Concern has arisen as to whether the lack of appropriate consideration to surface water in urban spatial planning is reducing our capacity to manage surface water flood risk. Appropriate tools are required that allow spatial planners to explore opportunities and solutions for surface water flooding at large spatial scales. An urban surface water balance model has been developed that screens large urban areas to identify flooded areas and which allows solutions to be explored. The model hypothesis is that key hydrological characteristics; storage volume and location, flow paths and surface water generation capture the key processes responsible for surface water flooding. The model uses a LiDAR DEM (Light Detection and Ranging Digital Elevation Model) as the basis for determining surface water accumulation in a catchment and has been developed so that it requires minimal inputs and computational resources. The urban surface water balance approach is applied to Keighley in West Yorkshire where several instances of surface water flooding have been reported. Data for validating surface water flood risk models is sparse because such flooding events are of short duration, very localized and distributed across the catchment. This research used a postal questionnaire, followed up with site visits to collect data on surface water flooding locations in Keighley. The validation exercise confirmed that the major processes responsible for flooding are largely well represented in the model for situations where interaction with the urban sewer network is well represented by the assumptions made in the model. A qualitative analysis based on field visits revealed that the degree of interaction with the sewer network varies spatially, and as the importance of the interaction of the sewer system increases, the accuracy of the model results are lowered. It also highlighted that local detail not present in the DEM, the presence of urban drainage assets and the performance of the sewer system, which are not be represented in the model, can determine the accuracy of model results. Model results were used as a basis to develop solutions to surface water flooding. A least cost path methodology was developed to identify managed flood routes as a solution. These were translated into model inputs in the form a modified DEM. It was shown that the simple and fast representation of flood routes and surface storage is of considerable benefit for scenario analysis.

In 1982, Israelachvili and Pashley reported the first measurements of a hitherto unknown attractive force between two mica surfaces hydrophobized in cetyltrimethylammonium bromide (CTAB) solutions. Follow-up experiments conducted by many investigators confirmed their results, while others suggested that the â hydrophobic forceâ is an artifact due to nanobubbles (or cavitation). Evidences for the latter included the discontinuities (or steps) in the force versus distance curves and the pancake-shaped nano-bubbles seen in atomic force microscopic (AFM) images. Recent measurements conducted in degassed water showed, however, smooth force versus distance curves, indicating that the hydrophobic force is not an artifact due to nanobubbles.1, 2 Still other investigators3, 4 suggested that the long-range attraction observed between hydrophobic surfaces is due to the correlation between the patches of adsorbed ionic surfactant and the patches of unoccupied surface. For this theory to work, it is necessary that the charged patches be laterally mobile to account for the strong attractive forces observed in experiment. In an effort to test this theory, AFM force measurements were conducted with gold substrates hydrophobized by self-assembly of alkanethiols and xanthates of different chain lengths. The results showed long-range attractions despite the fact that the hydrophobizing agents chemisorb on gold and, hence, the adsorption layer is immobile. When the gold surfaces were hydrophobized in a 1 à 10-3 M thiol-in-ethanol solution for an extended period of time, the force curves exhibited steps. These results indicate that the long-range attractions are caused by the coalescence of bubbles, as was also reported by Ederth.5 The steps disappeared, however, when the species adsorbed on top of the chemisorbed monolayer were removed by solvent washing, or when the gold substrates were hydrophobized in a 1 à 10-5 M solution for a relatively short period of time. AFM force measurements were also conducted between gold substrates coated with short-chain thiols and xanthates to obtain hydrophobic surfaces with water contact angles (ï ±) of less than 90o. Long-range attractions were still observed despite the fact that cavitation is thermodynamically not possible. Having shown that hydrophobic force is not due to coalescence of pre-existing bubbles, cavitation, or correlation of charged patches, the next set of force measurements was conducted in ethanol-water mixtures. The attractive forces became weaker and shorter-ranged than in pure water and pure ethanol. According to the Derjaguinâ s approximation6, an attractive force arises from the decrease in the excess free energy (ï §f) of the thin film between two hydrophobic surfaces.7 Thus, the stronger hydrophobic forces observed in pure water and pure ethanol can be attributed to the stronger cohesive energy of the liquid due to stronger H-bonding. Further, the increase in hydrophobic force with decreasing separation between two hydrophobic surfaces indicates that the H-bonded structure becomes stronger in the vicinity of hydrophobic surfaces. The force measurements conducted at different temperatures in the range of 10-40ºC showed that the hydrophobic attraction between macroscopic surfaces causes a decrease in film entropy (Sf), which confirms that the hydrophobic force is due to the structuring of water in the thin film between two hydrophobic surfaces. The results showed also that the hydrophobic interaction entails a reduction in the excess film enthalpy (Hf), which may be associated with the formation of partial (or full) clathrates formed in the vicinity of hydrophobic surfaces. The presence of the clathrates is supported by the recent finding that the density of water in the vicinity of hydrophobic surfaces is lower than in the bulk.8
Ph. D.

Thesis (Ph. D. - Chemical and Environmental Engineering)--University of Arizona, 2001.
We acknowledge that the writer has two page 7's in this resource. (List of figures). Includes bibliographical references (leaves 214-218).

The thesis consists of two parts. The first part discusses the initial value problem of a fifth-order Korteweg-de Vries type of equation w_t + w_xxx - w_xxxxx - ⁿ∑_j=1 a_jw^jw_x = 0, w(x, 0) = w₀(x) posed on a periodic domain x ∈ [0, 2π] with boundary conditions w_ix(0, t) = w_ix(2π, t), i = 0, 2, 3, 4 and an L²-stabilizing feedback control law w_x(2π, t) = αw_x(0, t) + (1 - α)w_xxx(0; t) where n is a fixed positive integer, a_j, j = 1, 2, ... n, α are real constants, and |α| < 1. It is shown that for w₀(x) ∈ H¹_α(0, 2π) with the boundary conditions described above, the problem is locally well-posed for w ∈ C([0, T]; H¹_α(0, 2π)) with a conserved volume of w, [w] = ∫^2π₀ w(x, t)dx. Moreover, the solution with small initial condition exists globally and approaches to [w₀(x)]/(2π) as t → + ∞. The second part concerns wave motions on water in a rectangular basin with a wave generator mounted on a side wall. The linear governing equations are used and it is assumed that the surface tension on the free surface is not zero. Two types of generators are considered, flexible and rigid. For the flexible case, it is shown that the system is exactly controllable. For the rigid case, the system is not exactly controllable in a finite-time interval. However, it is approximately controllable. The stability problem of the system with the rigid generator controlled by a static feedback is also studied and it is proved that the system is strongly stable for this case.
Ph. D.

Surface water and groundwater systems consist of interconnected reservoirs, rivers, and confined and unconfined aquifers. The integrated management of such resources faces several challenges: High dimensionality refers to the requirement of the large number of variables that need to be considered in the description of surface water and groundwater systems. As the number of these variables increases, the computational requirements quickly saturate the capabilities of the existing management methods. Uncertainty relates to the imprecise nature of many system inputs and parameters, including reservoir and tributary inflows, precipitation, evaporation, aquifer parameters (e.g., hydraulic conductivity and storage coefficient), and various boundary and initial conditions. Uncertainty complicates very significantly the development and application of efficient management models. Nonlinearity is intrinsic to some physical processes and also enters through various facility and operational constraints on reservoir storages, releases, and aquifer drawdown and pumping. Nonlinearities compound the previous difficulties. Multiple objectives pertain to the process of optimizing the use of the integrated surface and groundwater resources to meet various water demands, generate sufficient energy, maintain adequate instream flows, and protect the environment and the ecosystems. Multi-objective decision models and processes continue to challenge professional practice. This research draws on several disciplines including groundwater flow modeling, hydrology and water resources systems, uncertainty analysis, estimation theory, stochastic optimization of dynamical systems, and policy assessment. A summary of the research contributions made in this work follows: 1.High dimensionality issues related to groundwater aquifers system have been mitigated by the use of transfer functions and their representation by state space approximations. 2.Aquifer response under uncertainty of inputs and aquifer parameters is addressed by a new statistical procedure that is applicable to regions of relatively few measurements and incorporates management reliability considerations. 3.The conjunctive management problem is formulated in a generally applicable way, taking into consideration all relevant uncertainties and system objectives. This problem is solved via an efficient stochastic optimization method that overcomes dimensionality limitations. 4.The methods developed in this Thesis are applied to the Jordanian water resources system, demonstrating their value for operational planning and management.

The scope of this work is to implement a realistic looking ocean simulator with a ship floating on the surface. Foam, and ship wake is included to add to the realism. The application is designed to run on a normally equipped laptop with an ATI graphics card and Windows as the operation system. All calculations except the wake generation are performed in real time. The program, named ’OceanSimulator’, is written in C++ with OpenGL for visualization. The waves are represented with the JONSWAP spectrum and calculated using fast fourier transformation algorithm. The ship movement is calculated by use of transfer functions given in a RAO text file. The graphics card is programmed directly by use of shaders to get high flexibility regarding visual effects. Two different lighting approaches of the ocean are explored, cube mapping, and parameterization.

Our ability as a society to responsibly manage water resources for both humans and the environment relies on accurate predictive models. Current hydrologic models are unable to simulate important biogeochemical reactions that occur in systems where surface water and groundwater are coupled, where flowpaths alternate between highly contrasting surface and subsurface environments. Informed and responsible aquatic ecosystem management requires an understanding of the complex feedbacks between ecological properties and functions in ponds, streams, rivers and lakes, and the catchment hydrological processes affecting the quantity and quality of water entering aquatic systems. The types of flowpaths and the duration of water flow in a catchment determine the physical and chemical characteristics of water entering aquatic systems, which in turn affect the natural range of ecological properties and functions. The primary objective of this work was to create capacity for better prediction of the impacts of hydrologic variability on aquatic ecosystems. Three field studies were undertaken, representing different aquatic ecosystems (a river, stream, and lake) and different ecological functions (salmon spawning habitat use, wetted habitat availability, and nutrient cycling) occurring at different scales (point, regional and catchment). For each study, a combined hydrochemical and hydrometric approach was developed to describe the variability in flowpaths over space and time, and to quantify or infer the relative transit times of water received from the catchments. Water exiting a catchment is the convergence of many different flowpaths with many different transit times. It was found that the selected ecological processes could be discussed in terms of transit time, specifically the ratio of long to short transit times of water delivered to an aquatic system. These results were used to propose a conceptual model capable of predicting the impacts of climatic variability and change and anthropogenic activities on aquatic ecosystems through their effects on hydrologic processes. Further work is needed to quantify the transit time ratio and test the efficacy of the predictive model.

Thesis (Ph.D.)--Joint Program in Applied Ocean Science and Engineering (Massachusetts Institute of Technology, Dept. of Ocean Engineering; and the Woods Hole Oceanographic Institution), 2000.
Includes bibliographical references (p. 299-312).
by Sean Patrick McKenna.
Ph.D.

“Una alternativa per aconseguir una font d’energia lliure en carboni és la fotoproducció d’H2 mitjançant el trencament catalític de l’aigua (water splitting, WS, Eq. 1) fent servir la llum solar. 2H2O + hv --> 2H2 + O2 (Eq. 1) WS és un procés en el qual l’aigua és oxidada a dioxigen a l’ànode (reacció d’evolució d’oxigen, REO, Eq. 2), constituent llavors la font d’electrons per reduir protons a H2 al càtode (reacció d’evolució d’hidrogen, REH, Eq. 3). 2H2O --> O2 + 4H+ + 4e- (Eq. 2) 2H+ + 2e- --> H2 (Eq. 3) El desenvolupament de catalitzadors altament actius i eficients és essencial per a aconseguir una cinètica òptima d’aquestes dues semireaccions. Les nanopartícules (NPs) són veritables potencials catalitzadors gràcies a la seva alta estabilitat i rati superfície/volum, exposant grans quantitats de centres actius. En aquesta tesi, diferents nanocatalitzadors han estat sintetitzats mitjançant el mètode organometàl·lic, el qual és avantatjós per obtenir nanomaterials amb una superfície neta. Per tal d’entendre els factors que afecten a l’activitat electrocatalítica dels nanomaterials, s’han realitzat càlculs teòrics per DFT basats en conceptes ben acceptats (energia lliure d’adsorció d’hidrogen, δGH*, i gràfics “volcano”). Degut a que la presència de lligands a la superfície de les NPs pot influenciar l’activitat electrocatalítica, s’han realitzat càlculs DFT per determinar els modes més favorables de coordinació de diferents lligands i obtenint també els valor de δGH*, trobant-se una correlació satisfactòria entre les dades experimentals i les dades DFT. Diferents estudis confirmen que els suports de carboni conductors milloren l’activitat electrocatalítica restringint l’agregació dels nanocatalitzadors i millorant la transferència electrònica des del nanocatalitzador metàl·lic cap a l’elèctrode. En aquesta tesi, dos materials de carboni diferents, òxid de grafè reduït (OGr) i microfibres de carboni (FC) han estat utilitzats com a suports de NPs metàl·liques. A més a més, s’ha estudiat l’efecte del dopatge de N o P en OGr en la REH, obtenint un efecte sinergètic positiu entre els heteroàtoms i NPs de Ru. Contràriament al grafè, les FC són més fàcils de manipular i poden fer-se servir directament com a elèctrodes. Llavors, s’han sintetitzat NPs de Ru i de Co sobre dos tipus diferents de FC, diferenciant-se en la presencia o no de grups –COOH a la superfície de la fibra. Dues metodologies han estat utilitzades, in situ i ex situ, per tal de modificar la interfase entre les NPs i el suport de carboni, afegint diferents solvents (THF o 1-heptanol) en les NPs de Co, o lligands (4-fenilpiridina, 4PP) en les NPs de Ru. Els resultats evidencien que una interacció adequada entre les NPs i la superfície del suport és un element clau per obtenir una millorada activitat electrocatalítica, obtenint millor resultats en sistemes on tenen lloc interaccions π-π entre les NPs (Ru-4PP) i les estructures de carboni o enllaços d’hidrogen entre Co(OH)2 i els grups COOH a les FC. Una altra estratègia prometedora és l’adició d’un segon metall a una estructura metàl·lica, obtenint efectes electrònics sinergètics beneficiosos degut a canvis en l’entorn químic dels centres metàl·lics i disminuint l’energia d’adsorció dels reactius. En aquest sentit, sistemes bimetàl·lics, Ru@Ni-foam i NPs de RuCo han estat sintetitzats. La influencia en l’activitat catalítica en OER de diferents percentatges de dopatge de Ru en el sistemes Ru@Ni-foam ha estat estudiada. Finalment, els sistemes bimetàl·lics basats en NPs de RuCo han estat sintetitzats fent servir tres lligands diferents, 4’-(4-metilfenil)-2,2’:6’,2”-terpiridina, 4-PP i 1-heptanol. S’ha examinat la influencia del lligand i el rati entre metalls Ru/Co en la mida i morfologia de les NPs. Els estudis electrocatalítics obren noves portes per explorar l’interès dels sistemes bimetàl·lics com a catalitzadors per WS i la producció d’hidrogen.
Una solución para conseguir una fuente de energía libre de carbono es la fotoproducción de H2 mediante la división catalítica del agua (Water splitting, WS, Ecuación 1) utilizando la luz solar. 2H2O + hv --> 2H2 + O2 (Ecuación 1) WS es un proceso en el que el agua se oxida a dioxígeno en el ánodo (reacción de evolución del oxígeno, REO, Ecuación 2), constituyendo así la fuente de electrones para reducir los protones a H2 en el cátodo (reacción de evolución del hidrógeno, REH, Ecuación 3). 2H2O --> O2 + 4H+ + 4e- (Ecuación 2) 2H+ + 2e- --> H2 (Ecuación 3) El desarrollo de catalizadores de WS altamente activos y eficientes es esencial para la correcta cinética de estas dos semireacciones. Las nanopartículas (NPs) son verdaderos catalizadores potenciales debido a su alta estabilidad y relación superficie/volumen, exponiendo altas cantidades de sitios activos. En esta tesis doctoral se han sintetizado diferentes nanoelectrocatalizadores siguiendo el método organometálico, que resulta ventajoso para obtener nanomateriales de superficie limpia. Para entender los factores que afectan a la actividad electrocatalítica de los nanomateriales, se han realizado cálculos teóricos sobre la base de conceptos bien aceptados (energía libre de adsorción de hidrógeno, δGH*, y diagramas de volcán). Dado que los ligandos presentes en la superficie de las NPs metálicas pueden influir en la actividad electrocatalítica, se realizaron cálculos DFT para determinar los modos de coordinación más favorables de diferentes ligandos y obtener los valores de δGH*, obteniéndose correlaciones satisfactorias entre los datos experimentales y los de DFT. Diferentes estudios confirman que los soportes conductores de carbono mejoran la actividad electrocatalítica al restringir la agregación de los nanocatalizadores y mejorar la transferencia de electrones desde el nanocatalizador metálico al electrodo. En esta tesis doctoral se han utilizado dos materiales de carbono, el óxido de grafeno reducido (OGr) y las microfibras de carbono (FC), como soportes de NPs metálicas. Además, se ha estudiado el efecto del dopaje de N y P sobre el OGr en la REH, obteniendo un efecto sinérgico positivo entre heteroátomos y NPs de Ru. A diferencia del grafeno, las microfibras de carbono son más fáciles de manipular y pueden utilizarse directamente como electrodos. Así, se han sintetizado NPs de Ru y Co sobre dos microfibras diferentes, que difieren en la presencia o no de grupos -COOH en la superficie. Además, se han empleado dos metodologías diferentes, in situ y ex situ, para modificar la interfaz entre las NPs y el soporte de carbono mediante la adición de diferentes disolventes (THF o 1-heptanol) o ligandos (4-fenilpiridina, 4PP). Los resultados evidencian que una adecuada interacción entre las NPs y la superficie del soporte es clave para una mejor actividad catalítica, obteniéndose mejores resultados en los sistemas en los que tienen lugar interacciones π-π entre las estructuras Ru-4PP NPs/C o enlaces H entre las NPs de Co(OH)2 y -COOH en la FC. Otra estrategia prometedora es la adición de otro metal a una nanoestructura metálica, lo que conduce a efectos electrónicos beneficiosos al cambiar el entorno químico de los centros metálicos. En este sentido, se sintetizaron sistemas bimetálicos de Ru@Ni-espuma y NPs de RuCo. Se ha estudiado la influencia de diferentes porcentajes de dopaje de Ru en los sistemas de Ru@Ni-espuma sobre la actividad catalítica hacia la REO. Finalmente, se sintetizaron NPs de RuCo utilizando tres ligandos diferentes, 4’-(4-metilfenil)-2,2’:6’,2””-terpiridina, 4-PP y 1-heptanol, con el fin de determinar la influencia del ligando y de la ratio Ru/Co en el tamaño y la morfología de las NPs. Los estudios electrocatalíticos realizados abren una nueva puerta para explorar el interés de los nanocatalizadores bimetálicos en WS y la producción de hidrógeno.
One solution to achieve a carbon free energy source is the photoproduction of H2 by the catalytic water splitting (WS, Eq. 1) using sunlight. 2H2O + hv --> 2H2 + O2 (Eq. 1) WS is a process in which water is oxidized to dioxygen in the anode (oxygen evolution reaction, OER, Eq. 2), thus constituting the source of electrons to reduce protons to H2 in the cathode (hydrogen evolution reaction, HER, Eq. 3). 2H2O --> O2 + 4H+ + 4e- (Eq. 2) 2H+ + 2e- --> H2 (Eq. 3) Developing highly efficient and active WS catalysts is essential for the proper kinetics of these two reactions. Nanoparticles (NPs) are true potential catalysts due to their high stability and surface per volume ratio, exposing high amounts of active sites. In this PhD, different nanoelectrocatalysts have been synthesized by following the organometallic approach which is advantageous for obtaining clean-surface nanomaterials compared to other synthesis methodologies. To understand the factors affecting the electrocatalytic activity of the nanomaterials, theoretical DFT calculations have been performed on the basis of well accepted concepts (hydrogen adsorption free energy, δGH*, and volcano plots). Given that the ligands present on the surface of metal NPs can influence the electrocatalytic activity, DFT calculations were performed to determine the most favorable coordination modes of different ligands and to obtain the δGH* values of the resulting NPs. Successful correlations between experimental and DFT data have been obtained. Conductive C-based supports are known to enhance the electrocatalytic activity by restraining the aggregation of the nanocatalysts and improving the electron transfer from the metal nanocatalyst to the electrode. In this PhD, two different carbon materials, reduced graphene oxide (rGO) and carbon microfibers (CF) have been used as supports for metal NPs. Furthermore, the effect of N and P doping onto rGO has been studied towards the HER, obtaining a positive synergistic effect between the heteroatoms and Ru NPs. In contrast to graphene, CF are easier to handle and can be directly used as electrodes, thus avoiding the issues related to the NPs deposition onto macroscopic electrodes (GC, FTO). Thus, Ru and Co NPs have been synthesized on top of two different CF, differing in the presence or not of –COOH moieties onto the surface. Two different methodologies, in-situ and ex-situ, have been employed in order to tune the interface between the NPs and the C support by adding different solvents (THF or 1-heptanol) for Co NPs or ligands (4-phenylpyridine, 4PP) for Ru NPs. The results evidence that a proper interaction between the NPs and the support surface is key for an improved catalytic activity of the hybrid materials, obtaining better results in the systems where π-π interactions between Ru-4PP NPs/C structures or H-bonds between Co(OH)2 and COOH moieties in the CF take place. Another promising strategy is the addition of another metal onto a metallic nanostructure, leading to beneficial synergistic electronic effects by changing the chemical environment of the metal centers and decreasing the adsorption energy of the reactants. In this sense, bimetallic Ru@Ni-foam and RuCo NPs systems were synthesized. The influence on the catalytic activity towards OER of different percentages of Ru-doping in Ru@Ni-foam systems has been studied. Finally, RuCo bimetallic systems were synthesized by using three different ligands, 4’-(4-methylphenyl)-2,2’:6’,2”-terpyridine, 4-PP and 1-heptanol. The influence of the ligand and the Ru/Co metal ratio on the size and morphology of the NPs has been determined. Preliminary electrocatalytic tests have been performed, opening a new door to explore the interest of bimetallic nanocatalysts for the water-splitting and the production of hydrogen.
Universitat Autònoma de Barcelona. Programa de Doctorat en Química

Surface water bodies such as lakes, rivers and wetlands play an essential role in ecological balance, serve as freshwater supplies and are valued by the general public as places of natural beauty. Proper management of surface water bodies can be assisted by modelling of surface water and groundwater interactions. Different models of interaction between ground and surface water are presented in this work. We develop models suitable for two different scales, i.e., near field (local) and far field (regional). Green’s second identity and potential theory are employed to present solutions in the form of an integral equation or a set of integral equations. Different numerical techniques, either existing or new, are then used to obtain the final solution. Generic results allow us to analyse the influence of various hydrogeological factors on interaction between surface and subsurface water, as well as to highlight limitations of previous approaches.

Diese Arbeit ist eine umfassende und systematische Untersuchung der Adsorption von Wasser auf der Fe2O3(0001)-Oberfläche. Sie deckt eine Vielzahl der Probleme auf, die während des Anfangs der Wasseradsorption auf den Übergangsmetalloxidoberflächen auftreten. Dazu gehören die Stabilität der reinen Oberfläche, die Rolle der Oberflächendefekte, der Einfluss der kristallographischen und elektronischen Strukturen, die elementare Kinetik der adsorbierten Arten von Wasser auf der Oberfläche, die Eigenschaften bei niedrigem und hohem Bedeckungsgrad und die Auswirkungen der Wasserstoffbrückenbindung auf die Adsorption und das XPS-Spektrum. Niedrige und hohe Bedeckungsgrade von 0.25 bis 1 Monolage werden untersucht, um die Grundlage für die folgende Erhöhung der Wasserbedeckung, die normalerweise in Experimenten beobachtet wird, zu ermitteln. Das Einzeladsorptionsregime wurde erweitert, um eine echte Wasserdampfumgebung mittels der Gibbs-Energie zu berücksichtigen. Die Ensemblemethode wurde benutzt, um die durchschnittlichen Werte der energisch entarteten Adsorptionskonfigurationen zu interpretieren. Der Abstandsmatrixansatz wurde entwickelt, um die statistische Analyse zu ermöglichen. Die Methode reduziert mithilfe der Oberflächensymmetrie die Gesamtzahl der Adsorptionskonfigurationen, die zu berücksichtigen sind. Das XPS-Spektrum wird für verschiedene Wasserdampftemperaturen und Drücke simuliert. Es wird eine gute Übereinstimmung zwischen theoretischen und experimentellen Spektren erreicht und die geringen Unterschiede werden erklärt. Die Hauptmerkmale des XPS-Spektrums beim Anstieg von relativer Feuchtigkeit des Wasserdampfs werden beschrieben. Die Ähnlichkeiten und Unterschiede der Wasseradsorption auf Fe2O3 und Al2O3 werden betont und die wichtigsten Tendenzen werden abgeleitet. Auf Grund dieser Arbeit kann der Anfangsprozess der Fe2O3(0001)-Oberflächenbenetzung erklärt werden.
The present study is a comprehensive systematic theoretical investigation of the water adsorption on the Fe2O3(0001) surface. It covers a broad number of problems inherent to the initial stage of the water adsorption on the transition metal oxide surface: clean surface stability, the influence of surface oxygen defects, the role of the crystallographic and electronic structures on the adsorption configuration, elementary kinetics, the particular qualities of the low and high adsorption coverage regimes and the effect of the hydrogen bonding on adsorption and on the XPS spectra simulation. The low and high coverage regimes from 0.25 up to 1 monolayer water coverage were considered to form a basis for the following increase of water loading mainly observed in experiments. A single adsorption energy picture was expanded to take into account the water vapour environment through the Gibbs free energy. The statistical ensemble was employed to classify and interpret the averaged values of the adsorption configurations set rather than the ``invisible'' in experiment quantities intrinsic to the particular single adsorption configuration. In order to make the statistical analysis feasible an effective distance matrix scheme was developed. It helped to reduce the total number of structures to consider without loss of generality by virtue of the surface space symmetry. Based on the statistical contribution of each individual adsorption configuration, the O-1s XPS was simulated for the various water vapour environments. A good agreement between the simulated and experimental spectra was found. Wherever it was important, the similarities and differences between water adsorption on the Fe2O3, Al2O3 and Fe3O4 surfaces were stressed and the main tendencies were deduced. Based on the present study, the whole picture of the initial stage of the Fe2O3(0001) surface wetting process was established.

Considérant une particule isolée, la différence principale entre un colloïde actif et un colloïde passif réside dans le temps de persistance du régime balistique. La transition du régime balistique vers le régime diffusif est déterminée dans les deux cas par des coefficients de friction ou de manière équivalente par des coefficients de diffusion. Le mouvement d’une particule colloïdale passive micrométrique est diffusif lorsqu’il est observé sur des intervalles de temps d’au moins une microseconde, suffisamment longs pour que la direction de la quantité de mouvement soit rendue aléatoire par des collisions avec les molécules de solvant. A l’échelle macroscopique ces collisions se traduisent par un coefficient de friction de translation. Pour une particule colloïdale active, un mouvement diffusif est observé pour des intervalles de temps de plusieurs secondes, suffisamment longs pour que la direction d’auto-propulsion soit rendue aléatoire par la diffusion rotationnelle de la particule.Dans cette thèse, nous étudions le mouvement d’une particule colloïdale active déposée à la surface de l’eau. Des particules Janus aux propriétés catalytiques ont été préparées par dépôt de platine métal à la surface de particules de silice. La profondeur d’immersion des particules ainsi que leur orientation par rapport à la surface de l’eau ont été caractérisées et discutées en tenant compte des propriétés de mouillage non-uniformes de la surface des particules Janus. Le mouvement de particules isolées en présence de quantités variables d’eau oxygénée utilisée comme source d’énergie, a été enregistré par vidéo-microscopie optique et les trajectoires analysées en termes de déplacement carré moyen et de fonction d’auto-corrélation des vitesses. L’observation de deux types de trajectoires, rectilignes et circulaires, révèle la force effective ainsi que le couple induit par la décomposition catalytique de l’eau oxygénée à la surface de la particule Janus. Le résultat principal de ce travail est que le mouvement des particules actives confinées à l’interface persiste plus longtemps dans le régime balistique que celui de particules actives totalement immergées en solution. Ceci est dû au confinement qui réduit le nombre de degrés de liberté de rotation mais aussi aux conditions de mouillage partiel qui font apparaître des contributions supplémentaires à la friction de rotation
At the single-particle level, the main difference between active colloids and passive ones is the time scale over which the motion crosses over from ballistic to diffusive regime. In both cases, friction coefficients or equivalently diffusion coefficients determine this time scale. For instance, the motion of a passive colloid of 1m radius is diffusive when observed over lag times longer than a microsecond, once the direction of its momentum has been randomized by collisions with solvent molecules. At the macroscopic scale these collisions are accounted for by the translational friction coefficient. For an active colloid the effective diffusive behavior observed over lag times larger than few seconds results from the randomization of the direction of self-propulsion by rotational diffusion. In this thesis we investigated the motion of an active Janus colloid trapped at air-water interface. Spherical catalytic Janus colloids have been prepared through the deposition of platinum metal at the surface of silica particles. Immersion depth of the Janus colloid as well as their orientation with respect to the water surface, has been characterized and interpreted in terms of the non-uniform wetting properties of the Janus particles. The motion of the active Janus colloids in the presence of various concentration of hydrogen peroxide H2O2 as fuel was characterized by video microscopy and the trajectories analyzed through the mean square displacement and the velocity autocorrelation function. The types of trajectories, directional and circular ones that we observed in our experiments, revealed the effective force and torque induced by the catalytic decomposition of H2O2. At the water surface, active colloids perform more persistent directional motions as compared to the motions performed in the bulk. This has been interpreted as due to the loss of degrees of freedom resulting from the confinement at interface and also to the partial wetting conditions that possibly bring new contributions to the rotational friction at interface

The central aim for the research undertaken in this PhD thesis is the development of a model for simulating water droplet movement on a leaf surface and to compare the model behavior with experimental observations. A series of five papers has been presented to explain systematically the way in which this droplet modelling work has been realised. Knowing the path of the droplet on the leaf surface is important for understanding how a droplet of water, pesticide, or nutrient will be absorbed through the leaf surface. An important aspect of the research is the generation of a leaf surface representation that acts as the foundation of the droplet model. Initially a laser scanner is used to capture the surface characteristics for two types of leaves in the form of a large scattered data set. After the identification of the leaf surface boundary, a set of internal points is chosen over which a triangulation of the surface is constructed. We present a novel hybrid approach for leaf surface fitting on this triangulation that combines Clough-Tocher (CT) and radial basis function (RBF) methods to achieve a surface with a continuously turning normal. The accuracy of the hybrid technique is assessed using numerical experimentation. The hybrid CT-RBF method is shown to give good representations of Frangipani and Anthurium leaves. Such leaf models facilitate an understanding of plant development and permit the modelling of the interaction of plants with their environment. The motion of a droplet traversing this virtual leaf surface is affected by various forces including gravity, friction and resistance between the surface and the droplet. The innovation of our model is the use of thin-film theory in the context of droplet movement to determine the thickness of the droplet as it moves on the surface. Experimental verification shows that the droplet model captures reality quite well and produces realistic droplet motion on the leaf surface. Most importantly, we observed that the simulated droplet motion follows the contours of the surface and spreads as a thin film. In the future, the model may be applied to determine the path of a droplet of pesticide along a leaf surface before it falls from or comes to a standstill on the surface. It will also be used to study the paths of many droplets of water or pesticide moving and colliding on the surface.

The central aim for the research undertaken in this PhD thesis is the development of a model for simulating water droplet movement on a leaf surface and to compare the model behavior with experimental observations. A series of five papers has been presented to explain systematically the way in which this droplet modelling work has been realised. Knowing the path of the droplet on the leaf surface is important for understanding how a droplet of water, pesticide, or nutrient will be absorbed through the leaf surface. An important aspect of the research is the generation of a leaf surface representation that acts as the foundation of the droplet model. Initially a laser scanner is used to capture the surface characteristics for two types of leaves in the form of a large scattered data set. After the identification of the leaf surface boundary, a set of internal points is chosen over which a triangulation of the surface is constructed. We present a novel hybrid approach for leaf surface fitting on this triangulation that combines Clough-Tocher (CT) and radial basis function (RBF) methods to achieve a surface with a continuously turning normal. The accuracy of the hybrid technique is assessed using numerical experimentation. The hybrid CT-RBF method is shown to give good representations of Frangipani and Anthurium leaves. Such leaf models facilitate an understanding of plant development and permit the modelling of the interaction of plants with their environment. The motion of a droplet traversing this virtual leaf surface is affected by various forces including gravity, friction and resistance between the surface and the droplet. The innovation of our model is the use of thin-film theory in the context of droplet movement to determine the thickness of the droplet as it moves on the surface. Experimental verification shows that the droplet model captures reality quite well and produces realistic droplet motion on the leaf surface. Most importantly, we observed that the simulated droplet motion follows the contours of the surface and spreads as a thin film. In the future, the model may be applied to determine the path of a droplet of pesticide along a leaf surface before it falls from or comes to a standstill on the surface. It will also be used to study the paths of many droplets of water or pesticide moving and colliding on the surface.